Chemical Engineering and Processing 43 (2004) 357367

Determination of binary vaporliquid equilibria (VLE)

of three fast reacting esterification systems
M. Tischmeyer1 , W. Arlt
Institut fuer Verfahrenstechnik, Fachgebiet Thermodynamik und Thermische Verfahrenstechnik, Technische Universitaet Berlin,
Building TK7, Strasse des 17, Juni 135, D-10623 Berlin, Germany

Received 8 November 2002; received in revised form 18 February 2003; accepted 19 February 2003

Abstract

The simulation and safe layout of a reactive distillation process requires the knowledge of the chemical reaction and separate binary phase
equilibrium data. The latter are difficult to obtain experimentally since the products of reaction affect the binary equilibrium as soon as they
are formed. With the apparatus constructed and the modeling method described, the binary vaporliquid equilibria (VLE) are obtained for
systems with reaction rates showing half-life times of 30 min and below. Results for the binary VLE are presented for compounds of methanol
and ethanol with formic acid at 313333 K and isopropanol with formic acid at 313353 K. The proposed method can be applied to obtain
binary interaction parameters of reactive compounds for commonly used gE -models, if the half-life time of the non-catalyzed reaction at the
desired temperature is above 10 min.
2003 Elsevier B.V. All rights reserved.

Keywords: Fast reacting systems; Binary vaporliquid equilibria; Chemical esterification reaction

1. Introduction overcoming of azeotropic limitations;

Conventional chemical production processes are usually
performed in a sequence manner, i.e. first reaction and
then the distillation. In certain cases, this sequence may
be replaced by a reactive distillation in order to lower the
production costs or to improve the purity of the products.
Therefore, the (catalyzed) reaction must have sufficient
reaction rates at the conditions where distillation is practi-
cable. Several advantages can be achieved by this combined
process, the most important are:
reduced downstream processing for separation of the
product from residual components;
utilization of the heat of reaction directly for evaporation
of liquid phase;
increasing of the selectivity by removal of product(s), in
case of parallel or consecutive reactions;
Corresponding author. Tel.: +49-30-314-23977;
fax: +49-30-314-22406.
E-mail addresses: m.tischmeyer@vt.tu-berlin.de (M. Tischmeyer),
w.arlt@vt.tu-berlin.de (W. Arlt).
1 Co-corresponding author. Tel.: +49-30-314-24079;
fax: +49-30-314-22406.
lowering of resident time since the concentrations of re-
actants and thus the product yield is higher.
On the other hand, the process implies new limitations,
such as reactive azeotropes and multiple steady states (and
hence an increased effort of process control). A reliable
phase equilibrium model is crucial for the process synthe-
sis or to carry out a feasibility study. The emphasis of that
study would be to determine whether the reactive distillation
is preferable.
The simulation of a reactive column needs both as in-
put: reaction kinetics or equilibrium constants and binary
vaporliquid equilibrium data for well-known gE -models.
These data are usually not available because the reaction
prevents the experimental determination of binary phase
equilibrium data, using standard measurement technique.
For example, by a literature search for compounds of or-
ganic acids with alcohols, only 64 isothermal or isobar
vaporliquid equilibrium (VLE) data sets were found in the
DECHEMA data base [1] which were measured either in
chemical equilibrium or at very low temperatures. Only four
of them were found to be thermodynamically consistent
with the RedlichKister area test [1].

0255-2701/$ see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0255-2701(03)00115-6
358 M. Tischmeyer, W. Arlt / Chemical Engineering and Processing 43 (2004) 357367
In this work, our method of determining the binary phase
equilibria of reactive systems is described. The esterifica-
tion reactions of formic acid with methanol, ethanol and iso-
propanol are examined. These reactions have half-life times
of some minutes up to several hours, depending on the tem-
perature and the amount of formic acid present in the system.
2. Overview of existing approaches
Ppken et al. [2,3] are using a computer operated static
apparatus. They measured isothermal P, x-data of the binary
systems required for the methyl acetate production process.
Presumption for these measurements is that the VLE is es-
tablished much faster than the chemical equilibrium which
yields operating temperatures up to 323.15 K at max.
Alsmeyer et al. [4,5] have set-up a flow-through apparatus
ki
for VLE measurements in reactive systems which also allows
ij + 1  (2)
kj
the determination of reaction kinetics in the liquid phase.
The reactive mixture is forced into a steady state which
does not represent its chemical equilibrium but reaches phase
equilibrium between vapor and liquid. Both phases are then
ij = exp (3)
analyzed in situ by mid-infrared spectroscopy. While the gas
phase is measured in transmission, attenuated total reflection
is used for the liquid phase.
Another flow-type apparatus has been operated until 1998
by Reichl et al. [6]. It was set-up as non-recycle flow still and
due to the short residence time was used to determine iso-
baric VLE data of thermally unstable components and of re-
active mixtures. Two esterification systems (methyl formate
and ethyl acetate) and one etherification system (tert-amyl
methyl ether) were investigated.
Roederer et al. [7] investigated an isomeric reaction (-
and -isophorone) at 388, 423 and 493 K until 1999. They
performed investigations in a specialized stirred cell in form
of a closed loop reactor. For the VLE experiments, it was
possible to use the experimental set-up as a flow type cell.
The compostion of the phases were obtained with a Fourier
transforminfrared spectrometer. The reaction takes place
only by use of catalyst and was neglected during the VLE
measurements.
Lee and Kuo [8], Lee and Liang [9], and Lee and Lin [10]
investigated different esterification reactions which were cat-
alyzed to reach the chemical equilibrium. For measuring the
VLE an Othmer-type circulation still was used where the va-
por phase is condensed before sampling. The pressure was
kept constant, liquid and vapor concentrations were deter-
mined at different constant temperatures, a gas chromato-
graph was used for analysis.
Patel und Young [11] used a modified adiabatic calorime-
ter for a study of the ethylene oxide + nonyl phenol system.
During the reaction, the pressure was continuously measured
and stored. A linear extrapolation was used to obtain the
binary VLE data.
The measuring method applied in this work follows the
proposal by Patel and Young [11] for calorimetry. It is shown
that this method is appropriate for a certain class of reaction
systems used in the reactive distillation.
3. Theoretical background
3.1. Phase equilibrium calculations
For description of the VLE, a model was chosen:
xi i f0iL = yi iV P (1)
The activity coefficient i is calculated from a model for
the Gibbs excess enthalpy gE . The Wilson model [12] was
chosen according to the strongly non-ideal nature of the
system:
  xk
ln i = ln xj
j k j xj
with
 
vL0j ij
vL0i T
where vL0i and vL0j are the molar volume of liquids i and j as
given in [1] and ij the binary interaction parameters of the
model.
To calculate the liquid fugacity it is also necessary to in-
clude the standard state fugacity f0iL , which is the fugacity
of the pure liquid component i at system pressure and tem-
perature. It can be expressed by
vL0i (P P0i
LV )
f0i = 0i P0i exp
L LV LV
(4)
RT
where 0iLV is the fugacity coefficient of the component i at
saturated vapor pressure P0iLV , and exp(vL (P P LV )/RT) is
0i 0i
the Poynting correction, which accounts for the expansion
or compression of the liquid from saturated vapor pressure
to system pressure.
The fugacity coefficient iV is calculated with the virial
equation of state by the method of Hayden and OConnell
[13] to get the second virial coefficient. They assume that
the vapor is ideal except for association between molecules,
usually due to hydrogen bonding. The method incorporates
the chemical theory of dimerization. Therefore, it accounts
for strong association and solvation effects, including such
as found in systems containing organic acids like in the
present system.
3.2. Influence of reaction on quaternary VLE
The possible phase equilibrium conditions of a quaternary
mixture can best be depicted in a tetrahedron. All points
within the tetrahedron are possible phase equilibrium com-
positions for a system without reaction. When one or more
 M. Tischmeyer, W. Arlt / Chemical Engineering and Processing 43 (2004) 357367
reactions occur, the degree of freedom FG is reduced by the
number of independent reversible chemical equilibrium re-
actions, see Gibbs phase rule (5):
FG = 2 + C Ph R (5)
where C is the number of components, Ph the number of
phases and R the number of independent chemical equilib-
rium reactions.
In a quaternary system with two phases and one reversible
reaction where the temperature is given, the remaining de-
gree of freedom is two. This number is identical to the di-
mension of the concentration space in which the equilibrium
conditions are fulfilled (where either temperature or pres-
sure are kept constant). This part of the concentration space
is called reaction space [14]. The geometrical shape of the
reaction space varies with the type of reaction, the position
of the chemical equilibrium (i.e. the quantity of the equilib-
rium constant Ka ) and the presence of inert components.
The stoichiometric reaction mechanism is:
A A + B B C C + D D, (6)
where A and B are the reactants (alcohol and organic acid),
C and D the products (ester and water) and i the stoichio-
metric coefficients. The latter are unity for the esterification
reactions considered here. If the equilibrium constant Ka
(see Eq. (7)) has a quantity about unity and an ideal mix-
ture behavior (i.e. also Kx = 1), the reaction space forms a
saddle area as depicted in Fig. 1.
a C aD
Ka = (7)
aA aB
where ai are the activities
ai = xi i (8)
The saddle area is stretched between the non-reacting
binary systems AC, AD, BC and BD. The arrows rep-
resent the stoichiometric lines which show the change in
concentration caused by the forward reaction. Since the re-
action does not change the number of moles, all stoichiomet-
Fig. 1. Reaction space of an equimolar reaction A + B C + D at
constant pressure.
359
ric lines are parallel. Their endpoints represent the chemical
equilibrium concentrations corresponding to the initial com-
position of the components A and B. All reactions which
are started by mixing of pure A and B yield stoichiometric
lines within the triangle outlined by A, B, (C/D = 1/1).
The backward reaction (not depicted here for clarity in
reasons) would, if started by mixing of pure C and D, pro-
duce stoichiometric lines directing from the CD-border to
the chemical equilibrium surface.
4. Experimental
4.1. Chemicals
Isopropanol, methanol and ethanol used for experimental
procedure were of analytical grade (purity 99.9%, Merck).
Formic acid was given with 98% purity (Merck). For cal-
ibration of the gas chromatograph, methyl formate, ethyl
formate and isopropyl formate (purity >98%, Merck) and
distilled water were used. The chemicals were processed
without further purification except for degassing.
4.2. Equipment and experimental procedure
The experiments were carried out in a 550 cm3 static equi-
librium cell which is located in a thermostatic oil bath at a
given temperature with an accuracy of 0.1 K. The set-up
is given in Fig. 2 and explained below.
Stainless steel 1.4435, Teflon and glass have been used
for construction. The temperature inside the cell was
measured by a platinum resistance thermometer PT-100
(Conatex) with an accuracy of 0.01 K. The pressure was
measured using a calibrated high accuracy sensor head
(MKS Baratron Type 121A connected to the signal condi-
tioner Type PDR-D-1) attached to the top of the cell. The
sensor head and the connecting line from the cell to the
sensor were thermostated at 398.15 0.1 K. The sensor
was calibrated by the ambient pressure (measured with a
mercury manometer), high vacuum (104 Pa) and the vapor
pressure of pure water, methanol, ethanol and formic acid
at a temperature range of 313.15353.15 K. According to
these measurements, the experimental pressure is assessed
to be reliable within 0.5% of the measured value.
Phase equilibrium is reached quickly by mixing the two
phases intensively using a stirrer head with magnetic cou-
pling (bmd 075, Bchi GmbH). The measurement starts
by injection of the necessary amount of alcohol in order to
obtain a desired mole fraction of the mixture. The alcohol
is degassed and filled into the injection cylinder (manufac-
tured by the Laboratory for Thermophysical Properties of
the University of Oldenburg). When the equilibrium tem-
perature of the oil bath is established, the vapor pressure of
pure organic acid is measured. At the time t0 , the predefined
amount of alcohol is injected into the cell within <2 s by
means of the pressure pump, powered with 1 MPa from a
360 M. Tischmeyer, W. Arlt / Chemical Engineering and Processing 43 (2004) 357367

Fig. 2. Experimental set-up for measuring VLE data of fast reacting systems: (1) static cell; (2) injection cylinder; (3) pneumatic power supply for
injection; (4) liquid sample loop; (5) thermostatic oil bath; (6) alcohol reservoir and degassing device; (7) vacuum pump; (8) gas chromatograph; (9)
personal computers.

nitrogen vessel. The precision of the injection is controlled
by a linear transducer (Haidenhain, type ND221) with an
accuracy of 10 m which is calibrated to determine the
injected mass of alcohol at a given temperature.
With the addition of a second component, the equi-
librium is disturbed due to the heat of mixing and heat
of reaction. We checked with non-reacting mixtures like
acetic acid+water and methanol+water that the cell reaches
phase equilibrium after 60 s of mixing. The VLE diagram
of methanol + water at T = 315.4 K is given in Fig. 3.
For the non-reactive experiment, the injection cylinder was
filled with methanol, thermostated and injected step by step
into the cell, which contained pure water at the beginning.
The triangles show the experimental data, the circles are
the P, x-data calculated at the actually measured cell tem-
peratures after each injection. Hence, they incorporate the
temperature disturbance through mixing effects and differ
slightly from the values calculated at averaged temperature
(see continuous line). The mean absolute pressure deviation
here is 0.29% and the mean relative deviation is 1.27%,

Fig. 3. Experimental and calculated phase equilibrium of methanol + water at 315.4 K: (triangle) experimental data; (circle) values calculated at
cell-temperature; (continuous and stroked lines) P, x- and P, y-curves calculated at averaged temperature, model parameters taken from Gmehling and
Onken [1].
 M. Tischmeyer, W. Arlt / Chemical Engineering and Processing 43 (2004) 357367
Fig. 4. Curve shape of an experiment with a low boiling organic acid in
the cell and alcohol injected.
which shows that the apparatus is capable of high accuracy
VLE-measurements.
For the determination of a reactive VLE, pressure and
temperature are monitored continuously during the ongoing
reaction, liquid and vapor samples are taken in short inter-
vals and the gas phase is analyzed immediately. An exam-
ple for the recorded temperature and pressure curves during
a typical reaction experiment (formic acid with ethanol at
xi0 = 0.5, T = 333 K) is given in Fig. 4.
The liquid samples are withdrawn every minute at the
pump circuit by connecting an evacuated sample vial. The
reaction is stopped immediately in the sample vial by ad-
dition of 5 g 1,4-dioxane per 1 g sample liquid and cooling
down to 263 K. The stop of the reaction was verified by
comparing the analysis of a sample right after withdraw-
ing with the analysis of the same sample after 10 h. Since
the results were identical, liquid samples are analyzed after
the experiment by the use of a gas chromatograph HP-GC
5890A Series II with splitsplitless-injector, TCD and FID
detector and a six-port valve (for gas phase sampling). A
HP-FFAP capillary column, length: 25 m, i.d.: 0.53 mm, film
thickness: 0.1 m is used with helium 5.0 as carrier gas
(Messer-Griesheim). An auto injector type G1895A, Agilent
Technologies, is installed in order to inject samples.
Online gas phase samples were taken additionally every
12 min during the experiments although they are not essen-
tial to obtain the binary VLE curves. When xi , P and T are
known, yi can be calculated by fitting a gE -model and a con-
venient vapor phase model to the experimental pressure data
at given xi and T. The deviation of the calculated pressure
to the measured value is minimized by adjusting the binary
interaction parameters of the gE -model. However, experi-
mental yi data can be used to verify the model quality.
4.3. Obtaining binary VLE parameters
Since it is not possible to measure the reacting binary
phase equilibrium directly, another method has to be used
for regressing binary interaction parameters. In our method,
the phase equilibrium is measured during the reaction right
from the beginning. Liquid samples are taken as frequent as
361
Fig. 5. Six pairs of interaction parameters in quaternary esterification
system.
possible especially during the first minutes of the reaction.
This yields quaternary VLE data which are measured as
close as possible to the reacting binary phase.
To apply a phase equilibrium model at these conditions
the interaction parameters of all occurring binaries in the
system have to be taken into account. Most of the required
binary data are available in literature (see Fig. 5 for formic
acidethanol system) so that Wilson parameters could be re-
gressed. Missing parameters were estimated using modified
UNIFAC [15]. In case of the formic acidisopropanol sys-
tem, VLE data for all binary systems (except acidalcohol)
were available.
The Wilson model was applied to calculate the activity
coefficients although it is not capable of LLE calculation.
Since no phase split occurred in the liquid samples taken dur-
ing experiments (which are the basis for VLE calculations),
the model was used mainly at homogeneous phase equilib-
rium conditions. However, the esterwater binary shows a
liquidliquid immiscibility which has to be calculated by the
gE -model as well. The constant pressure within the mixing
gap can be fitted by a very slight slope so that a sufficient
approximation is achieved (see Fig. 6).
This estimation is necessary since it is possible that during
the optimization procedure the phase split area is modified
in a way that some data points lie within the mixing gap (of
the model). In this case, the NRTL or UNIQUAC equations
would produce unreasonable results if used without checking
the number of phases by a flash algorithm.
A flash calculation was also implemented and used
with the NRTL-model and LLE parameters taken from the
DECHEMA data base [1]. The mixing gap was described
very well with these parameters. A phase split algorithm
was also used to check whether a second liquid phase occurs
during the model fitting procedure, but always yielded a
negative result. The mixture was homogeneous at all exam-
ined concentrations. However, by using LLE parameters for
ethyl formate + water the VLE of the reacting system could
not be calculated. The relative deviations of the computed
pressure to experimental values exceeded 100%. Only if
the ethyl formatewater parameters were also fitted to the
362 M. Tischmeyer, W. Arlt / Chemical Engineering and Processing 43 (2004) 357367

Fig. 6. Comparison of Wilson regression to experimental LLE data (experimental data by Marsh [17]).

experimental data, a sufficient result could be achieved, but
then the mixing gap disappeared by the VLE parameters
obtained for ethyl formate + water. Since the fitting quality
still was superior by using Wilson, the models which are ca-
pable of LLE calculation were not used. The same behavior
was found in the methanol and isopropoanol systems.
For a compilation of all used Wilson interaction param-
eters see Tables 13, the ideal gas constant R is given in
cal/(mol K) according to the format of the DECHEMA data
base.
To obtain the desired binary interaction parameters for
the organic acidalcohol pair, only these two are fitted to
the P, T, xi -data of the quaternary mixture while all other
parameters remain unchanged. Since the VLE data were
taken close to the binary conditions, the resulting parameters
are most suitable for calculating the binary VLE.
The vapor phase association was taken into account by
the chemical theory. The degree of association is represented
by the ij parameter which is taken from Prausnitz [16]
for binary i and j phases (see Table 4). If no association

Table 1
Wilson parameters used in formic acidmethanol system
[23] [24] [25] [26] [27]

Compound 1 Methanol Methanol Formic acid Formic acid Methyl formate

Compound 2 Methyl formate Water Methyl formate Water Water

Source DECHEMA DECHEMA FITTED EXP DECHEMA FITTED EXP

(a) (b) (a) (b)

T (K) 303.2 313.05 333.15 318.2 318.2 333.15 318.2373.85

12 755.6936 34.8965 184.8143 1365.5711 1073.6764 1157.1753 635.6215
21 157.7282 490.3910 653.4817 811.3106 1074.6210 1159.0655 2579.0911

Table 2
Wilson parameters used in formic acidethanol system
[28] [29] [26] [17]

Compound 1 Ethanol Ethanol Formic acid Formic acid Ethyl formate

Compound 2 Ethyl formate Water Ethyl formate Water Water

Source DECHEMA DECHEMA UNIFAC DECHEMA FITTED EXP

(a) (b) (a) (b)

T (K) 318.15 313.15 328.15 318.15 333.15 320.0

12 712.7894 173.3876 339.1783 115.7602 1073.6764 1157.1753 3262.02
21 186.8666 890.3253 881.1112 297.3702 1074.6210 1159.0655 2374.16
 M. Tischmeyer, W. Arlt / Chemical Engineering and Processing 43 (2004) 357367 363

Table 3
Wilson parameters used in formic acidisopropanol system
[30] [31] [30] [26] [32]

Compound 1 Isopropanol Isopropanol Formic acid Formic acid Isopropyl formate

Compound 2 Isopropyl formate Water Isopropyl formate Water Water

Source DECHEMA DECHEMA DECHEMA DECHEMA FITTED EXP

(a) (b) (a) (b)

T (K) 328.15 308.16 328.18 328.15 318.15 333.15 273.2333.4

12 625.7902 385.2801 642.8480 227.5687 1073.6764 1157.1753 3890.37
21 127.8289 1178.1219 1218.7931 202.2207 1074.6210 1159.0655 2093.03

Table 4
Binary interaction parameters for chemical theory [13]
Isopropanolethanolmethanol Formic acid Isopropyl Water
formateethyl
formatemethyl
formate
ij
Watera 1.55 2.5 1.3 1.7
Isopropyl formateb
Ethyl formatea
Methyl formatea 1.3 2 0.53
Formic acida 2.5 4.5
ii
Isopropanol 1.32
Ethanol 1.40
Methanol 1.63
a Prausnitz [16].
b No value available, estimated by analogy to ethyl formate and different acetates.

Table 5 coefficients were available they were estimated based on

Pure component parameters for Wilson model and chemical theory
data available for similar components.
Parameters Isopropanol Formic Isopropyl Water Further pure component parameters used for calculation
acid formate of i and iV with the Wilson model and the chemical theory
vL0i (cm3 /mol)a 76.92 37.91 100.95 18.07 are given in Table 5.
Mw (g/mol)a 60.096 46.03 88.1 18.02 The three coefficients Ai , Bi and Ci of the Antoine equa-
Tc (K)b 508.32 574 513.03c 647.37
Pc (bar)b 47.64 61 41.1c 221.2
tion used for calculation of the pure component vapor pres-
rgd 2.726 1.48 3.39e 0.615 sure are listed in Table 6.
dmd 1.66 1.52 1.89e 1.83
Ethanol Ethyl Methyl Methanol
formate formate Table 6
vL0i /(cm3 /mol)a 58.68 80.88 62.11 40.73 Antoine coefficients Ai , Bi and Ci for pure components P0i
LV
(bar) =
Mw (g/mol)a 46.07 74.08 60.052 32.042 exp(Ai (Bi /(Ci + T (K))))(1013.25/760)
Tc (K)b 516.26 508.5 487.2 512.6 Ai Bi Ci
Pc (bar)b 63.8 47.4 59.98 79.9
rgd 2.25 2.8 2.2f 1.536 Isopropanola 18.6929 3640.20 53.54
dmd 1.69 1.7 1.8 1.7 Formic acida 16.9882 3599.58 26.09
a
Isopropyl formateb 17.6710 3585.41 16.68
DECHEMA data base [1]. Watera 18.3036 3816.44 46.13
b
VDI-Wrmeatlas [18].
c Calculated by method of Lydersen [19].
Ethanola 18.9119 3803.98 41.68
d Prausnitz et al. [16].
Ethyl formatea 16.1611 2603.30 54.15
e Estimated by comparison with n-propyl formate.
Methanola 18.5875 3626.55 34.29
f Estimated by comparison of the isopropanol, ethanol, methanol se-
Methyl formatea 16.5104 2590.87 42.60
a Reid et al. [20].
quence with the isopropyl formate, ethyl formate and methyl formate
b DECHEMA data base [1].
sequence.
364 M. Tischmeyer, W. Arlt / Chemical Engineering and Processing 43 (2004) 357367

5. Results methanol + formic acid methyl formate + water

P, T, xi -data were measured during the reactions of: (at 313, 333 and 353 K).

Fig. 7 exemplary shows the measured pressure over

isopropanol + formic acid isopropyl formate + water
time curves for the methanolformic acid system at
(at 313 and 333 K) 313 K. Initial methanol concentrations change between
xi0 = 0.1 and 0.9. The discrete pressure points cor-
ethanol + formic acid ethyl formate + water respond to the time points where liquid samples were
(at 313 and 333 K) taken.

Fig. 7. P(t) diagrams for the methanolformic acid system at 313 K: (circle) experimental; (dash) calculated.
 M. Tischmeyer, W. Arlt / Chemical Engineering and Processing 43 (2004) 357367 365

Table 7
Regressed binary interaction parameters for the Wilson model
Components i, j

Methanolformic acid Ethanolformic acid Isopropanolformic acid

Temperature ( C) 40 60 40 60 40 60 80
Wilson ij 1322.2905 2202.9381 489.8492 156.5872 949.8210 1246.1398 1446.7360
Wilson ji 972.8247 1651.3409 57.8520 325.6978 562.4923 1600.1542 2102.0758

Pmean over all data (%) 2.2 6.6 12.3 4.4 2.1 3.7 2.6

Pmax over all data (%) 10.4 23.1 31.0 12.0 7.2 7.9 7.2

Pmean and
Pmax are the relative mean and maximum deviations of the calculated pressure and measured data calculated by |Pexp Pcalc |/Pexp (bar).
The ethanolformic acid reaction at 313 K was the first one examined. The apparatus (especially the accuracy and speed of liquid sampling) was advanced
and improved after completing the measurement of this phase equilibrium. Since each experiment consists of approximately nine reaction runs with about
12 liquid samples each, the amount of data points to be fitted by the model is immense. Deviations larger as compared to standard VLE measurements
were inevitable. The methanol + formic acid system at 333 K shows the fastest reaction rate. At high formic acid concentrations, the half-life time is
about 23 min. With this system, the maximum reaction rate to be examined by our measuring method is clearly reached.

Fig. 8. Calculated binary VLE diagram of the methanolformic acid system.

A complete set of all measured data is given by Tis- use of Eq. (1) with the Wilson gE -model for liquid phase
chmeyer [21]. The respective liquid concentrations x1 x4 at and the chemical theory for vapor phase. The relative devi-
these time points and the measured temperatures are used to ation of all experimental to calculated pressure data is then
calculate the system pressure and vapor concentrations by minimized during the model fitting procedure by variation

Fig. 9. Calculated binary VLE diagram of the ethanolformic acid system.

366 M. Tischmeyer, W. Arlt / Chemical Engineering and Processing 43 (2004) 357367

Fig. 10. Calculated binary VLE diagram of the isopropanolformic acid system.

of the binary interaction parameters of the reacting pair. Bi- Appendix A. Nomenclature
nary parameters for the Wilson model were obtained at 313
and 333 K for all reacting systems and at 353 K for the iso- a activity
propanol system. In case of the ethanolformic acid binary a12 , a21 binary interaction parameters for gE -models
phase, experimental hE -data measured by Zhao et al. [22] Ai , Bi , Ci Antoine coefficients, P (bar) and T (K)
were also included in the regression. The resulting binary dm dipole moment (Debye)
parameters are given in Table 7. Vapor phase data are not EA,ij energies of activation for reaction ij
reproduced here due to problems in the determination of the f fugacity (Pa)
compositions. g Gibbs energy per mole (J/mol)
In Figs. 810, the resulting binary phase equilibria of the gij energies of interaction between an ij pair
reacting acidalcohol pairs can be seen. All show a min- of molecules (J/mol)
imum pressure azeotrope at low to medium alcohol con- hmix enthalpy per mole (J/mol)
centrations which shifts to lower alcohol concentrations at k12 reaction rate constants of the
higher temperatures. esterification (mol/s)
k21 reaction rate constants of the hydrolysis
(mol/s)
6. Conclusions Ka chemical equilibrium constant in terms
of activities
Quaternary P, T, xi -data have been measured for the Kf chemical equilibrium constant in terms
reacting systems isopropanol + formic acid (313353 K), of fugacities
ethanol + formic acid (313333 K) and methanol + Kx chemical equilibrium constant in terms
formic acid (313333 K). A static cell with the possibility of mole fractions
of adding thermostated, degassed components and imme- Mw molecular weight (g/mol)
diate mixing as well as a quaternary regression method n number of components
have been used. Wilson gE -model parameters for the re- ni number of moles of component i
acting binary systems were obtained. Calculated values P pressure (Pa)
and experimental data are in very good agreement in five PLV vapor pressure (Pa)
out of seven cases. The new regressed parameters for the r reaction rate (mol/s)
chosen gE -model can be recommended for accurate com- rg radius of gyration (nm)
putation of the equilibrium conditions, e.g. in simulation R universal gas constant (J/mol K)
processes. t time (s)
The results show that the applied method can be rec- t0 time of mixing, start of the reaction (s)
ommended to determine the binary interaction param- T temperature (K)
eters of reacting systems with half-life times down to v molar volume (m3 /mol)
10 min. Temperature deviations due to mixing effects x liquid mole fraction
(exothermic reactions) are covered by the regression X transformed liquid coordinate
method since each data point is evaluated at its own y vapor mole fraction
temperature. Y transformed vapor coordinate
 M. Tischmeyer, W. Arlt / Chemical Engineering and Processing 43 (2004) 357367 367

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