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Fluid Phase Equilibria 266 (2008) 21–30

Determination of liquid–gas partition coefficients of BuA

and MMA by headspace-gas chromatography utilizing
the phase ratio variation method
Zoi Kechagia a , Costas Kiparissides a,∗ , Ioannis G. Economou b
a Department of Chemical Engineering and Chemical Process Engineering Research, Aristotle University of Thessaloniki,
P.O. Box 472, Thessaloniki, Greece
b Molecular Thermodynamics and Modeling of Materials Laboratory, Institute of Physical Chemistry,

National Center for Scientific Research “Demokritos”, GR-15310 Aghia Paraskevi Attikis, Greece
Received 13 November 2007; received in revised form 15 January 2008; accepted 17 January 2008
Available online 26 January 2008

Abstract
The phase variation method is described and applied in order to determine liquid/gas partition coefficients of monomers in aqueous solutions
as well as the effect of the presence of one monomer to the partition coefficient of the other. The method is based on the relationship between
reciprocal peak area and the phase ratio in the vial containing the sample solution. It involves regression analysis of headspace gas chromatography
measurements of a number of sample vials with a variation of phase ratios. The method is applied in the case of the monomers butyl acrylate and
methyl methacrylate. Experimental data for the partition coefficient of the two acrylates are modeled with the Statistical-Associating-Fluid Theory
(SAFT).
© 2008 Elsevier B.V. All rights reserved.

Keywords: Gas chromatography; Partition coefficient determination; SAFT theory

1. Introduction and accurate way to establish partition coefficients for volatile

The partition coefficient is the ratio of the concentration of a
volatile compound in two phases and although it can be derived
from quantitative analysis of both phases, a variety of procedures
appear in the literature that can be utilized in order to calculate
the partition coefficients of different substances in liquid–gas
systems. Partition coefficients depend on the physicochemical
properties of both compound and phase that contains it and on
physical parameters such as temperature.
In equilibrium headspace chromatography, a liquid or solid
sample is thermostated in a closed vessel until the volatile com-
ponents reach equilibrium between the liquid sample and the gas
above it (which is called ‘headspace’). Subsequently, a fraction
of the headspace is introduced into the GC column for analysis.
The equilibrium is controlled by the partition coefficient thus,
equilibrium headspace analysis should provide a relatively easy
∗ Corresponding author. Tel.: +30 2310 996211; fax: +30 2310 996198.
E-mail address: cypress@vergina.eng.auth.gr (C. Kiparissides).
components in gas liquid systems [1–3]. Owing to the increasing
interest in such partition systems, there is a need to apply an auto-
matic technique in order to measure the partition coefficients.
Rohrschneider [4] first used an automated headspace instrument
to measure the partition coefficients of six reference compounds
with different polarities in 80 solvents, using a reference sys-
tem. This procedure, however, is not generally applicable, as it
depends on the availability of data for any desired temperature
and its accuracy depends on the reproducibility of the reference
system.
The advantages of headspace gas chromatography (HSGC)
are twofold [5–8]. As a clean homogeneous sample is intro-
duced into the gas chromatograph, the method permits the
determination of volatile compounds present in an essentially
non-volatile matrix, which could not be introduced directly into
the instrument. Furthermore, by the proper selection of the equi-
librium conditions, mainly the temperature, the concentration
of the volatile compounds can be enhanced in the headspace,
facilitating the determination of trace concentrations in the
sample [9–13]. Przyjazny et al. [14] presented a method for

0378-3812/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2008.01.015
22 Z. Kechagia et al. / Fluid Phase Equilibria 266 (2008) 21–30

the determination of organic compounds by headspace gas m∗L

chromatography after sorption on solid sorbents and liquid cL∗ = (2)
VL
desorption.
∗ m∗G
A different technique, called Vapor Phase Calibration, cG = (3)
involves the analysis of a sample of the headspace by GC in VG
the usual way and the determination of the volatile component where m∗L and m∗G are the amounts of the volatile component in
by calibration with an external vapor standard. Kolb et al. pre- the two phases at equilibrium and VL and VG are the volumes of
sented a brief review of the literature concerning the utilization liquid and mobile phases in the column.
of this technique [15]. Jones at al. [16] determined the partition The volume of the sample in the vial is VS is defined:
coefficient of ethyl acetate in water at 0 ◦ C from independent
analyses in the headspace vial and the amount in the gas phase. VS = VL + VG (4)
The gas phase was calibrated against an external liquid standard The phase ratio, r, of the vial containing the sample can be
injected by a microsyringe. Kieckbursch and King [17] also used expressed as
a microsyringe for analyzing the liquid phase. The combina-
tion of headspace injection by gas syringe and liquid injection VG VS − V L
r= = (5)
by microsyringe needs very careful calibration between both VL VL
sampling devices and is hard to automate. At equilibrium the volatile component is distributed between
McAuliffe [18] used a different technique in order to mea- the two phases (gas and sample phase). An asterisk is used to
sure the partition coefficient in two-phase systems. The multiple indicate equilibrium conditions.
headspace extraction procedure (MHE) [19–21] can be carried The partition coefficient using Eqs. (1)–(4) can be expressed
out automatically and involves numerous variations. Namieśnik as [27]
et al. [22] in a review paper presented methods for the isola-
tion and/or concentration of volatile organic compounds from cL∗ m∗L VG m∗L
K= ∗ = = r (6)
water samples for trace organic analysis by gas chromatography. cG m∗G VL m∗G
Śliwka et al. [23] presented the parameters (phase ratio and range
Combining equations, the following expression is derived, for
of partition coefficient values where the method can be applied)
the concentration of the analyte in the liquid (stationery) phase
that must be examined for the selection of the optimum head-
of the sample vial, at equilibrium, cL∗ , as a function of the concen-
space method. The standard addition method presented involves
tration of the analyte in the original sample in the vial, cL , the
a two-stage analysis at a constant sample temperature [24].
distribution coefficient and phase fractions:
Finally another possibility to determine the partition  
coefficient of a volatile in a gas–liquid system involves equili- cL 1
∗ = 1 + r (7)
brium headspace gas chromatography (EHS-GC) measurements cL K
without the use of an external vapor standard. The latest method
is based on the relationship between the partition coefficient and In the case that the concentrations are expressed as mass per
the sample fraction in the vial that represents the ratio of sample mass, as is the case of the measurements performed by this study,
volume to vial volume. This technique is called the phase varia- the equation is modified accordingly.
  
tion method and was used by Kolb and co-workers [25,26] in cL d d 1
order to determine liquid–gas partition coefficients of hexane = ∗+ r (8)
cL∗ d d∗ K
and chlorobenzene in various temperatures.
The present work utilizes the phase variation method, in order where d and d* are the densities of the initial sample and of the
not only to determine the liquid–gas partition coefficients of sample after equilibrium.
methyl methacrylate and butyl acrylate at various temperatures
to examine whether they follow an Arhenius type dependence 3. Experimental measurements
with temperature, but also to establish the effect of the pre-
sence of one monomer at different concentrations to the partition 3.1. Instrumentation
coefficient of the other.
All chromatographic measurements were performed using
an HP 6890 gas chromatographic system equipped with an FID
2. Theory of the phase variation method detector and a split/splitless capillary sample injector, fitted with
an HP 7694 headspace autosampler and interfaced to an HP
The partition coefficient is defined as the ratio of the equili- Chemstation data managing system. The volume of the head-
brium concentration in the liquid phase (cL∗ ) to its equilibrium space vials was 22.4 ml. The aqueous samples were thermostated
concentration in the mobile (gas) phase, at column temperature for 2 days in a Heraeous vacutherm in order to attain equili-
[26]: brium and were analyzed utilizing the full evaporation technique
(FET) [28,29]. A capillary HP-INNOWAX column with bonded
cL∗
K= (1) polyethylene glycol phase (df = 1 ␮m) was used. The headspace
∗
cG autosampler and gas chromatograph conditions, optimized for
 Z. Kechagia et al. / Fluid Phase Equilibria 266 (2008) 21–30 23

Table 1 internal standards have been tested in order to optimize the

HP 7694 headspace autosampler conditions for the FET technique accuracy of the FET/GC analysis (see Table 3). 2-Pentanone
Temperatures (Fluka) was selected as the internal standard to be used for all
Oven: 120 ◦ C measurements.
Sample valve: 140 ◦ C
Transfer line: 140 ◦ C 3.2.3. Analysis
Times Ten microliters of the aqueous monomer solutions and 10 ␮l
GC cycle: 30 min of the aqueous solution of 2-pentanone were placed into the
Sample equilibration: 10 min headspace vial and were analyzed using the FET.
Vial pressurization: 0.13 min
Loop fill: 0.02 min
3.2.4. Calibration
Loop equilibration: 0.05 min
Linear least-squares regression is commonly used for the
Sample inject: 0.08 min
estimation of the mathematical function relating the analytical
Shaking speed signal to the analyte concentration. For a good estimation of
Low
the linear calibration model it is necessary to obtain the calibra-
tion line from a series of (equally spaced) replicates of different
the specific systems under investigation, MMA/BuA, are shown standard solutions. Furthermore, three injections (instrumental
in Tables 1 and 2. The analytes used were of the purest available replicates) are typically required for each experimental replicate.
grade. Fig. 1 shows a schematic of three different calibration data
sets, which were reported in the literature to provide essentially
identical calibration lines and experimental errors. In order to
3.2. Sample preparation
minimize the high number of replicates (experimental and ins-
trumental) required for model estimation, a corner-weighted
3.2.1. Aqueous solutions of monomers
calibration data set can be implemented, using fewer experi-
Aqueous solutions of butyl acrylate, methyl methacrylate of
mental and instrumental replicates without any loss of analytical
300–500 ␮g ml−1 (300–500 ppm, wt/wt) and aqueous solutions
information [30].
containing both acrylates at various concentration ratios were
In the corner-weighted calibration adopted in this work, the
prepared. Increasing volumes (1, 2, 3 and 4 ml) of these solutions
concentration range used was 200–1000 ppm. Since the FET
were placed into headspace vials; thus each vial represented a
was utilized for gas chromatographic analysis, the two injections
different phase ratio.
were obtained by analyzing duplicate samples prepared in two
different GC vials using the same internal standard and final
3.2.2. Aqueous solutions of internal standard monomer solutions.
Aqueous solutions of 2-pentanone were prepared with
concentrations of 1000 ␮g ml−1 . For GC analysis using FET, 3.3. Standard deviation analysis
10 ␮l of monomer and IS solutions were introduced in the head-
space auto sampler for conditioning and analysis. Different The chemical calibration established by applying linear least-
squares regression shows different sources of error, as illustrated
Table 2 in Fig. 2. The overall error, s0 , consists of: (a) regression error,
HP 6890 gas chromatograph conditions for the FET technique and (b) residual error [31,32]. The residual error is formed by
Oven temperature program
(a) the lack-of-fit error, sL and (b) the pure error that consists
3 min at 50 ◦ C, ramp to 90 ◦ C with 10 ◦ C/min, hold for 2 min, ramp of (a) the procedural error, sP , resulting from dilution errors
to 120 ◦ C with 10 ◦ C/min, hold for 2 min, post-run at 220 ◦ C for 10 min in sample preparation and (b) the instrumental error, sI . The
Injection equations providing the errors are

Mode: splitless 
Temperature: 200 ◦ C  SS0
Overall error : s0 =     (9)
Pressure: 1.94 psi I Ji Kij
Purge flow: 30 ml/min i=1 j=1 k=1 K ij − 2
Purge time: 1 min 
Gas: helium 
 SSI
Instrumental error : sI =  
Column I Ji Kij

Capillary, HP-INNOWax Polyethylene Glycol i=1 j=1 k=1 K ij −1

Nominal length: 30 cm (10)
Nominal diameter: 530 ␮m
Nominal film thickness: 1 ␮m
Nominal initial pressure 3.74 psi Procedural error : sP
Mode: constant flow (5 ml/min) 

 SSP
Detector =    Ji (11)
I
FID, constant makeup flow (25 ml/min) i=1 (J i − 1) × j=1 (K /J
ij i )
Temperature: 250 ◦ C
24 Z. Kechagia et al. / Fluid Phase Equilibria 266 (2008) 21–30

Table 3
Monomers and internal standard tested
Monomer Internal standard tested

Retention time (min) Retention time (min) Tb,p (◦ C) Water solubility

MMA 5.01 Butanone 3.47 79.6 v

BuA 7.78 Cyclohexane 2.01 80.7 i
Cyclohexanone 10.82 155.6 s
Hexane 5.08 68.9 i
2-Propanol 3.79 82.4 ∞
2-Pentanone 4.62 102 s

Fig. 1. Schematic of three calibration data sets, where i is the concentration level, and j, k are the experimental and instrumental replicates, respectively.

Fig. 2. Schematic of the different sources of error in chemical calibration using linear least-squares regression.

The symbols are explained at the end of the paper and the
various terms are given elsewhere and are not repeated here
[31–33].
The analytical signals obtained at the different experimental
and instrumental replicates for BuA are presented in Table 4,
and the calibration curve obtained for BuA is depicted in Fig. 3
and for MMA in Fig. 4, respectively.

4. Statistical associating fluid theory (SAFT)

In this work, the statistical-associating-fluid theory (SAFT)

was used to model the liquid–gas partition coefficients of BuA
and MMA in water. SAFT is an equation of state widely used for
phase equilibrium calculations for hydrogen bonding and poly-
mer systems. It is rooted to statistical mechanics and accounts
explicitly for repulsive interactions, weak attractive interactions Fig. 3. Corner-weighted calibration curve of BuA using the full evaporation
(van der Waals forces) and hydrogen bonding between like and technique and 2-pentanone as internal standard.
 Z. Kechagia et al. / Fluid Phase Equilibria 266 (2008) 21–30 25

Table 4
Analytical signals obtained for the center-weighted calibration
Nominal concentration level i (ppm) Experimental replicate j Instrumental replicate k Signal (monomer/IS area)

200 1 1 0.1485
2 1 0.1501
3 1 0.1197
400 1 2 0.3904, 0.3635
2 2 0.3759, 0.3868
600 1 2 0.5910, 0.5953
800 1 2 0.8742, 0.8614
2 2 0.8849, 0.8707
1000 1 1 0.9387
2 1 0.9849
3 1 1.0615

unlike molecules. Mathematically, SAFT is expressed by the v00 is the spherical segment size, u0 /k is the dispersion energy
following equation for the residual Helmholtz free energy per parameter, εhb /k is the association energy and κ is the association
mole: volume. All five parameters are fitted to saturated liquid density
and vapor pressure data from low temperature up to close to the
ares (T, ρ) a(T, ρ) aideal (T, ρ) aref (T, ρ) adisp (T, ρ)
= − = + critical point. In this work, water is modeled as a four hydrogen
RT RT RT RT RT bonding site fluid whereas both BuA and MMA are modeled as
ahs (T, ρ) achain (T, ρ) aassoc (T, ρ) adisp (T, ρ)
= + + + two hydrogen bonding site fluids. In Table 5, the pure component
RT RT RT RT parameters are shown.
(12)
SAFT extension to mixtures is straightforward based on the
where T and ρ are the temperature and density of the system, res- van der Waals one fluid theory [34]. For the cross-association
pectively and the residual Helmholtz free energy is with respect interactions (hydrogen bonding between unlike species), the
to the Helmholtz free energy for the ideal gas at the same T and following combining rules are used:
ρ. Superscripts hs, chain, assoc, and disp refer to hard-sphere 
interactions, chain formation, association (hydrogen bonding), εAB εAB
hb εhb
BB κAA + κBB
hb
= κAB = (13)
and dispersion interactions, respectively. If the Helmholtz free k k k 2
energy of the fluid is known, all other thermodynamic proper-
where superscript AB denotes hydrogen bonding between a
ties, such as pressure, chemical potential, etc., can be calculated
molecule of species A and a molecule of species B. Further-
using standard thermodynamic equations. The expressions for
more, in the dispersion term for mixtures a binary interaction
the various terms in Eq. (12) are given elsewhere [33] and are
parameter, kij , is used that is fitted to binary phase equilibrium
not repeated here. SAFT is a five parameter EoS for pure com-
data:
ponents: m is the number of spherical segments per molecules,  u u 1/2
uij ii jj
= (1 − kij ) (14)
k k k

5. Results and discussion

Fig. 4. Corner-weighted calibration curve of MMA using the full evaporation
technique and 2-pentanone as internal standard.
The calibration curves obtained for BuA and MMA are depic-
ted in Figs. 3 and 4 respectively. Corner-weighted calibration
was used, as it is known to decrease experimental work without
loss of analytical information. The corresponding values of stan-
dard deviations and sums squares calculated for the different
sources of error are presented in Table 6. The overall error
is 5.3% and 4.7% for the BuA and MMA calibration curves,
respectively, which are acceptable percentages for this type of
measurements.
The partition coefficient measurements were carried out at
three different temperatures. At each temperature the solution
was analyzed from eight different vials, every two correspon-
ding to different phase ratios. A number of solution series were
used in order to verify the results. The sample phase fractions
as well as the volume of the vial used were determined accor-
26 Z. Kechagia et al. / Fluid Phase Equilibria 266 (2008) 21–30

Table 5
SAFT pure component parameters for the components examined here and percentage average absolute deviation (% AAD) between experimental data [40] and
SAFT correlation for the vapor pressure (Psat ) and saturated liquid density (ρliq ).

Component m v00 (cm3 /mol) u0 /k (K) εHB /k (K) κ T (K) Psat (% AAD) ρliq (% AAD)

Water 2.853 3.304 167.10 1634.7 0.337 278–641 0.88 1.66

MMA 4.590 11.615 214.03 510.8 1.399 263–558 3.14 2.28
BuA 5.377 12.496 178.74 1566.2 1.560 278–592 2.60 2.70

ding to investigations by Kolb and Ettre [26], after ensuring
that the values selected in the present work both satisfy the
easily attainment of equilibrium and a representative sample
aliquot.
A very large sample volume increases the time needed for
equilibrium, while it has to be enough in order to ensure a repre-
sentative sample aliquot inserted in the column. The sample
volume in the vial was selected to range from 1 to 4 ml in order
to obtain a significant concentration of the analyte in the head-
space. It was found that larger sample volumes greatly increased
the time needed to reach equilibrium, without a significant effect
on the quantitative analysis.
Specifically the determination of the partition coefficients
depends on peak area differences, resulting from changing the
phase ratio values. For a partition coefficient of K = 10 it was
calculated, using the phase ratio variation method’s equations,
that filling the vial with 4 ml of the sample the concentration
of the analyte in the headspace vial will be 2.15 times of that
when the sample occupies only 1 ml of the vial volume. This
difference permits the calculation of the partition coefficients
from the peak areas observed at the gas chromatograph. Fur-
thermore it was calculated that by changing the sample volume
by 0.1 ml a variation of the concentration of the analyte in the
headspace vial of 2.6% was observed thus providing a good
sample to sample reproducibility, since balances and pipettes of
high accuracy were used (±0.1 mg and ±0.5 ␮l, respectively).
The size of the sample vial was selected to be 20 ml in order to
have enough headspace gas available for transfer into the column
as well as to obtain sample homogeneity and therefore analyze
a representative aliquot.
The measurements were carried out by the FET, using 2-
pentanone as internal standard, in order to minimize the effects
of the quantity variations of the sample introduced in the gas
Table 6
Values of standard deviations and sums squares for BuA and MMA calculated
for the different sources of error
Standard deviations and sum squares BuA
Instrumental error
SSI 0.00061
sI 0.00687
Procedural error
SSP 0.00388
sP 0.00645
Overall error
SS0 0.03425
s0 0.05341
chromatograph, due to changes in the external parameters, such
as the pressure in the vial.
The FET allows us to reduce the sample size and increase the
temperature, thus reducing the effect of the sample matrix. It thus
ensures that salts and mineral acids will never enter and conta-
minate the analytical instrumentation. Furthermore, the sample
matrix does not affect the calibration of the analytical procedure,
creating the potential for universal standardization. Even though
in the specific system examined there is no matrix effect, the fact
that the response of each component remains uniform regardless
of the matrix present, permits that the results be used in order to
examine the stripping process of BuA and MMA polymers and
copolymers. This work is underway at the Aristotle University
of Thessaloniki group and will be presented soon.
The use of liquid concentration measurements allows us also
to determine components of low volatility, that will be present
in other systems examined. It is generally more convenient to
dispense microliters of sample into a headspace vial at room
temperature than to provide fast injection through a small ope-
ning of a hot injection port. Furthermore when measurements
were carried out using the gas phase the results were of lower
accuracy (especially in the case that no internal standard was
used), even though care was taken that the carrier gas inlet pres-
sure was higher than the pressure reached in the headspace vial
and the filling sample loop time was carefully selected. On the
other hand, when the concentration was measured in the liquid
phase more reproducible results were observed.
5.1. Temperature dependence of the partition coefficient
It is known that the relationship between log K and the inverse
of temperature, 1/T may be considered linear, even though a
slight curvature may be occasionally observed [5,35–37]. Typi-
cal of this slight curvature are the examples of the plots of
chlorobenzene, toluene and n-xylene in water [1,25]. Thus the
existence of such relationship between log K and 1/T is an indica-
tion of the correctness of the measurements [38]. Determination
of the liquid–gas partition coefficient of an analyte at various
MMA
temperatures will permit extrapolation within a reasonable range
to other temperatures. This is especially important for the deter-
0.00506 mination of partition coefficients values at temperatures higher
0.01837
than the maximum temperature of the thermostat of the head-
space auto sampler (150 ◦ C).
0.00119
The results of the present study are presented in the overall
0.00356
tables (Tables 7 and 8). A typical diagram from which the results
are derived is depicted in Fig. 5. The figure represents the ratio
0.03033
0.04655
of the concentration of the initial vial to the equilibrium concen-
tration in the liquid phase versus the volume ratio of the vial
Table 7
Liquid/gas partition coefficients of BuA at various temperatures and various mass fractions in the initial solution
Temperature (K) Concentration ratio of Klg of BuA Klg of BuA Intercept b0 Slope b1 Standard Standard error 95% confidence interval 95% confidence Correlation
BuA:MMA in the initial (expt.) (SAFT) error, sy of estimate, sy,x of b0 interval of b1 factor R2
solution
333.15 0:100 – – – – – – – – –
20:80 6.52 9.09 0.6445 0.0988 0.622 0.080 [0.335, 0.644] [0.072, 0.125] 0.9833
30:70 7.06 9.09 0.6899 0.0977 0.610 0.071 [0.388, 0.992] [0.072, 0.124] 0.9867
50:50 7.33 9.10 0.9953 0.1357 0.969 0.083 [0.691, 1.137] [0.109, 0.162] 0.9927
80:20 9.23 9.10 1.0541 0.1141 0.732 0.081 [0.786, 1.323] [0.093, 0.136] 0.9880
100:0 9.49 9.10 1.0414 0.1097 0.748 0.051 [0.712, 1.371] [0.084, 0.136] 0.9953

343.15 0:100 – – – – – – – – –
20:80 5.12 8.53 0.7635 0.1489 0.996 0.101 [0.371, 1.156] [0.132, 0.165] 0.9897
30:70 5.76 8.53 1.1446 0.1986 1.096 0.124 [0.496, 1.793] [0.171, 0.227] 0.9872
50:50 5.90 8.54 1.0014 0.1696 1.102 0.088 [0.626, 1.376] [0.140, 0.199] 0.9935
80:20 8.34 8.54 1.2850 0.1539 0.894 0.100 [0.841, 1.729] [0.114, 0.193] 0.9874

Z. Kechagia et al. / Fluid Phase Equilibria 266 (2008) 21–30

100:0 8.98 8.54 1.3562 0.1509 0.971 0.124 [0.962, 1.752] [0.118, 0.184] 0.9836
353.15 0:100 – – – – – – – – –
20:80 4.78 8.08 0.6248 0.1306 0.817 0.088 [0.254, 0.996] [0.115, 0.146] 0.9882
30:70 5.02 8.09 0.8309 0.1654 1.116 0.101 [0.484, 1.178] [0.138, 0.193] 0.9918
50:50 5.36 8.09 1.3450 0.2515 1.222 0.196 [0.832, 1.858] [0.232, 0.270] 0.9851
80:20 7.24 8.09 1.3888 0.1918 1.251 0.149 [0.903, 1.875] [0.154, 0.230] 0.9858
100:0 7.59 8.10 1.4529 0.1914 1.363 0.150 [0.860, 2.046] [0.168, 0.215] 0.9878

Table 8
Liquid/gas partition coefficients of MMA at various temperatures and various mass fractions in the initial solution
Temperature (K) Concentration ratio of Klg of MMA Klg of MMA Intercept b0 Slope b1 Standard Standard error of 95% confidence interval 95% confidence Correlation
BuA:MMA in the initial (expt.) (SAFT) error, sy estimate, sy,x of b0 interval of b1 factor R2
solution
333.15 0:100 13.10 13.78 0.7954 0.0607 0.435 0.030 [0.547, 1.044] [0.042, 0.080] 0.9952
20:80 11.95 13.79 0.9369 0.0784 0.493 0.055 [0.692, 1.182] [0.057, 0.099] 0.9876
30:70 11.04 13.79 0.8720 0.0790 0.494 0.037 [0.628, 1.116] [0.058, 0.100] 0.9943
50:50 9.51 13.79 0.7273 0.0765 0.530 0.040 [0.521, 0.933] [0.063, 0.091] 0.9944
80:20 8.30 13.80 0.8810 0.1061 0.681 0.068 [0.631, 1.131] [0.086, 0.126] 0.9899
100:0 – – – – – – – – –
343.15 0:100 11.97 12.48 1.6612 0.1387 1.026 0.152 [1.188, 2.135] [0.102, 0.176] 0.9781
20:80 11.08 12.48 1.4133 0.1275 0.851 0.092 [1.085, 1.755] [0.113, 0.141] 0.9881
30:70 9.34 12.48 1.3354 0.1429 0.789 0.062 [0.869, 1.802] [0.123, 0.163] 0.9939
50:50 7.82 12.49 1.1026 0.1412 0.918 0.117 [0.793, 1.417] [0.117, 0.166] 0.9850
80:20 7.55 12.49 1.2250 0.1621 0.944 0.098 [0.728, 1.721] [0.119, 0.205] 0.9891
100:0 – – – – – – – – –
353.15 0:100 10.86 11.42 1.1465 0.1056 0.613 0.079 [0.817, 1.476] [0.092, 0.119] 0.9834
20:80 10.29 11.42 1.3084 0.1272 0.796 0.130 [0.946, 1.669] [0.112, 0.142] 0.9696
30:70 8.38 11.42 1.2139 0.1449 0.978 0.092 [0.910, 1.518] [0.121, 0.169] 0.9910
50:50 6.65 11.43 1.2433 0.1869 1.157 0.093 [0.877, 1.609] [0.173, 0.200] 0.9935
80:20 6.30 11.43 1.3244 0.2103 1.368 0.131 [0.793, 1.856] [0.169, 0.252] 0.9907
100:0 – – – – – – – – –

27
28 Z. Kechagia et al. / Fluid Phase Equilibria 266 (2008) 21–30

Fig. 5. Concentration ratios of BuA in the liquid phase at the initial solution and
at equilibrium vs. volume ratio of the vial. The concentration ratio of BuA/MMA Fig. 7. Liquid/gas partition coefficients of MMA vs. mass fractions of MMA
in the initial solution is equal to 30/70. (mass of MMA/mass of BuA + MMA) in the initial solution for various tempe-
ratures.

(volume of gas phase/volume of liquid phase). As can be obser-

ved there exists a linear relationship between these parameters
that has the form
y = b0 + b1 x (15)
Statistical analysis has been carried out for all the set of results
received. The confidence interval, t s, at a 95% probability level
is presented in order to characterize better the uncertainty in the
experimental data [39]. The upper and lower entries represent
the best and worst cases, respectively. The coefficients of Eq.
(24) (b0 and b1 ) are well within the limits set by the analy-
sis carried out and the statistical analysis results are satisfying.
Specifically in the overall table the standard error, standard error
of estimate of y from x and confidence intervals of b0 and b1 at
a 95% probability level for all measurements are presented.
As it can be seen in Figs. 6–9 the presence of the one mono-
mer has an important effect at the partition coefficient of the Fig. 8. Semi log diagram presenting liquid/gas partition coefficients of BuA vs.
other. Additionally, the partition coefficients of the butyl acry- reciprocal of temperature for various mass fractions of BuA (mass of BuA/mass
of BuA + MMA) in the initial solution.
late and methyl methacrylate have Arhenius-type dependence
with temperature (Figs. 8 and 9). Therefore, the determination of

Fig. 9. Semi log diagram presenting liquid/gas partition coefficients of MMA

Fig. 6. Liquid/gas partition coefficients of BuA vs. mass fractions of BuA (mass vs. reciprocal of temperature for various mass fractions of MMA (mass of
of BuA/mass of BuA + MMA) in the initial solution for various temperatures. MMA/mass of BuA + MMA) in the initial solution.
 Z. Kechagia et al. / Fluid Phase Equilibria 266 (2008) 21–30 29

the monomer partition coefficients at various temperatures and ∗

cG concentration of the analyte in the gas phase of the
concentration ratios permits the extrapolation in a wide range of sample vial, that is in equilibrium with the sample
temperatures and concentration ratios. cL concentration of the analyte in the original sample in
As mentioned above the experimental data can be described the vial
using linear least-square fit. The intercept of this fit according ∗
cL concentration of the analyte in the liquid (stationery)
to Eq. (8) can be used to determine the density ratios of the phase of the sample vial, at equilibrium
analyte in the initial sample and in the sample after equilibrium. GC gas chromatography
Therefore, the phase variation method can be used in order to HS headspace
determine thermodynamic parameters. K partition coefficient of the analyte
Kij instrumental replicate at concentration level i and expe-
5.2. SAFT modeling rimental replicate j
MHE multiple headspace extraction
The binary interaction parameter, kij , for the mixtures r phase ratio in the vial
water–BuA and water–MMA was fitted to the binary data mea- sI regression standard deviation of instrumental error
sured here (Table 7). It is kij = 0.043 (water–BuA) and kij = −0.01 SSI sum of squares of the instrumental error
(water–MMA). Using these parameters, SAFT correlates the sP regression standard deviation of procedural error
binary data of Tables 7 and 8 (corresponding to relative concen- SSP sum of squares of the procedural error
trations of 0:100 and 100:0) reasonably well. These parameters sy standard error
were subsequently used for ternary mixture calculations. In this sy,x standard error of estimate of y from x
case we have set kij = 0.0 (MMA–BuA) since no experimental s0 regression standard deviation of overall error
data exist for the binary MMA–BuA mixture and, furthermore, SS0 sum of squares of the overall error
the two components are chemically similar. As a result, calcula- VL volume of the liquid phase in the vial
tions for the ternary system shown in Tables 7 and 8 are purely VG volume of the gas phase in the vial
predictive (all parameters were evaluated from the correspon- VS total volume of the sample in the vial
ding binary mixtures).
SAFT predicts that the addition of a second acrylate in very Acknowledgement
small quantities in the binary water–BuA and water–MMA mix-
tures has practically no effect to the vapor–liquid equilibrium We gratefully acknowledge the EC for supporting this
of the mixture. In other words, the model predicts that inter- research under the BRITE/EURAM Project BE97-4286.
molecular interactions between MMA and BuA are minimal
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