Chemosphere 90 (2013) 2035–2040

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Solubilities of selected organic electronic materials in pressurized hot water

and estimations of aqueous solubilities at 298.15 K
Pavel Karásek, Barbora Hohnová, Josef Planeta, Lenka Št’avíková, Michal Roth ⇑
Institute of Analytical Chemistry of the ASCR, v. v. i., Veveří 97, 60200 Brno, Czech Republic

h i g h l i g h t s

" Aqueous solubilities of hole transport materials were measured at high temperature.
" Room-temperature solubility estimates were extrapolated from high temperature data.
" Room-temperature aqueous solubilities appear to be extremely low.

a r t i c l e i n f o a b s t r a c t

Article history: Increasing production and disposal of organic light-emitting diode (OLED) displays for smartphones and
Received 11 July 2012 tablets may have impact on the environment depending on the aqueous solubility of the pertinent chem-
Received in revised form 4 October 2012 icals. Here, aqueous solubilities are presented for several compounds, mostly aromatic amines, used as
Accepted 17 October 2012
hole transport materials in the OLED displays. Solute selection includes 1,4-bis(diphenylamino)benzene,
Available online 21 November 2012
tetra-N-phenylbenzidine, 4,40 -bis(N-carbazolyl)-1,10 -biphenyl, 1,3,5-tris(diphenylamino)benzene, and
9,10-bis(phenylethynyl)anthracene. The solubilities are those in pressurized hot water (PHW), i.e., mea-
Keywords:
sured at elevated temperature (up to 260 °C) and pressure. The semi-quantitative estimates of room-tem-
Aqueous solubility
OLED display
perature solubilities of the solutes have been obtained from extrapolations of the solubilities in PHW. For
Hole transport material the compounds studied, the estimated aqueous solubilities at room temperature do not exceed
Aromatic amine 2  1011 g of the solute per 1 kg of water. Aqueous solubilities of triphenylamine have also been mea-
Pressurized hot water sured and used to upgrade a recent group-contribution model of aqueous solubilities of organic nonelec-
trolytes with the parameters for the nitrogen atom in aromatic amines.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction are reported for several of these materials including 1,4-bis

Steady growth in production of communication devices includ-
ing smartphones and tablets has been accompanied by rising
demand for organic light-emitting diode (OLED) displays. Naturally,
the growing production of the OLED displays leads to increasing
rate of their disposal. The chemicals used in the OLED displays
may have impact on the environment depending on their respec-
tive aqueous solubilities. Therefore, aqueous solubility data of the
individual compounds involved are of increasing interest and
significance.
The development of OLED displays has involved a large number
of diverse compounds (Shinar and Savvateev, 2004; Shirota, 2006).
An important class of chemicals employed in OLED production are
aromatic amines used as hole transport materials (Strohriegl and
Grazulevicius, 2002). In the present work, aqueous solubilities
⇑ Corresponding author. Tel.: +420 532290171; fax: +420 541212113.
E-mail address: roth@iach.cz (M. Roth).
(diphenylamino)benzene, tetra-N-phenylbenzidine, 4,40 -bis(N-
carbazolyl)-1,10 -biphenyl, and 1,3,5-tris(diphenylamino)benzene.
In addition, aqueous solubilities of the parent compound, triphen-
ylamine, are also reported here as well as the solubilities of 9,
10-bis(phenylethynyl)anthracene used as a charge transport and
photosensitizing material (Gill, 1983). Structures of these solutes
are shown in Fig. 1.
In the literature, there are no quantitative data on the aqueous
solubilities of either the hole transport materials mentioned above
or 9,10-bis(phenylethynyl)anthracene. All these compounds are
organic solids with high melting points, and a suitable technique
to measure their aqueous solubilities has been the ‘‘generator col-
umn’’ method based on slow passage of the solvent through a bed
packed with the solid solute to generate saturated aqueous solution
(May et al., 1978). This procedure has now been a well-established
method to measure the solubilities of solids in liquid solvents
(Fonseca et al., 2011). At or near the room temperature
(298.15 K), the aqueous solubilities of the present solutes are gen-
erally small and prohibitively difficult to measure directly. To

0045-6535/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.chemosphere.2012.10.085
2036 P. Karásek et al. / Chemosphere 90 (2013) 2035–2040
N N
1,4-bis(diphenylamino)benzene
N N
4,4'-bis(N-carbazolyl)-1,1'-biphenyl
triphenylamine
Fig. 1. Solute structures.
obtain readily measurable solubilities, therefore, the operating
temperature of the measurements had to be raised, and the exper-
imental solubility data reported below are those in pressurized hot
water (PHW). The generator column method has frequently been
used to measure the solubilities of organic nonelectrolyte solids
in PHW (Miller and Hawthorne, 1998; Miller et al., 1998; Anders-
son et al., 2005; Srinivas et al., 2010; Zhang et al., 2010), and we
have previously applied an optimized version of this method in
combination with gas chromatography (GC) to determine the
aqueous solubilities of several classes of aromatic and other com-
pounds (Karásek et al., 2006a, 2007, 2008). In the present work, be-
cause of rather low volatility of the compounds studied,
quantification has been carried out using high performance liquid
chromatography (HPLC) rather than GC.
2. Experimental section
2.1. Materials
Triphenylamine (98%) and 9,10-bis(phenylethynyl)anthracene
(99%) were purchased from Alfa Aesar (Karlsruhe, Germany). 1,4-
Bis(diphenylamino)benzene (97%), tetra-N-phenylbenzidine
(97%), 4,40 -bis(N-carbazolyl)-1,10 -biphenyl (97%), 1,3,5-tris(diphen-
ylamino)benzene (97%), and tris(4-carbazoyl-9-ylphenyl)amine
(97%) were obtained from Sigma–Aldrich (Prague, Czech Republic).
Prior to use, the solutes were recrystallized from toluene. Acetoni-
trile (HPLC grade, 99.9%) was purchased from Riedel deHaën
N N
tetra-N-phenylbenzidine
N N
1,3,5-tris(diphenylamino)benzene
9,10-bis(phenylethynyl)anthracene
(Prague, Czech Republic), toluene (HPLC grade, 99.8%) was ob-
tained from Penta (Chrudim, Czech Republic), and methanol (HPLC
grade, 99.9%) was purchased from Lach-Ner (Neratovice, Czech
Republic). Water was purified with a reverse osmosis system Ultra
Clear UV (SG Wasseraufbereitung und Regenerierstation GmbH,
Barsbüttel, Germany). Glass beads (diameter 0.57–0.70 mm) mixed
with the solid solute before packing the extraction cell of the appa-
ratus were purchased from GlassDekorService (Valašské Meziříčí,
Czech Republic).
2.2. Apparatus to generate aqueous solutions
The in-house constructed apparatus to generate hot aqueous
solutions has been described (Karásek et al., 2006a) and employed
(Karásek et al., 2007, 2008) earlier and it has been used in the pres-
ent study without any modification except for routine mainte-
nance. The essential features of the apparatus include a vertically
mounted, 1.4-mL volume, stainless-steel extraction cell housed in
a thermostating cover, and the use of proper length (approximately
1.3 m) of fused-silica capillary (75 lm i.d.) as the flow restriction
device at the outlet of the extraction cell.
2.3. Procedure to generate aqueous solutions
Following the method employed previously, the crystalline sol-
ute was thoroughly mixed with glass beads (diameter 0.57–
0.70 mm) and charged into the extraction cell. After mounting
the cell in the apparatus, the system was flushed with nitrogen
 P. Karásek et al. / Chemosphere 90 (2013) 2035–2040
to remove air and then slowly filled with water, and subsequently
the desired operating temperature and pressure were allowed to
establish. The water pump was operated in constant flow mode
so that the operating pressure resulted from the interplay between
the flow rate set by the pump and the hydraulic resistance of the
flow restrictor at the system outlet. The length of the 75 lm i.d.
fused silica tubing employed as the restrictor was always selected
so that the mass flow rate of water through the system was less
than 0.015 g s1 to ensure proper equilibration between the solid
solute and the aqueous phase. This value was based on preliminary
test of the flow-rate dependence of the resultant solubility that
was carried out with 1,4-bis(diphenylamino)benzene at 433.2 K.
Because of rather low aqueous solubilities of the present solutes
and also because of difficult calibration at elevated temperature and
pressure we did not attempt a direct analysis of the hot aqueous
solutions, opting for an indirect procedure instead. Although time
consuming, the indirect procedure makes it possible to accumulate
sufficient amount of the aqueous solution to allow a reliable quan-
tification of the solute Therefore, after the selected operating tem-
perature and pressure have stabilized, five samples of the
aqueous effluent were collected into pre-weighed separate vials
each of which contained a known amount of cold water to prevent
evaporation of the hot effluent from the outlet restrictor. After cool-
ing down to room temperature, each vial was weighed so that the
mass of aqueous effluent could be obtained from the difference.
2.4. Processing of aqueous solutions
Depending on the extraction temperature and the expected sol-
ubility of the solute, a known amount (1–30 mL) of toluene was
added to each vial, and the solute was allowed to transfer to tolu-
ene during 3 weeks with agitation of the vials in regular time inter-
vals. Afterwards, a 1000-lL portion of the toluene layer was
withdrawn and centrifuged for 90 s at 15 000 rpm to separate
any residues of the aqueous layer. Subsequently, a 500-lL portion
of the toluene layer was allowed to evaporate, and the solute was
transferred to acetonitrile containing a pre-estimated amount of
the internal standard. The acetonitrile solution was then injected
for analysis by HPLC.
2.5. HPLC apparatus and procedure
The apparatus was an Agilent 1200 Series HPLC (Agilent, Wald-
bronn, Germany) equipped with a diode array UV–VIS detector,
quaternary pump with solvent degasser, and a Kinetex column
(length 100 mm, i.d. 3 mm) packed with 2.6 lm core–shell parti-
cles of pentafluorophenyl-bonded silica (Phenomenex, Torrance
(CA), USA). The injection volume was 10 lL. The mobile phase
was composed of acetonitrile (solvent A) and water containing
5% (v/v) of methanol (solvent B). The same gradient program was
employed for all solutes: the start with the 50:50 (v/v) A:B mixture
was followed by a 5-min. linear gradient to 90:10 (v/v) A:B mix-
ture, the 90:10 composition was kept for 6 min. and followed by
a 2-min. period at the starting 50:50 composition prior to the next
injection.
Tris(4-carbazoyl-9-ylphenyl)amine was used as the internal
standard in the determination of all solutes except triphenylamine
where 1,4-bis(diphenylamino)benzene served as the internal
standard.
The operating wavelengths for UV detection were 295 nm for
triphenylamine and 1,4-bis(diphenylamino)benzene, 350 nm for
tetra-N-phenylbenzidine, 235 nm for 4,40 -bis(N-carbazolyl)-1,
10 -biphenyl, 300 nm for 1,3,5-tris(diphenylamino)benzene and
270 nm for 9,10-bis(phenylethynyl)anthracene. The wavelength
used for the tris(4-carbazoyl-9-ylphenyl)amine internal standard
was 235 nm.
2037
3. Results and discussion
3.1. Solubilities in PHW
To our knowledge, no data have yet been available on the aque-
ous solubilities of the solutes studied here.
Numerical results of the solubility measurements are compiled
in the electronic Supplementary Information file. As different ways
to express concentrations have been preferred in different disci-
plines, the results are presented in several forms – equilibrium
mole fraction of the solute, equilibrium mass fraction of the solute,
solute molality, and equilibrium mass of the solute per 1 kg of
water. Fig. 2 shows graphical presentation of the experimental re-
sults with previous data for anthracene (Karásek et al., 2006a)
shown for reference. The temperature dependence of the individ-
ual solute data sets has been described with the least-squares fits
via the modified Apelblat equation (Apelblat and Manzurola,
1999),
ln x ¼ a þ bðT 0 =TÞ þ c lnðT=T 0 Þ ð1Þ
where x is the mole fraction solubility of the solute, T0 = 298.15 K
and the values of the coefficients a, b and c together with their stan-
dard errors as obtained by multilinear regression are given in Table 1.
Because of its three adjustable parameters, Eq. (1) is relatively flex-
ible in fitting the experimental data on solubilities of solids in liquids
and has frequently been used for the purpose (Wang and Wang,
2004; Karásek et al., 2006a; Razmara et al., 2010; Srinivas et al.,
2010; Zhang et al., 2010). Note that Eq. (1) describes the temperature
course of natural logarithm of the solute solubility whereas Fig. 2
shows decadic logarithms of the solubility. Overall, at a particular
temperature, the solute solubility decreases with rising molar mass
of the solute (see the Supplementary Information). However, in the
heaviest solutes of this study, 1,3,5-tris(diphenylamino)benzene,
tetra-N-phenylbenzidine and 4,40 -bis(N-carbazolyl)-1,10 -biphenyl,
the effect of molar mass tends to become blurred because of differ-
ent rates of the change in solubility with temperature. The mean val-
ues of the relative change in solubility with temperature, (@ln x/@T)r,
across the measurement temperature ranges for the individual sol-
utes are 0.0744 K1, 0.115 K1, 0.126 K1, 0.0971 K1, 0.142 K1
and 0.113 K1, for triphenylamine, 1,4-bis(diphenylamino)benzene,
tetra-N-phenylbenzidine, 4,40 -bis(N-carbazolyl)-1,10 -biphenyl, 1,3,
Fig. 2. Temperature dependence of solute solubilities (decadic logarithms of
equilibrium mole fractions). (s) anthracene (Karásek et al., 2006a); (d) triphen-
ylamine; (h) 1,4-bis(diphenylamino)benzene; (+) tetra-N-phenylbenzidine; ()
4,40 -bis(N-carbazolyl)-1,10 -biphenyl; () 1,3,5-tris(diphenylamino)benzene; (r)
9,10-bis(phenylethynyl)anthracene. Data of anthracene are shown for reference.
The lines serve just to guide the eye.
2038 P. Karásek et al. / Chemosphere 90 (2013) 2035–2040

Table 1
Least-squares estimates of the coefficients a, b, and c of Eq. (1) and the standard errors (SE) of the estimates, with Tmin and Tmax indicating the minimum and the maximum
temperatures of the solute solubility measurements, respectively.

Solute Triphenylamine 1,4-bis(diphenylamino) Tetra-N- 4,40 -bis(N-carbazolyl)- 1,3,5-tris(diphenylamino) 9,10-bis(phenylethynyl)

benzene phenylbenzidine 1,10 -biphenyl benzene anthracene
Tmax (K) 313.2 403.2 433.2 433.2 453.2 433.2
Tmin (K) 393.2 463.2 493.2 533.2 513.2 513.2
a 40.229 351.15 199.72 96.965 186.59 95.839
SE of a 10.778 100.41 74.24 24.98 21.53 60.10
b 19.067 331.18 166.53 61.376 259.53 58.076
SE of b 10.881 106.04 79.94 27.19 23.49 65.04
c 42.395 278.41 165.67 84.880 91.754 90.204
SE of c 9.259 73.22 51.62 16.90 14.53 41.22

Table 2
Least-squares estimates of the coefficients e and f of Eq. (2) and the standard errors (SE) of the estimates.

Solute Triphenylamine 1,4 bis(diphenylamino) Tetra-N 4,40 -bis(N carbazolyl)- 1,3,5 tris(diphenylamino) 9,10 bis(phenylethynyl)
benzene phenylbenzidine 1,10 -biphenyl benzene anthracene
e 43.259 68.957 77.792 65.059 86.959 71.206
SE of e 0.3080 2.070 1.054 0.4818 3.019 0.8309
f 0.074411 0.11531 0.12585 0.097113 0.14252 0.11326
SE of f 0.0008699 0.004774 0.002258 0.0009947 0.006242 0.001729

Table 3
Estimates of solute solubilities at 298.15 K.

Solute Solubility
Mole fraction, x Mass fraction, w Molality, m (mol kg1) Mass of solute (g) per 1 kg of water
10 8
Triphenylamine 7  10 1  10 4  108 1  105
1,4-Bis(diphenylamino)benzene 1  1015 2  1014 5  1014 2  1011
Tetra-N-phenylbenzidine 3  1018 9  1017 2  1016 9  1014
4,40 -Bis(N-carbazolyl)-1,10 -biphenyl 2  1016 6  1015 1  1014 6  1012
1,3,5-Tris(diphenylamino)benzene 5  1020 2  1018 3  1018 2  1015
9,10-Bis(phenylethynyl)anthracene 6  1017 1  1015 3  1015 1  1012

5-tris(diphenylamino)benzene and 9,10-bis(phenylethynyl)anthra-
cene, respectively. The temperature slope of solubility in 4,40 -
bis(N-carbazolyl)-1,10 -biphenyl is considerably lower than in the
other heavy solutes, possibly because of different electronic struc-
ture resulting from the presence of carbazolyl-type nitrogen atoms
and absence of amine-type nitrogens (see Fig. 1).
3.2. Estimation of solute aqueous solubilities at 298.15 K
In the present study, the solute solubilities have been measured
at elevated temperatures. As there are no data on the solute solu-
bilities at 298.15 K, it might be useful to provide gross estimates by
extrapolating the present high-temperature data although, be-
cause of the large temperature interval to be spanned, such an
extrapolation is rather daring and the estimates certainly suffer
from very large uncertainty. Therefore, the estimated values
should rather be understood as qualified estimations of the upper
limit of the aqueous solubility of the particular solute at 298.15 K.
Although Eq. (1) has been very useful for interpolating the experi-
mental data, the standard errors in the coefficients determined by
multilinear regression (see Table 1) are rather high. Consequently,
the use of Eq. (1) with the parameters from Table 1 to extrapolate
the experimental data over large temperature intervals would not
be reliable. To obtain more robust estimates of low-temperature
solubilities, therefore, the extrapolations have not been based on
Eq. (1) but on simple linear fits of the experimental data with Eq.
(2),
ln x ¼ e þ fT
The parameters e and f are listed in Table 2 and the estimated
solubilities at 298.15 K are compiled in Table 3. The effect of pres-
sure in the estimated solubilities at 298.15 K has been neglected as
it is much smaller than the uncertainty of extrapolation over the
large interval between 298.15 K and the lower limit of the temper-
ature range of the experimental data. Overall, the estimated aque-
ous solubilities of the hole transport materials at 298.15 K are
extremely small so that, most probably, they do not constitute
any immediate environmental concern.
3.3. Triphenylamine activity coefficient estimation
The solubility of a solid solute in a liquid solvent can be used to
estimate the solute activity coefficient from Eq. (3) (Prausnitz et al.,
1999; Karásek et al., 2006b),
   
DHfus Tt DC P T t Tt Vs  Vl
ln csat ¼ 1 þ  1  ln þ P  ln x
RT t T R T T RT
ð3Þ
where csat is the Raoult law activity coefficient of the solute in the
saturated solution, R is the molar gas constant, T is the solution tem-
perature, Tt is the triple-point temperature of the solute, DHfus is the
molar enthalpy of fusion of the solute at Tt, DCP is the difference be-
tween the molar isobaric heat capacities of the pure subcooled li-
quid solute and the pure solid solute, Vs and Vl are the molar
volumes of the pure solid solute and the pure subcooled liquid
solute, respectively, and P is the pressure. Eq. (3) applies if there
ð2Þ
are no solid–solid phase transitions in the pure solute within the
 P. Karásek et al. / Chemosphere 90 (2013) 2035–2040 2039

where, again, T0 = 298.15 K. The model has been developed from an

essentially isobaric set of csat values, and therefore, the effect of
pressure has not been treated explicitly. Employing the previous
group contributions for aromatic carbon atoms (Karásek et al.,
2010), the csat data for triphenylamine obtained in the present work
have been used to derive the Ci parameters for the nitrogen atom in
tertiary aromatic amines; the least-squares regression yields

CNðtaromÞ ¼ 54:738  57:365ðT 0 =TÞ  42:585 lnðT=T 0 Þ ð6Þ

where the temperature range is that of the source experimental

data, 313 K < T < 393 K. Fig. 3 shows the temperature dependence
of the Ci contributions for all the groups available to date. It should
be noted that the N(t-amine) group shows the steepest rate dCi/dT
(hydrophilicity loss with rising temperature) among all the groups
shown in Fig. 3.

Fig. 3. Temperature dependence of group contributions Ci. (s) CH(aromatic); (d) 4. Conclusion
C(aromatic); (j) CH2(ring); (h) N(pyridine); (4) S(ring); (+) O(ring); (r) NH(pyr-
role); (.) C@O(ring); () CH(alicyclic); (}) N(tert-amine). Solubilities in PHW have been measured of several compounds
used as hole transport materials or dopants in electro-optical de-
vices. The solutes and their respective temperature ranges of the
temperature interval from T to Tt. The last-but-one term on the
solubility measurements included 1,4-bis(diphenylamino)benzene
right-hand side of Eq. (3) accounts for the effect of elevated pressure
(403–463 K), tetra-N-phenylbenzidine (433–493 K), 4,40 -bis(N-carbaz-
assuming that both the solid solute and the subcooled liquid solute
olyl)-1,10 -biphenyl (433–533 K), 1,3,5-tris(diphenylamino)benzene
are incompressible and that their respective vapor pressures are
(453–513 K) and 9,10-bis(phenylethynyl)anthracene (433–513 K).
negligible with respect to the total pressure P. Among the present
The pressure of the solubility measurements ranged from 5.0 to
solutes, experimental values of DHfus and Tt are only available for
7.5 MPa. The results suggest that aqueous solubilities of these
triphenylamine, and experimental values of DCP are not available
compounds at 298.15 K are very low, generally below 2  1011 g
for any solute of this study. Therefore, the conversion of solubilities
of the solute per 1 kg of water.
to activity coefficients was performed only for triphenylamine, and,
In addition to the data for hole transport materials, the aqueous
following a previous recommendation for polycyclic aromatic
solubility of triphenylamine has been measured within 313 to
hydrocarbons (Pappa et al., 2005), the approximation DCP = 0 -
393 K. The solubility data were converted to the activity coeffi-
J mol1 K1 was adopted. The triple point temperature of triphenyl-
cients of triphenylamine in the aqueous solution, and these were
amine was approximated by the melting point temperature of
used to upgrade an earlier group-contribution model of activity
399.9 K as given in the NIST Chemistry WebBook (Linstrom and
coefficients in saturated aqueous solutions with the parameters
Mallard, 2011) with the primary source from Chickos et al.
for the nitrogen atom in tertiary aromatic amines.
(1991). The enthalpy of fusion of triphenylamine (24.89 kJ mol1)
was taken from the NIST Chemistry WebBook (Linstrom and Mal-
Acknowledgments
lard, 2011) with the primary source from Acree (1991). The molar
volume of the subcooled liquid triphenylamine was evaluated from
We acknowledge with thanks the funding of this work by the
the modified Rackett equation (Spencer and Adler, 1978) using the
Czech Science Foundation (Projects P206/11/0138, P503/11/P523
critical properties estimated from the Joback correlation (Joback
and P106/12/0522) and by the Academy of Sciences of the Czech
and Reid, 1987; Poling et al., 2001), and the molar volume of the so-
Republic (Institutional Support RVO:68081715).
lid triphenylamine was obtained using the correlation of Goodman
et al. (2004).
The resultant values of the activity coefficients are included in Appendix A. Supplementary material
the electronic Supplementary Information file. Activity coefficients
of organic solutes have often been described with diverse kinds of Supplementary data associated with this article can be found, in
group contribution models that build the activity coefficient value the online version, at http://dx.doi.org/10.1016/j.chemosphere.
from additive contributions of the individual groups in the solute 2012.10.085.
molecule (Fredenslund et al., 1975, 1977; Fornari et al., 2008;
Gmehling, 2009). Employing the solubility data in PHW as gener- References
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