1508 Ind. Eng. Chem. Res.

2003, 42, 1508-1516

Chemical Equilibrium and Liquid-Liquid Equilibrium in Aqueous

Solutions of Formaldehyde and 1-Butanol
Roger Peschla,† Baudilio Coto Garćı́a,‡ Michael Albert,§ Cornelius Kreiter,| and
Gerd Maurer*
Lehrstuhl für Technische Thermodynamik, Fachbereich Maschinenbau und Verfahrenstechnik,
Universität Kaiserslautern, D-67653 Kaiserslautern, Germany

A thermodynamic model for liquid-liquid phase equilibrium and chemical equilibrium in the
formaldehyde + water + 1-butanol system is presented. The model is an extension of the vapor-
liquid phase equilibrium model for the formaldehyde + water + methanol system. Formaldehyde
reacts with water and alcohols to form oligomers. New experimental results (from NMR
spectroscopic investigations) are reported for the chemical equilibrium in liquid formaldehyde
+ 1-butanol and formaldehyde + water + 1-butanol systems at temperatures from 278 to 348
K. New liquid-liquid phase equilibrium data are reported for temperatures of 298, 313, and
333 K. The model is able to reliably describe the liquid-liquid phase equilibrium, as well as the
specification in the liquid phases.

Introduction Formaldehyde undergoes similar chemical reactions

Formaldehyde is one of the most versatile intermedi-
ates in the chemical industry. The largest amount of
formaldehyde is used for the production of formaldehyde
polymers, i.e., polyacetal plastics and resins. The quality
of the polymers strongly depends on the water concen-
tration before polymerization. Anhydrous formaldehyde
is of fundamental importance when high-quality prod-
ucts are required. The common method of “drying”
formaldehyde is to convert it to trioxane, a stable cyclic
intermediate of formaldehyde that is usually purified
by distillation and crystallization. Because trioxane
depolymerizes to produce formaldehyde, it can be used
for almost all formaldehyde reactions, particularly when
anhydrous formaldehyde is required. Another possibility
for reducing the amount of water in formaldehyde
solutions is to use reactive extraction with monohydric
alcohols. A liquid-liquid phase split takes place when
the alcohol chain is sufficiently hydrophobic. 1-Butanol
is the first (in terms of increasing size) aliphatic
monohydric alcohol that is not completely miscible with
water. Because of its extraordinary reactivity, which
differs substantially from that of higher homologues and
aliphatic ketones, formaldehyde is predominantly present
as methylene glycol [MG, HO(CH2O)H] and poly(oxy-
methylene) glycols [MGn, HO(CH2O)nH), n > 1] in
aqueous solutions.
CH2O + H2O a HO(CH2O)H (I)
HO(CH2O)n-1H + HO(CH2O)H a
HO(CH2O)nH + H2O (II)
* To whom correspondence should be addressed. E-mail:
gmaurer@rhrk.uni-kl.de. Phone: +49-631-2052410. Fax: +49-
631-2053835.
†
Present address: MiRO Mineralölraffinerie Oberrhein,
D-76187 Karlsruhe, Germany.
‡ been continuously updated and extended by, for ex-
Present address: ESCET, Universidad Rey Juan Carlos,
E-28934 Mostoles, Madrid, Spain.
§
Present address: Degussa AG, VT-T, D-63403 Hanau,
Germany.
|
Present address: Fachbereich Chemie, Universität Kai-
serslautern, D-67653 Kaiserslautern, Germany.
10.1021/ie020743o CCC: $25.00 © 2003 American Chemical Society
Published on Web 02/08/2003
with alcohol as it does with water, resulting in the
formation of hemiformal [HF, HO(CH2O)R] and poly-
(oxymethylene) hemiformals [HFn, HO(CH2O)nR), n >
1], where, for example, R- represents CH3- in the case
of methanol and CH3(CH2)3- in the case of 1-butanol.
CH2O + ROH a HO(CH2O)R (III)
HO(CH2O)n-1R + HO(CH2O)R a
HO(CH2O)nR + ROH (IV)
In an equilibrated ternary liquid mixture of formalde-
hyde, water, and an alcohol, all chemical reaction
equilibria are observed simultaneously. The interchange
between formaldehyde in poly(oxymethylene) glycols
and formaldehyde in poly(oxymethylene) hemiformals
can be described (at least in principle) by taking into
account the usually very small concentration of form-
aldehyde monomers through chemical reactions I and
III.
The above chemical reactions have an essential influ-
ence on the properties of formaldehyde-containing aque-
ous solutions, and they need to be taken into account
in any thermodynamic model intended for formaldehyde-
containing systems. Because of the small amount of
monomeric formaldehyde in the liquid phase, the effects
of reactions I and III on the binary formaldehyde +
water and formaldehyde + alcohol systems can be
neglected, whereas the properties of the ternary system
formaldehyde + water + alcohol are strongly influenced
by these reactions (because of the formaldehyde-
interchange effect).
A physicochemical model1 that considers both chemi-
cal reactions as well as physical interactions in the
liquid phase has been shown to be very successful in
describing the vapor-liquid equilibria and enthalpies
of formaldehyde-containing mixtures. This model has
ample, Hasse et al.,2,3 Hahnenstein et al.,4-6 Albert et
al.,7-10 and Maiwald et al.11
This model was adopted for describing the phase
equilibrium in the formaldehyde + water + 1-butanol
system.

Experimental Procedures
Chemical Equilibrium. Information on transforma-
tion of formaldehyde into its reaction products with
water or alcohol is accessible from nuclear magnetic
resonance (NMR) spectroscopic investigations. Using a
high-resonance-frequency NMR spectrometer, it is pos-
sible to separate signals from -CH2 groups bound in
different poly(oxymethylene) glycols and poly(oxymeth-
ylene) hemiformals. Experimental studies to determine
chemical reaction equilibrium properties for reactions
II and IV in formaldehyde-containing solutions with
water and/or methanol have been performed by Hahn-
enstein et al.,5 Balashov et al.,12 Albert et al.,8 and
Maiwald et al.11 To our knowledge, no investigations of
chemical equilibria in mixtures involving formaldehyde
and 1-butanol have been reported to date.
NMR spectra of formaldehyde-containing solutions
yield different peaks from -CH2 groups (in both 13C and
1H NMR spectroscopy) depending on the chain length
of the poly(oxymethylene) glycols or/and poly(oxymethy-
lene) hemiformals present. The peak areas are obtained
by integration of the spectra. It is assumed that the area
of a peak is proportional to the total amount of the
species responsible for the peak. This results in a direct
relation between the peak area fraction and the mole
fraction of true species in the solution.
Binary formaldehyde + 1-butanol stock solutions were
prepared by dissolving paraformaldehyde in 1-butanol
at high temperature. These solutions were stored over
molecular sieves for several days to remove the water
liberated from the paraformaldehyde. All solid residues
and the molecular sieves were then removed by filtra-
tion. The remaining amount of water in the formalde-
hyde + 1-butanol solutions was estimated by gas
chromatography and/or a modified Karl Fischer titration
to below 0.003 g‚g-1 . The stoichiometric formaldehyde
concentration was determined using the sodium sulfite
method with a relative uncertainty of less than 1%. The
formaldehyde stock solutions were diluted with 1-bu-
tanol and/or bidistilled water. The NMR tubes used
were half-filled to reduce the vapor phase and, conse-
quently, an essential change in the liquid composition.
To ensure equilibrium, all samples were kept in a
thermostated bath for several days (weeks for the lowest
temperatures) at the temperature of the NMR spectro-
scopic investigations.
13C NMR spectroscopy was performed with a Bruker
AMX 400 NMR spectrometer (400.13 MHz), fully de-
coupled from the 1H nucleus. The temperature of a probe
was determined from the set point of the temperature-
control system. The temperature-determination proce-
dure was checked by comparison with data for the
influence of temperature on the chemical shift of pure
liquid ethylene glycol (cf. Günther13). The uncertainty
of the temperature measurement found by this method
is (1 K. Benzene-d6 (in sealed capillaries in the NMR
sample tubes) was used both as a lock and as a reference
substance.
NMR spectroscopic investigations of the chemical
reaction equilibrium in the binary formaldehyde + 1-
butanol system were carried out at stoichiometric form-
aldehyde concentrations from ∼0.2 to ∼0.5 mol‚mol-1.
The range of compositions covered in the ternary
formaldehyde + water + 1-butanol system was limited
by the phase splitting occurring in that system. Mea-
surements were carried out for formaldehyde and 1-bu-
tanol compositions ranging from about 0.3 to 0.4
Ind. Eng. Chem. Res., Vol. 42, No. 7, 2003 1509
mol‚mol-1 and from 0.28 to 0.36 mol‚mol-1, respectively.
The temperature range of the experimental work was
from 278 to 348 K.
The 13C NMR spectrum of the binary formaldehyde
+ 1-butanol solution is very similar to the spectrum of
the formaldehyde + methanol system. Peak assign-
ments were adopted from a previous work.4,5 Some
difficulties arose in the investigations of the ternary
formaldehyde + water + 1-butanol system because the
peaks given by one of the -CH2 endgroups in poly-
(oxymethylene) hemiformals give a chemical shift (be-
tween 85 and 87 ppm) very similar to that of the peaks
caused by the -CH2 endgroups in poly(oxymethylene)
glycols. In some cases, the resulting overlapping of
peaks did not allow for a reasonably accurate separation
and integration. At high formaldehyde concentrations,
the peak areas could be reproduced to within about 1%.
For dilute formaldehyde solutions, however, peaks cor-
responding to higher poly(oxymethylene) hemiformals
were very small, and the reproducibility decreased.
Liquid-Liquid Equilibrium. Experimental work
on the liquid-liquid equilibrium of the formaldehyde
+ water + 1-butanol system was performed at 298 K.
For temperatures of 313 and 333 K, some liquid-liquid
phase equilibrium data are available from Lavrova and
Lesteva.14 Liquid two-phase systems were prepared in
thermostated glass vessels by diluting formaldehyde
stock solutions with water and 1-butanol. The total mass
of the two-phase systems was typically between 90 and
120 g, and the organic-phase formaldehyde concentra-
tion was up to 0.235 mol‚mol-1. The two-phase systems
were intensively stirred at constant temperature for up
to 5 days. Afterward, the systems were allowed to
separate for another 5 days before samples were taken
from the coexisting liquid phases. The formaldehyde
content of a sample was analyzed by applying the
sodium sulfite method. The concentration of water in a
liquid sample was determined either by a modified Karl
Fischer titration15 or by gas chromatography.15
Modeling
The model applied to correlate the experimentally
determined data for the chemical equilibrium, as well
as for the liquid-liquid phase equilibrium of the form-
aldehyde + water + 1-butanol system, was adopted from
previous work on the system formaldehyde + water +
methanol.1,7-10 The outline of the extension of the model
to describe the equilibrium in partially miscible aque-
ous-alcoholic formaldehyde-containing mixtures is shown
in Figure 1. The model takes into account chemical
reactions as well as differences in interactions between
all species in both liquid phases, i.e., a liquid phase is
treated as a real, chemically reactive mixture of water
(W), 1-butanol (1B), formaldehyde momoners (FA),
methylene glycol (MG1), poly(oxymethylene) glycols
(MGn), hemiformal (HF1), and poly(oxymethylene) hemi-
formal (HFn). The chemical potential of a component in
a liquid phase is normalized according to Raoult’s law
i.e., the reference state for the chemical potential of
species i is the same for both phases. The influence of
pressure on the properties of a species i in a liquid phase
is neglected. The condition for liquid-liquid phase
equilibrium is therefore
xi′γi′ ) xi′′γi′′
i ) FA, W, 1B, MG1, MGn, HF1, HFn (1)
1510 Ind. Eng. Chem. Res., Vol. 42, No. 7, 2003

pSFA pSW vap

KMG1 ) S
KMG1 (6)
pMG 1
p0

pSFA pS1B vap

KHF1 ) S 0 KHF1 (7)
pHF1p

The stoichiometric composition of a liquid phase

follows from mass balances in that phase

ntotal ∞ ∞
x̃FA )
ñtotal
∑
(xFA + ixMGi + ixHFi)
i)1 i)1
∑ (8)

ntotal ∞
x̃W )
ñtotal i)1
∑
(xW + xMGi) (9)

ntotal ∞

∑
Figure 1. Scheme for modeling the liquid-liquid equilibrium of
the formaldehyde + water + 1-butanol system x̃1B ) (x1B + xHFi) (10)
ñtotal i)1

The nonideality of the liquid phase is taken into account

through the UNIFAC group contribution method.16 The where
following chemical reaction equilibria are considered: ntotal ∞ ∞
the formation of methylene glycol and hemiformal from
the reactions of formaldehyde with water and 1-butanol, ñtotal
) (1 + ∑
i)1
ixMG + ∑ixHF )-1
i
i)1
i
(11)
respectively, and the polymerizations of methylene
glycol and hemiformal to poly(oxymethylene) glycols and Model Parameters. The chemical reaction equilib-
poly(oxymethylene) hemiformals, respectively. Although rium constant for the formation of methylene glycol from
the amount of formaldehyde present as monomers is water and formaldehyde in the vapor phase (KMG vap
) was
very small, the chemical reaction equilibria for the 17
taken from Hall and Piret. The chemical reaction
1

formation of methylene glycol and hemiformal are very constant for the formation of hemiformal from 1-butanol
important, as they provide the transfer from formalde- vap
and formaldehyde in the vapor phase (KHF ) was ap-
hyde in poly(oxymethylene) glycols to formaldehyde in 1
proximated by the constant for the formation of hemi-
poly(oxymethylene) hemiformals (and vice versa). As in formal from methanol and formaldehyde, which was
the model for the formaldehyde + water + methanol taken from Kogan.18
system, further chemical reactions (resulting, for ex- The chemical reaction equilibrium constants (KMGn,
ample, in methylal and dimethoxy ether) are neglected n g 2) for the formation of poly(oxymethylene) glycols
as they are of minor importance under the conditions (reaction II; cf. eq 4) were taken from an earlier
of interest in the present work. publication by Albert et al.9 on the vapor-liquid phase
Chemical reaction equilibrium is taken into account behavior of the binary formaldehyde + water system.
through “true” chemical reaction equilibrium constants, These chemical reaction equilibrium constants are listed
i.e., using activities in Table 1. The vapor pressures of formaldehyde (pSFA),
water (pSW), and methylene glycol (pMG S
1
) were also
xMG1 γMG1 9
taken from Albert et al. The vapor pressure of 1-butanol
KMG1 ) (2) (pS1B) was taken from a technical data sheet from
xFAxW γFAγW
BASF.19 The vapor pressure data (as parameters of the
Antoine equation) are listed in Table 2. The activity
xHF1 γHF1 coefficients were calculated according to the UNIFAC
KHF1 ) (3) model. Formaldehyde, water, methylene glycol, 1-bu-
xFAx1B γFAγ1B
tanol, and hemiformal were treated as single UNIFAC
groups. Poly(oxymethylene) glycols [HO(CH2O)nH] were
xMGnxW γMGnγW assumed to consist of (n - 1) formaldehyde groups, one
KMGn ) ng2 (4) -CH2 group, and two HO- groups. Poly(oxymethylene)
xMGn-1xMG1 γMGn-1γMG1 hemiformals [CH3(CH2)3O(CH2O)nH] were spilt into (n
- 1) formaldehyde groups and one hemiformal group
xHFnx1B γHFnγ1B [CH3(CH2)3O(CH2O)H]. The group arrangement is also
KHFn ) ng2 (5) given in Table 3. The sizes and surface parameters of
xHFn-1xHF1 γHFn-1γHF1 all groups are given in Table 4. Albert et al.9 used the
same group assignment for the binary formaldehyde +
water system. Therefore, UNIFAC parameters ai,j for
Literature data were obtained for the formation of interactions between groups (i, j) ) CH2O, H2O, HO-
vap vap
methylene glycol, KMG 1
, and hemiformal, KHF 1
, in the (CH2O)H, OH, and CH2 were adopted from Albert et al.9
vapor phase. Those data were converted into values of Many more group interactions parameters are required.
KMG1 and KHF1 via Those between 1-butanol and water were assumed to
 Ind. Eng. Chem. Res., Vol. 42, No. 7, 2003 1511

Table 1. Chemical Reaction Equilibrium Constants Table 5. UNIFAC Interaction Parameters ai,j/K
ln K ) A + B/(T/K) j
reaction A B source i 1 2 3 4 5 6 7
vap
KMG -16.984 5233.2 Kogan18 1 - 774.81 189.21 237.70 83.36 0.00 0.00
vap
KHF
1
-20.263 7368.3 Hall and Piret17 2 -142.35 - 189.52 -229.10 300.00 a2,6 312.34
KMG2
1
0.00498 869.5 Albert et al.9 3 59.20 -191.82 - -229.10 300.00 0.00 4.59
4 28.06 353.50 353.50 - 156.40 0.00 615.46
KMGn, n g 3 0.01908 544.5 Albert et al.9
5 251.50 1318.00 1318.00 986.50 - 0.00 0.00
KHFn, n g 2 0.34739 -605.7 this work
6 0.00 a6,2 0.00 0.00 0.00 - 17.40
Table 2. Antoine Coefficients for Pure-Component Vapor 7 0.00 -66.02 4.08 3.90 0.00 -36.08 -
Pressures ai,j/K ) A + B(T/K)
ln(pSi /kPa) ) A + B/[(T/K) + C] function A B
component A B C source a2,6 -674.46 3.1628
formaldehyde 14.4625 -2204.13 -30.00 Albert et al.9 a6,2 531.75 -1.8132
water 16.2886 -3816.44 -46.13 Albert et al.9
methylene glycol 19.5527 -6189.19 -9.15 Albert et al.9 hemiformal and the UNIFAC interaction parameters
1-butanol 15.2021 -3138.95 -94.255 BASF19 from the liquid-liquid equilibrium data. Finally, these
hemiformal 18.7262 -6505.73 0.00 this work first estimates were used as initial values for a simul-
taneous adjustment of all parameters to NMR and
Table 3. Division of Components into UNIFAC Groups
phase equilibrium data. The final results are given in
component UNIFAC group(s) S
Table 1 (KHFn, n g 2), Table 2 (pHF 1
), and Table 5
formaldehyde 1 CH2O (UNIFAC interaction parameters).
water 1 H2O As hemiformal does not exist as a pure compound,
methylene glycol 1 HO(CH2O)H its vapor pressure is not directly accessible by experi-
poly(oxymethylene) glycol (n - 1) CH2O, 1 CH2, 2 HO ng2
ments. The vapor pressure of hemiformal is required
1-butanol CH3(CH2)3OH vap
hemiformal CH3(CH2)3O(CH2O)H only to convert the (first estimate) for KHF 1
to KHF1 (cf.
poly(oxymethylene) CH3(CH2)3O(CH2O)H, ng2 eq 7). Therefore, fitting the hemiformal vapor pressure
hemiformal (n - 1) CH2O to NMR data as well as liquid-liquid equilibrium data
is essentially an adjustment to the experimental infor-
Table 4. UNIFAC Size and Surface Parameters
mation. The quality of predictions for the vapor-liquid
group no. r q equilibrium data of, for example, the binary formalde-
CH2O 1 0.9183 0.780 hyde + 1-butanol system is still open, as experimental
H2O 2 0.9200 1.400 data are not available.
HO(CH2O)H 3 2.6744 2.940 From NMR spectroscopic investigations of chemical
HO- 4 1.0000 1.200 reaction equilibrium, true species composition data for
-CH2 5 0.6744 0.540
CH3(CH2)3OH 6 3.4543 3.052
the binary formaldehyde-1-butanol system were used
CH3(CH2)3O(CH2O)H 7 4.3726 3.832 for the simultaneous parameter determination described
above. The peak areas determined by NMR spectroscopy
depend on temperature and were fitted to literature were converted into concentrations, assuming that the
data for the liquid-liquid equilibrium of the binary peak areas are proportional to the numbers of the
water + 1-butanol system.14,20,21 To reduce the number corresponding groups and that the constant of propor-
of adjustable parameters, some interaction parameters tionality is the same for all NMR-active -CH2 groups.
were neglected (i.e., both UNIFAC group interaction However, because no peak due to formaldehyde mono-
parameters were set to zero), including all parameters mers is present and because it is not possible to
between formaldehyde on one side and 1-butanol and distinguish between the peaks caused by poly(oxym-
hemiformal on the other side; all parameters between ethylene) glycols and poly(oxymethylene) hemiformals
1-butanol on one side and methylene glycol, the HO- containing more than four formaldehyde groups, some
group, and the -CH2 group on the other side; and the additional assumptions were required to qualitatively
interaction parameters between hemiformal and the ascribe the peak areas to the concentrations of formal-
-CH2 group. dehyde oligomers. As described previously by Hahnen-
With these simplifications, the remaining, unknown stein et al.5 and applied by Albert et al.,8 the experi-
model parameters are as follows: the chemical reaction mental results for the peak areas obtained in investiga-
equilibrium constants for the formation of poly(oxy- tions of the formaldehyde + 1-butanol system were used
methylene) hemiformals (KHFn, n g 2); the vapor pres- to estimate (for a given temperature and average
S
sure of hemiformal (pHF 1
); and eight UNIFAC param- formaldehyde concentration) a pseudo-chemical equi-
eters for binary interactions between hemiformal on side librium constant, Kx,HFi, for chemical reaction IV. It was
and H2O, methylene glycol, the HO- group, and 1-bu- assumed that this constant does not depend on the
tanol on the other side. number of formaldehyde groups in the poly(oxymeth-
These parameters were fitted simultaneously to the ylene) hemiformal. These results were then used (in-
new NMR data for the chemical reaction equilibrium stead of the direct NMR data), along with the experi-
(specification in a single liquid phase) and the liquid- mental results for the liquid-liquid equilibrium, to
liquid equilibrium data of the ternary formaldehyde + determine the true chemical reaction equilibrium con-
water + 1-butanol system. This parameter adjustment stants. In the modeling of the liquid-liquid equilibrium
process started with the determination of first estimates data, poly(oxymethylene) glycols with more than 16
for the chemical equilibrium constants for poly(oxy- formaldehyde segments and poly(oxymethylene) hemi-
methylene) hemiformal formation from the NMR data, formals with more than 10 formaldehyde segments were
followed by first estimates for the vapor pressure of neglected. However, the quality of the experimental
1512 Ind. Eng. Chem. Res., Vol. 42, No. 7, 2003

Table 6. Chemical Equilibrium (Specification) for the Formaldehyde + 1-Butanol System: Comparison of Model
Calculations with Experimental Dataa
xHF1 xHF2 xHF3
T x̃FA (mol‚mol-1) ∆xHF1 (mol‚mol-1) ∆xHF2 (mol‚mol-1) ∆xHF3
(K) (mol‚mol-1) exp cal (%) exp cal (%) exp cal (%)
278.15 0.5446 0.4897 0.4783 -2.3 0.1763 0.1757 -0.3 0.0635 0.0646 1.7
0.3416 0.4053 0.4004 -1.2 0.0471 0.0486 3.3 0.0055 0.0059 7.4
0.1959 0.2171 0.2233 2.8 0.0121 0.0095 -21. 0.0007 0.0004 -42.
298.15 0.5446 0.4581 0.4595 0.3 0.1745 0.1745 0.01 0.0665 0.0663 -0.3
0.3416 0.3954 0.3885 -1.7 0.0502 0.0522 4.0 0.0064 0.0070 9.7
0.1959 0.2184 0.2203 0.9 0.0116 0.0108 -7.0 0.0006 0.0005 -12.
0.5351 0.4627 0.4630 0.1 0.1693 0.1692 -0.1 0.0620 0.0618 -0.3
0.5282 0.4698 0.4651 -1.0 0.1654 0.1652 -0.1 0.0582 0.0587 0.8
0.5282 0.4825 0.4651 -3.6 0.1657 0.1652 -0.3 0.0569 0.0587 3.1
0.2495 0.2843 0.2854 0.4 0.0214 0.0209 -2.2 0.0016 0.0015 -4.0
0.3939 0.4331 0.4337 0.1 0.0795 0.0793 -0.3 0.0146 0.0145 -0.7
0.5282 0.4789 0.4651 -2.9 0.1656 0.1652 -0.3 0.0573 0.0587 2.4
0.2495 0.2825 0.2854 1.0 0.0221 0.0209 -5.3 0.0017 0.0015 -9.7
0.3939 0.4218 0.4337 2.8 0.0820 0.0793 -3.3 0.0159 0.0145 -8.8
0.4538 0.4504 0.4647 3.2 0.1187 0.1170 -1.4 0.0313 0.0295 -5.9
0.5282 0.4773 0.4651 -2.6 0.1656 0.1652 -0.3 0.0574 0.0587 2.2
323.15 0.5446 0.4528 0.4387 -3.1 0.1741 0.1726 -0.9 0.0669 0.0679 1.5
0.3416 0.3810 0.3749 -1.6 0.0545 0.0560 2.7 0.0078 0.0084 7.1
0.1959 0.2162 0.2166 0.2 0.0125 0.0123 -1.8 0.0007 0.0007 -0.5
0.2495 0.2747 0.2787 1.5 0.0249 0.0234 -6.2 0.0023 0.0020 -14.
0.3939 0.4181 0.4159 -0.5 0.0827 0.0829 0.2 0.0164 0.0165 0.7
0.5282 0.4478 0.4438 -0.9 0.1645 0.1640 -0.3 0.0604 0.0606 0.3
0.2495 0.2768 0.2787 0.7 0.0242 0.0234 -3.4 0.0021 0.0020 -6.7
0.3939 0.4272 0.4159 -2.7 0.0808 0.0829 2.6 0.0153 0.0165 7.9
0.4538 0.4434 0.4436 0.1 0.1194 0.1191 -0.3 0.0321 0.0320 -0.4
0.5282 0.4524 0.4438 -1.9 0.1647 0.1640 -0.5 0.0599 0.0606 1.1
348.15 0.2495 0.2687 0.2721 1.3 0.0270 0.0255 -5.7 0.0027 0.0024 -11.
0.3939 0.4002 0.3996 -0.1 0.0860 0.0854 -0.8 0.0185 0.0182 -1.5
0.2495 0.2680 0.2721 1.5 0.0273 0.0255 -6.7 0.0028 0.0024 -14.
0.3939 0.4068 0.3996 -1.8 0.0848 0.0854 0.7 0.0177 0.0182 3.0
0.4538 0.4388 0.4247 -3.2 0.1197 0.1200 0.3 0.0327 0.0339 3.7
0.5282 0.4293 0.4247 -1.1 0.1632 0.1620 -0.7 0.0621 0.0618 -0.5
a From NMR spectroscopy.

data does not allow any distinction to be made between
nine different chemical reaction constants (KHF2, ...,
KHF10). Therefore, sensitivity studies were performed to
determine the optimum number of different chemical
reaction equilibrium constants. It was found that a
single constant was sufficient, i.e.
KHF2 ) KHF3 ) ‚‚‚ ) KHF9 ) KHF10
Thus, the thermodynamic model for describing the
liquid-phase properties of the formaldehyde + 1-butanol
system is somewhat simpler than that for the formal-
dehyde + water system. In the latter system, two
different values for the chemical reaction equilibrium
constants of poly(oxymethylene) glycol formation were
used (KMG2 and KMG3 ) KMG4 ) KMG5 ) ‚‚‚ ) KMG15 )
KMG16).
Comparison with Experimental Results
Chemical Equilibrium (Specification). The new
experimental data from NMR spectroscopic investiga-
tions are compared to the correlation results in Table
6, as well as in Figures 2-5 (formaldehyde + 1-butanol)
and Table 7(formaldehyde + water + 1-butanol). Table
6 gives the experimental results for the mole frac-
tions of hemiformal (HF1) and the two oligomers HF2
(containing two formaldehyde segments) and HF3
(containing three formaldehyde segments) in liquid
mixtures of formaldehyde and 1-butanol at 278, 298,
323, and 348 K as measured by NMR spectroscopy in
comparison to the correlation. The experimental data
cover stoichiometric formaldehyde concentrations be-
tween 20 and 55 mol %. In these solutions, formalde-
hyde is predominantly present as hemiformal. The
relative deviations between the calculated and experi-
mental mole fractions exceed 4% only when the mole
fraction is below 3%. Relative deviations of more than
10% are observed only when the mole fraction is below
1%.
(12)
Table 7 gives, in an analogous manner, the experi-
mental data for the concentrations of eight oligomers:
four oligomers containing formaldehyde and water, as
well as the analogous four oligomers containing form-
aldehyde and 1-butanol. Fifteen NMR spectroscopic
investigations were performed at temperatures between
278 and 348 K with aqueous solutions containing
formaldehyde and butanol (stoichiometric mole fractions
between 30 and 40 mol % and between 25 and 37 mol
%, respectively). In such solutions, formaldehyde is
predominantly present as hemiformal (HF1). The rela-
tive deviations between the calculated and experimental
mole fractions of hemiformal are below 5%. About as
much formaldehyde is converted to HF2 as to methylene
glycol (MG1), but the concentrations of these species are
only about 5 mol %. The relative deviations between the
NMR data and the calculations for these concentration
is generally better than 10%, particularly at higher
formaldehyde concentrations. However, the deviations
might increase to more then 20% at low formaldehyde
concentrations. The mole fractions of the higher oligo-
mers decrease by approximately a factor of 3 (for MGi)
and 4 (for HFi) as the number of formaldehyde groups
in the oligomers increases from i to (itl). There is no
systematic deviation between experiment and calcula-
 Ind. Eng. Chem. Res., Vol. 42, No. 7, 2003 1513

Table 7. Chemical Reaction Equilibrium (Specification) in Liquid Phases of the Formaldehyde + Water + 1-Butanol
System: Comparison of Model Calculations with Experimental NMR Data
Poly(oxyl methylene) Glycols
xMG1 xMG2 xMG3 xMG4
T x̃FA x̃1B (mol‚mol-1) ∆xMG1 (mol‚mol-1) ∆xMG2 (mol‚mol-1) ∆xMG3 (mol‚mol-1) ∆xMG4
(K) (mol‚mol-1) (mol‚mol-1) exp cal (%) exp cal (%) exp cal (%) exp cal (%)
278.15 0.4063 0.3567 0.0181 0.0249 37 0.0065 0.0145 120 0.0015 0.0052 248 0.0004 0.0019 370
0.3168 0.2781 0.0336 0.0398 18 0.0157 0.0199 26 0.0047 0.0060 28 0.0014 0.0018 29
0.2923 0.2566 0.0314 0.0430 37 0.0125 0.0203 62 0.0032 0.0058 80 0.0008 0.0016 105
298.15 0.4063 0.3567 0.0253 0.0253 -0.1 0.0120 0.0126 5 0.0038 0.0041 7.8 0.0012 0.0013 11
0.3168 0.2781 0.0381 0.0404 5.9 0.0183 0.0177 -3.2 0.0058 0.0049 -15 0.0019 0.0014 -28
0.2923 0.2566 0.0388 0.0436 12 0.0175 0.0182 4.1 0.0052 0.0048 -7.5 0.0016 0.0013 -21
323.15 0.4063 0.3567 0.0269 0.0269 0.1 0.0119 0.0124 4.6 0.0037 0.0039 4.9 0.0011 0.0012 10.
0.3168 0.2781 0.0448 0.0425 -5.1 0.0230 0.0177 -23 0.0082 0.0048 -42 0.0029 0.0013 -55
0.2923 0.2566 0.0411 0.0458 11 0.0173 0.0183 5.7 0.0051 0.0047 -7.9 0.0015 0.0012 -19
0.4141 0.3699 0.0244 0.0243 -0.5 0.0106 0.0112 5.6 0.0032 0.0035 8.8 0.0010 0.0011 8.3
0.3212 0.2870 0.0388 0.0409 5.4 0.0172 0.0170 -1.1 0.0053 0.0046 -13 0.0016 0.0012 -22
0.2949 0.2635 0.0482 0.0445 -7.7 0.0253 0.0177 -30 0.0092 0.0045 -51 0.0033 0.0012 -65
348.15 0.4141 0.3699 0.0227 0.0266 17 0.0081 0.0123 52 0.0021 0.0039 86 0.0005 0.0012 148
0.3212 0.2870 0.0404 0.0440 8.9 0.0168 0.0187 12 0.0050 0.0052 3.6 0.0015 0.0014 -4.6
0.2949 0.2635 0.0413 0.0477 15 0.0159 0.0195 23 0.0044 0.0051 16 0.0012 0.0013 12
Poly(oxymethylene) Hemiformals
xHF1 xHF2 xHF3 xHF4
T x̃FA x̃1B (mol‚mol-1) ∆xHF1 (mol‚mol-1) ∆xHF2 (mol‚mol-1) ∆xHF3 (mol‚mol-1) ∆xHF4
(K) (mol‚mol-1) (mol‚mol-1) exp cal (%) exp cal (%) exp cal (%) exp cal (%)
278.15 0.4063 0.3567 0.2980 0.2960 -0.7 0.0957 0.0883 -7.7 0.0307 0.0263 -14 0.0099 0.0079 -21
0.3168 0.2781 0.2018 0.1995 -1.2 0.0539 0.0499 -7.5 0.0144 0.0125 -13 0.0038 0.0031 -18
0.2923 0.2566 0.1801 0.1764 -2.0 0.0494 0.0416 -16 0.0136 0.0098 -28 0.0037 0.0023 -38
298.15 0.4063 0.3567 0.2876 0.2837 -1.3 0.0911 0.0906 -0.6 0.0288 0.0289 0.4 0.0091 0.0092 1.4
0.3168 0.2781 0.1933 0.1922 -0.6 0.0515 0.0526 2.2 0.0137 0.0144 5.1 0.0037 0.0039 6.6
0.2923 0.2566 0.1717 0.1705 -0.7 0.0447 0.0442 -1.1 0.0116 0.0115 -1.1 0.0030 0.0030 -0.9
323.15 0.4063 0.3567 0.2754 0.2688 -2.4 0.0911 0.0906 -0.6 0.0301 0.0305 1.4 0.0100 0.0103 2.8
0.3168 0.2781 0.1822 0.1816 -0.3 0.0463 0.0531 15 0.0118 0.0155 31 0.0030 0.0045 51
0.2923 0.2566 0.1644 0.1611 -2.0 0.0452 0.0447 -1.1 0.0124 0.0124 0.1 0.0034 0.0034 1.4
0.4141 0.3699 0.2894 0.2826 -2.4 0.0955 0.0949 -0.6 0.0315 0.0319 1.3 0.0104 0.0107 3.1
0.3212 0.2870 0.1923 0.1887 -1.9 0.0543 0.0550 1.3 0.0153 0.0161 4.9 0.0043 0.0047 8.9
0.2949 0.2635 0.1619 0.1660 2.5 0.0360 0.0459 27 0.0080 0.0127 59 0.0018 0.0035 95
348.15 0.4141 0.3699 0.2782 0.2678 -3.8 0.0973 0.0933 -4.1 0.0340 0.0325 -4.4 0.0119 0.0113 -4.8
0.3212 0.2870 0.1851 0.1771 -4.3 0.0549 0.0537 -2.2 0.0163 0.0163 -0.2 0.0048 0.0049 2.7
0.2949 0.2635 0.1632 0.1554 -4.8 0.0474 0.0446 -5.9 0.0138 0.0128 -7.2 0.0040 0.0037 -8.1

Figure 2. Specification in liquid mixtures of formaldehyde and Figure 3. Specification in liquid mixtures of formaldehyde and
1-butanol at 278 K: experimental results (O, NMR spectroscopy) 1-butanol at 298 K: experimental results (O, NMR spectroscopy)
and model calculations (solid lines). and model calculations (solid lines).

tion for these mole fractions, but because the concentra-
tions are sometimes very small, the relative deviations
can rise to more than 50%, but they are never much
larger than the experimental uncertainty.
Liquid-Liquid Equilibrium. The UNIFAC results
for the liquid-liquid equilibrium of the binary, nonre-
active system water + 1-butanol are shown in Table 8
and Figure 6. The model represents the experimental
results for the mole fraction of butanol in the coexisting
phases with relative deviations of about 2% at temper-
atures up to about 350 K, i.e., in the range of temper-
atures of interest in the present work. However, it is
obvious that the influence of temperature on the mis-
cibility gap is not sufficiently well described at higher
temperatures, resulting in an upper critical end-point
temperature for the liquid-liquid equilibrium that is
much too large. A better description at higher temper-
atures would have required a more complicated expres-
sion for the influence of temperature on the interaction
parameters.
1514 Ind. Eng. Chem. Res., Vol. 42, No. 7, 2003

Table 8. Liquid-Liquid Equilibrium of the Water +

1-Butanol System: Comparison between Calculated and
Experimental Data
x1B′ x1B
T (mol‚mol-1) ∆x1B′′ (mol‚mol-1) ∆x1B
(K) exp cal (%) exp cal (%) ref
273.15 0.0271 0.0242 -11 0.5112 0.5140 0.6 20
278.15 0.0250 0.0227 -9.2 0.4989 0.5110 2.4 21
283.15 0.0230 0.0215 -6.6 0.5061 0.5071 0.2 20
0.0232 0.0215 -7.5 0.4981 0.5071 1.8 21
288.15 0.0213 0.0204 -4.0 0.4952 0.5023 1.4 21
293.15 0.0197 0.0195 -0.8 0.4980 0.4969 -0.2 20
0.0202 0.0195 -3.1 0.4919 0.4969 1.0 21
0.0210 0.0195 -6.8 0.4914 0.4969 1.1 21
298.15 0.0189 0.0188 -0.7 0.4888 0.4910 0.4 21
0.0185 0.0188 1.3 0.4942 0.4910 -0.6 21
0.0189 0.0188 -0.4 0.4906 0.4910 0.1 this work
303.15 0.0179 0.0181 1.3 0.4861 0.4846 -0.3 20
Figure 4. Specification in liquid mixtures of formaldehyde and 0.0182 0.0181 -0.3 0.4834 0.4846 0.2 21
1-butanol at 323 K: experimental results (O, NMR spectroscopy) 308.15 0.0175 0.0176 0.5 0.4767 0.4777 0.2 21
and model calculations (solid lines). 313.15 0.0167 0.0171 2.5 0.4717 0.4705 -0.3 20
0.0169 0.0171 1.4 0.4715 0.4705 -0.2 21
0.0166 0.0171 3.0 0.4702 0.4705 0.1 14
323.15 0.0163 0.0164 0.6 0.4562 0.4551 -0.2 20
0.0165 0.0164 -0.7 0.4568 0.4551 -0.4 21
333.15 0.0162 0.0159 -1.8 0.4381 0.4388 0.2 20
0.0167 0.0159 -4.6 0.4401 0.4388 -0.3 21
0.0165 0.0159 -3.5 0.4391 0.4388 -0.1 14
343.15 0.0166 0.0156 -6.0 0.4152 0.4218 1.6 20
0.0172 0.0156 -9.4 0.4190 0.4218 0.7 21
353.15 0.0175 0.0155 -12 0.3890 0.4042 3.9 20
0.0177 0.0155 -12 0.4030 0.4042 0.3 21
363.15 0.0195 0.0155 -22 0.3600 0.3863 7.3 20
373.15 0.0232 0.0156 -32 0.3290 0.3680 12 20
383.15 0.0295 0.0158 -46 0.2875 0.3496 22 20
393.15 0.0440 0.0162 -63 0.2180 0.3310 52 20
398.15 0.0710 0.0164 -77 0.1490 0.3217 116 20

maximum formaldehyde concentrations in the coexist-

Figure 5. Specification in liquid mixtures of formaldehyde and
1-butanol at 348 K: experimental results (O, NMR spectroscopy)
and model calculations (solid lines).
ing phases was about 14 mol % (in the aqueous phase)
and about 25 mol % in the butanol-rich liquid phase.
The model nicely describes the ternary liquid-liquid
phase equilibrium, but the formaldehyde concentration
is underestimated in the aqueous phase and overesti-
mated in the organic phase, i.e., the slopes of a liquid-
liquid tie lines in Figures 7-9 are somewhat too large.

Figure 6. Liquid-liquid phase equilibrium of the binary system
water + 1-butanol: experimental results (0, Lavrova and Leste-
va;14 ], v. Erichsen;20 3, Sœrensen and Arlt21) and model calcula-
tions (solid lines).
The new liquid-liquid phase equilibrium data for the
formaldehyde + water + 1-butanol system are given in
Table 9 and Figures 7-9. The stoichiometric formalde-
hyde concentration in the butanol-rich phase is always
higher than that in the coexisting aqueous phase. The
miscibility gap decreases with increasing formaldehyde
concentration, resulting in a closed miscibility gap. The
Conclusion
A thermodynamic model for the liquid-liquid phase
equilibrium of the formaldehyde + water + 1-butanol
system is presented. The model takes into account the
rather complex chemical equilibrium caused by chemical
reactions of formaldehyde with water as well as with
butanol. Information on the chemical reaction equili-
brium is obtained from NMR spectroscopic investiga-
tions. Physical interactions also have an essential
influence on the partitioning of formaldehyde between
the coexisting phases and were therefore also taken into
account (through the UNIFAC model). Chemical reac-
tion equilibrium constants for the formation of poly-
(oxymethylene) glycols were adopted from earlier work
on aqueous solutions of formaldehyde. New NMR spec-
troscopic data were used to determine the chemical reac-
tion equilibrium constants for the formation of oligomers
of formaldehyde and butanol [i.e., poly(oxymethylene)
hemiformals]. Although the concentration of formalde-
hyde monomers is very small and can be neglected in
the mass balances in most cases, formaldehyde mono-
mers play an important role, as their concentration
governs the partitioning of formaldehyde between poly-
(oxymethylene) glycols and poly(oxymethylene) hemi-
 Ind. Eng. Chem. Res., Vol. 42, No. 7, 2003 1515

Table 9. Liquid-Liquid Equilibrium of the Formaldehyde + Water + 1-Butanol System: Comparison between
Calculated and Experimental Data
x̃FA′ x̃1B′ x̃FA′′ x̃1B′′
T (mol‚mol-1) ∆x̃FA′ (mol‚mol-1) ∆x̃1B′ (mol‚mol-1) ∆x̃FA′′ (mol‚mol-1) ∆x̃1B′′
(K) exp cal (%) exp cal (%) exp cal (%) exp cal (%)
298.15 0.0000 0.0000 - 0.0189 0.0188 -0.5 0.0000 0.0000 - 0.4906 0.4910 0.1
0.0073 0.0074 1.4 0.0181 0.0195 7.7 0.0539 0.0525 -2.6 0.4668 0.4529 -3.0
0.0163 0.0154 -5.5 0.0183 0.0186 1.6 0.1071 0.1083 1.1 0.4044 0.4049 0.1
0.0246 0.0232 -5.7 0.0181 0.0189 4.4 0.1363 0.1404 3.0 0.3677 0.3755 2.1
0.0393 0.0358 -8.9 0.0206 0.0189 -8.3 0.1725 0.1822 5.6 0.3149 0.3296 4.7
0.0849 0.0794 -6.5 0.0200 0.0223 12 0.2319 0.2411 4.0 0.2221 0.2245 1.1
0.0664 0.0612 -7.8 0.0193 0.0206 6.7 0.2162 0.2264 4.7 0.2586 0.2648 2.4
0.1036 0.0986 -4.8 0.0229 0.0256 12 0.2409 0.2478 2.9 0.1941 0.1937 -0.2
0.1347 0.1311 -2.7 0.0317 0.0334 5.4 0.2388 0.2431 1.8 0.1457 0.1449 -0.6
0.1422 0.1391 -2.2 0.0338 0.0364 7.7 0.2352 0.2334 -0.8 0.1345 0.1272 -5.4
313.15 0.0000 0.0000 - 0.0166 0.0171 3.0 0.0000 0.0000 - 0.4702 0.4705 0.1
0.0037 0.0028 -24 0.0166 0.0168 1.2 0.0292 0.0304 4.1 0.4421 0.4474 1.2
0.0077 0.0056 -27 0.0166 0.0165 -0.6 0.0540 0.0568 5.2 0.4196 0.4261 1.6
0.0160 0.0141 -12 0.0167 0.0171 2.4 0.0966 0.1016 5.2 0.3762 0.3893 3.5
0.0272 0.0234 -14 0.0172 0.0174 1.2 0.1330 0.1415 6.4 0.3372 0.3507 4.0
0.0351 0.0312 -11 0.0174 0.0182 4.6 0.1534 0.1640 6.9 0.3117 0.3270 4.9
0.0484 0.0424 -12 0.0180 0.0188 4.4 0.1785 0.1903 6.6 0.2830 0.2926 3.4
0.0517 0.0455 -12 0.0182 0.0191 5.0 0.1836 0.1956 6.5 0.2756 0.2847 3.3
0.0667 0.0588 -12 0.0188 0.0206 9.6 0.2010 0.2137 6.3 0.2485 0.2539 2.2
0.0889 0.0824 -7.3 0.0220 0.0247 12 0.2195 0.2315 5.5 0.2089 0.2133 2.1
333.15 0.0000 0.0000 - 0.0165 0.0159 -3.6 0.0000 0.0000 - 0.4391 0.4388 -0.1
0.0041 0.0034 -17 0.0163 0.0161 -1.2 0.0272 0.0282 3.7 0.4113 0.4181 1.7
0.0082 0.0069 -16 0.0164 0.0164 0.0 0.0497 0.0517 4.0 0.3924 0.3999 1.9
0.0182 0.0157 -14 0.0168 0.0170 1.2 0.0914 0.0975 6.7 0.3453 0.3601 4.3
0.0302 0.0254 -16 0.0171 0.0180 5.3 0.1241 0.1327 6.9 0.3141 0.3245 3.3
0.0539 0.0479 -11 0.0194 0.0210 8.3 0.1691 0.1798 6.3 0.2553 0.2623 2.7
0.0588 0.0519 -12 0.0196 0.0215 9.7 0.1745 0.1852 6.1 0.2469 0.2519 2.0
0.0732 0.0673 -8 0.0226 0.0244 8.0 0.1908 0.1997 4.7 0.2174 0.2201 1.2
0.0928 0.0842 -9 0.0250 0.0276 10 0.1983 0.2042 3.0 0.1865 0.1806 -3.2

Figure 7. Liquid-liquid phase equilibrium of the ternary system Figure 9. Liquid-liquid phase equilibrium of the ternary system
formaldehyde + water + 1-butanol at 298 K: experimental results formaldehyde + water + 1-butanol at 333 K: experimental results
(0) and correlations (O). (0) and correlations (O).

methylene) hemiformals are determined from experi-

Figure 8. Liquid-liquid phase equilibrium of the ternary system
formaldehyde + water + 1-butanol at 313 K: experimental results
(0) and correlations (O).
formals. Therefore, predictions for the specification of
formaldehyde in aqueous solutions of butanol from
binary data alone (formaldehyde + water, formaldehyde
+ butanol, or water + butanol) are not reliable. This
problem can be solved when the chemical reaction
equilibrium constants for the formation of poly(oxy-
mental data for the specification in the binary system
formaldehyde + 1-butanol as well as in the ternary
system formaldehyde + water + 1-butanol. Further-
more, physical interactions between groups present
only in the ternary mixture are important. These
parameters can only be determined from experimental
data of the ternary system. Experimental results from
both NMR spectroscopic and liquid-liquid phase equi-
librium investigations were used to determine the model
parameters. The model reliably describes the phase
equilibrium and the specification of the formaldehyde
+ water + 1-butanol system at temperatures from 298
to 333 K.
Nomenclature
A, B ) parameters in equations for the chemical reaction
equilibrium constant as well as for the influence of
temperature on the UNIFAC interaction parameters
A, B, C ) parameters in the Antoine vapor-pressure
equation
1516 Ind. Eng. Chem. Res., Vol. 42, No. 7, 2003

ai,j ) UNIFAC parameter for interactions between groups (3) Hasse, H.; Maurer, G. Kinetics of the Poly(oxymethylene)
i and j Glycol Formation in Aqueous Formaldehyde Solutions. Ind. Eng.
cal ) calculated result Chem. Res. 1991, 30, 2195-2200.
exp ) experimental result (4) Hahnenstein, I.; Hasse, H.; Liu, Y.-Q.; Maurer, G. Thermo-
FA ) formaldehyde dynamic Properties of Formaldehyde Containing Mixtures for
HF1 ) hemiformal (reaction product of formaldehyde and Separation Process Design. AIChE Symp. Ser. 1994, 90, 141-157.
1-butanol) (5) Hahnenstein, I.; Hasse, H.; Kreiter, C. G.; Maurer, G. 1H-
HFn ) poly(oxymethylene) hemiformal with n formalde- and 13C-NMR-Spectroscopic Study of Chemical Equilibria in
hyde groups Solutions of Formaldehyde in Water, Deuterium Oxide, and
Methanol. Ind. Eng. Chem. Res. 1994, 33, 1022-1029.
KHF1 ) chemical reaction equilibrium constant for the
formation of HF1 (6) Hahnenstein, I.; Hasse, H.; Albert, M.; Kreiter, C. G.;
vap Maurer, G. NMR Spectroscopic and Densimetric Study of Reaction
KHF 1
) chemical reaction equilibrium constant for the Kinetics of Formaldehyde Polymer Formation in Water, Deuterium
formation of HF1 in the vapor phase Oxide, and Methanol. Ind. Eng. Chem. Res. 1995, 34, 440-450.
KHFn ) chemical reaction equilibrium constant for the
(7) Albert. M. Thermodynamische Eigenschaften formaldehyd-
formation of HFn haltiger Mischungen. Ph.D. Dissertation, University of Kaiser-
KMG1 ) chemical reaction equilibrium constant for the slautern, Kaiserslautern, Germany, 1998.
formation of MG1
vap (8) Albert, M.; Coto Garćia, B.; Kreiter, C. G.; Maurer, G.
KMG 1
) chemical reaction equilibrium constant for the Vapor-Liquid and Chemical Equilibria of Formaldehyde-Water
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groups Liquid and Liquid-Liquid Equilibrium in Aqueous and Methanolic
n ) number of formaldehyde segments in the oligomer Solutions of Methylal. J. Chem. Eng. Data 2001, 46, 897-903.
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ñtotal ) total stoichiometric number of moles Ch.; Kreiter, C. G.; Maurer, G.; Hasse, H. Quantitative NMR
pSi ) vapor pressure of pure component i Spectroscopy of Complex Liquid Mixtures: Methods and Results
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Temperatures up to 383 K. Ind. Eng. Chem. Res. 2003, 42 (2), 259-
1B ) 1-butanol 266.
p0 ) standard pressure (0.1 MPa)
(12) Balashov, A. L.; Danov, S. M.; Golovkin, A. Yu.; Krasnov,
q ) UNIFAC surface parameter
V. L.; Ponomarev, A. N.; Borisova, I. A. Equilibrium mixture of
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W ) water solutions. Russ. J. Appl. Chem. 1996, 69 (2), 190-192.
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