Efcient determination of crystallisation and melting points at low cooling

and heating rates with novel computer controlled equipment

Philipp Wachter
a
, Hans-Georg Schweiger
a,b
, Franz Wudy
a
, Heiner J. Gores
a,
*
a
Institut fr Physikalische und Theoretische Chemie der Universitt Regensburg, Universittsstrae 31, D-93040 Regensburg, Germany
b
Continental Automotive Systems Division, Sickingenstrae 29-38, D-10553 Berlin, Germany
a r t i c l e i n f o
Article history:
Received 17 February 2008
Received in revised form 17 May 2008
Accepted 19 May 2008
Available online 28 May 2008
Keywords:
Phase transition points
Organic solvents
Ionic liquids
Crystallisation aids
Fast computer-controlled equipment
a b s t r a c t
We studied melting and solidication points of 14 pure solvents and two ionic liquids with a recently
constructed automatic computer-controlled equipment, which is able to record simultaneously temper-
aturetime functions of up to 30 samples at very low heating and cooling rates down to 1.5 K h
1
. The
effects of viscosity of the studied samples and of carbon bres as an added crystallisation aid were also
investigated. Equilibrium temperatures for the solidliquid phase transition are in accordance with liter-
ature for materials that were often checked, such as acetonitrile, showing the quality of our new equip-
ment, whereas the value of the transition temperature of some other materials differed from published
results. It is shown that both the viscosity of the material and carbon bres as crystallisation aids have an
effect on supercooling. The value given for the equilibrium point of the ionic liquid trioctylmethylammo-
nium triuorocetate T
tr
= (285.62 0.1) K is new.
2008 Elsevier Ltd. All rights reserved.
1. Introduction
Phase transition temperatures are not only important proper-
ties for the characterisation of materials but they also play a vital
role in technical applications. For example, the operating range of
several electrochemical devices for energy storage and transforma-
tion, such as lithium-ion-batteries, double layer capacitors, and
photo-electrochemical or dye-sensitised solar cells is limited by
the freezing temperature of the applied electrolyte. Therefore the
knowledge of precise liquid to solid phase transition temperatures
plays an essential role in the formulation of these electrolytes.
The main problem of all discussed methods is the determina-
tion of an equilibrium property (a freezing point) by heating or
cooling, whereas the system does not reside in the equilibrium
state. The determination of invariant points (degree of freedom
f = 0) in single component systems (triple points) can be readily
performed with high accuracy, often better than 5 mK. Therefore
values of the reference temperature on the international tempera-
ture scale (ITS) are based on these points, such as the triple point
temperature of water at 273.160 K. It is commonly known, that
univariant points (f = 1) can be measured often with high precision.
Recently, differential thermal analysis (DTA) and differential
scanning calorimetry (DSC) were applied mainly to investigate of
melting and freezing points [13]. These methods are fast and re-
quire only small sample volumes but are also less accurate [4]. Due
to the small sample volumes, they are subject to systematic errors.
Additionally, the applied cooling rates may enhance effects of
supercooling on the substances studied.
The effects of supercooling can be a severe source of errors, if li-
quid to solid phase transitions are observed. For common solvents,
supercooling can reach levels of 15 K and more. If phase transition
temperatures of ionic liquids are measured, the supercooling effect
is even worse and can provoke errors up to 200 K [5], making the
determination of phase transition temperatures almost impossible.
A further disadvantage of these methods is the use of very small
sample masses in the range of (1 to 100) mg. As a result of these
small sample masses, the effects that are caused by the wall of
the sample vessel become strongly apparent. In addition, even
marginal amounts of impurities play a major role, because they
strongly falsify the true phase transition temperatures.
A good homogenisation of the sample is an absolute must, if
phase transitions in mixtures are examined, so that the composi-
tion of the solution remains constant and corresponds to the equi-
librium composition. Conventional DTA/DSC devices have no
homogenisation equipment at all, restricting the ability to investi-
gate multi-component systems.
As an alternative to the above-mentioned methods, the investi-
gation of cooling curves may be appropriate as presented by An-
drew et al. [6]; other examples of this approach are shown in the
literature [4,7]. This method requires the transfer of a sample into
a stirred container and observation of the change of the tempera-
ture within the sample, while the sample is being very slowly
0021-9614/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2008.05.012
* Corresponding author. Tel.: +49 941 943 4746/9402 8040; fax: +49 9402 8035.
E-mail addresses: Heiner.Gores@Chemie.Uni-Regensburg.de, w.heitzer_h.j.gores
@t-online.de (H.J. Gores).
J. Chem. Thermodynamics 40 (2008) 15421547
Contents lists available at ScienceDirect
J. Chem. Thermodynamics
j our nal homepage: www. el sevi er. com/ l ocat e/ j ct
cooled down or heated up. Applying this procedure, a noticeable
increase of the accuracy occurs, because larger sample volumes
can be used. As shown by Rossini et al. [4], the melting point of
pure substances showing no supercooling effects can be measured
with an uncertainty of 10 mK. By this method, it is possible to
determine the melting point of acetonitrile with an uncertainty
of (13) mK [8,9]. To reach this level of accuracy, a huge effort must
be made to eliminate all systematic errors, such as heat conduction
via the thermometer, the Joule heating of the thermometer, insuf-
cient equilibration, and pressure effects. Due to the depression of
the freezing point caused by impurities, the required purity level
of the investigated substances is tremendous. For example, Rich-
ards observed a freezing point depression of 30 mK caused by dis-
solved air in benzene [10].
The observation of melting processes by this method is also dif-
cult, just like their determination using DTA/DSC, unless the sample
is mixed sufciently [11]. A solid, which is in the sample container,
melts beginning from an edge of the sample container towards the
centre, where the temperature sensor is usually attached. This sen-
sor is then still surrounded by the solid, despite the melting process
has already started. Therefore, the melting points determined with
this method are usually strongly affected by errors that can be only
reducedby an effective mixing device. Large cooling or heating rates
are leading to T(t) curves that can be interpretedeasily but are prone
toerrors, e.g. duetosupercooling. If lowrates arechosen, the thermal
effect of the phase change is blurred by the heat transfer to the sur-
roundings thereby making interpretation of the curves impossible.
This results in increased errors in the range from 0.1 K [4] up to 1 K
[1214] and they can reach up to 10 K [4].
Another similar non-equilibrium method is described by Schr-
dle et al. [15], making use of a photo detector to determine the
phase transitions. However, this method is limited to transparent
samples and gives no information if supercooling has occurred.
In this article, we present a new apparatus based on the mea-
surement of cooling and heating curves. With this apparatus, the
rapid and simultaneous investigation of up to 30 samples is possi-
ble, therefore enabling the investigation of the inuence of various
parameters, such as viscosity, cooling and heating rate, and crystal-
lisation aids on phase transition points or supercooling in adequate
times.
2. Theory
The test sample is treated by a temperature prole linear in
time for all methods presented above, while the change of the sam-
ples temperature is recorded over time. If a phase transition occurs
in a single component system, a halt is observed due to the phase
transition enthalpy. Because in this experiment, retarded crystalli-
sation or supercooling can occur, a curve similar to the one shown
in gure 1 is commonly observed. Therefore, it may be necessary to
determine the crystallisation point by extrapolation of the horizon-
tal or quasi-horizontal parts of the curves, also illustrated in gure
1. The intersection point of the two curves determines the crystal-
lisation point. Of course, supercooling effects cannot be noticed in
heating curves. But these experiments point out homogenisation of
the samples to be the crucial factor. This problem cannot be solved
easily, because samples containing large amounts of solid phase
have to be mixed.
3. Experimental
3.1. Apparatus and measurements
The temperature of the liquids was measured with a home-built
fast multi-channel precision thermometer, which was recently de-
scribed, along with its calibration [16]. This device measures tem-
peratures of 30 temperature sensors, the so called thermistors
(BetaTHERM Betacurve 30K6A1) over the temperature range of
(193 to 313) K. Over the temperature range from (223 to 283) K,
it provides accuracy better than 30 mK. Temperatures are recorded
with a constant sampling rate of 1 data point per second. The ther-
mometer is controlled by a MS Windows computer and home-built
FIGURE 1. Plot of temperature against time to show the cooling curve of
c-butyrolactone (GBL) with added carbon bres recorded at a cooling rate of 30
K h
1
(), extrapolation of the linear parts (-- -) for determination of the
crystallisation temperature.
FIGURE 2. Measuring cell: Inner Pyrex tube (A), magnetic stirrer (B), glass tube
with thermistor (C), SQ 18 closure with Teon coated rubber seal (D), thermal
insulation (E), outer Pyrex tube (F), connector for the thermistor (G).
P. Wachter et al. / J. Chem. Thermodynamics 40 (2008) 15421547 1543
software, enabling long term data recording of the temperature
measurements.
In gure 2, the measuring cell for T(t)-measurements is shown.
About 2 cm
3
of the sample is placed within the inner Pyrex tube
(A in gure 2). A Teon coated magnetic stirrer bar (B) is used for
mixing the liquid. Temperature is measured with the thermistor
(C), which is located inside a thin glass tube. The inner glass tube
(A) is closed with a SQ 18 screwcap and a Teon coated rubber seal
(D). The inner tube is centred in the outer tube (F) with o-rings,
leaving airspace (E) for thermal insulation. The cell is connected
using shielded twisted pair cable and a shielded connector to the
thermometer. The planetary stirring device shown in gure 3 has
a capacity of 21 measuring cells. A similar stirring device based
on alternating magnetic eld and with a capacity of 30 measuring
cells was constructed additionally.
The magnetic stirring bar is driven by a cobalt samarium mag-
net whose holder is connected with a gear wheel. The 21 gear
wheels are arranged in two concentric circles. The gear wheels in
the inner circle drive the gears in the outer circle. The inner wheels
are driven by an auxiliary wheel, which in turn is driven by the
centre drive wheel itself. An electrical motor drives this wheel
via a drive shaft. The measuring cells were lled and sealed tightly
in a glove box under an inert argon atmosphere. To investigate the
possibility of reducing effects of supercooling through application
of crystallisation aids, as suggested by Ding et al. [17], each sub-
stance was examined with and without the addition of carbon -
bres used in double layer capacitors. Furthermore, the effect of
these carbon bres on crystallisation and melting points was
studied.
The stirring device with the measuring cells is placed inside the
bath of a thermostat. This thermostat, described by Barthel et al.
[18,19], consists of an insulated bath lled with approximately
60 dm
3
silicone oil (Baysilon M5

, Bayer) in which a mechanical

stirrer, a heat exchanger, a source of heat, and a platinum resis-
tance thermometer are immersed. Via the heat exchanger, a cryo-
stat (Unistat 390w, Huber, Germany), which acts as cold bath, is
coupled to the measurement thermostat. A thorough mixing of
the bath is ensured by the mechanical stirrer. Measurements at
FIGURE 3. Planetary stirring device for 21 sample tubes. Magnetic stirring bar (A), cobalt samarium magnet (B), gear wheel (C), electrical engine (D), and drive shaft (E).
1544 P. Wachter et al. / J. Chem. Thermodynamics 40 (2008) 15421547
temperature gradients are enabled by the applied cryostat. The
cryostat is able to carry out heating- and cooling-experiments with
variably adjustable rates, respectively. The temperature range is
limited to a minimum of 183 K and a maximum of 323 K.
As mentioned above, the supercooling effects for a given mate-
rial relate to the magnitude of the applied cooling rates. To verify
this dependence and to examine its extent, every sample was
investigated at three different cooling rates. Furthermore the
inuence of different cooling and heating rates on crystallisation
and melting points was studied, by application of (1.5, 10, and
30) K h
1
as cooling rates and (1.5, 10, and 30) K h
1
as heating
rates. The measurements were conducted within a temperature
range between 193 K up to (293 or 313) K, if necessary. In order
to reduce the inuence of statistical outliers, every sample was
cooled down and heated up at least 10 times up to a maximum
of 62 times. As a result, crystallisation and melting points and their
errors could be determined with satisfying accuracy.
3.2. Materials
All materials were used as received and stored in a glove box
under inert argon atmosphere. Water contents of the investigated
substances that were liquid at room temperature were determined
via KarlFischer titration using a DL 18 titrator from Mettler (Gies-
sen, Germany) and are shown in table 1.
4. Results
The determined crystallisation and melting points are com-
pared in table 2 to literature values. The results show good accor-
dance with those from the literature; as well they show small
values of standard deviations in a range between (0.03 and 1) K.
This demonstrates the precision of the measuring method men-
tioned above. The magnitude of the standard deviations correlates
strongly with the differences between the literature values for
given materials. The melting points obtained by heating curves
are normally slightly lower than the crystallisation points obtained
by cooling curves, except for the studied ionic liquids due to their
addiction to strong supercooling. Therefore if it is not possible to
obtain reliable crystallisation points, melting points offer a poten-
tial alternative.
Decreasing the cooling rate results in most cases in a reduction
of supercooling effects, as shown in gure 4 for EMIOTf and GBL,
but there is no clear effect on the crystallisation points by this
reduction of supercooling. In general, there is no distinct conse-
quence on the location of crystallisation and melting points by var-
iation of cooling and heating rates, apart from arising problems in
evaluating cooling and heating curves for very low cooling and
heating rates, due to diffuse transitions.
Application of carbon bres as an aid to crystallisation leads to a
strong decrease of supercooling. For instance the decrease from
10.73 K down to 2.84 K for GBL is shown in gure 4, except for sub-
TABLE 1
List of studied materials in with corresponding acronym, mass fraction water,
supplier and purity grade
Acronym Material 10
6
w Supplier/purity
grade
AN Acetonitrile 38.5 Merck selectipur
GBL c-Butyrolactone 42 Merck selectipur
DEC Diethyl carbonate 17 Merck selectipur
DME Dimethoxyethane 72 Merck selectipur
DMC Dimethyl carbonate 45 Merck selectipur
EC Ethylene carbonate Merck selectipur
EMC Ethyl methyl carbonate 26 Merck selectipur
EP Ethylpropionate 160 Merck selectipur
DO 1,4-Dioxane 30 Merck seccosolv
DMSO Dimethylsulfoxide 50 Merck seccosolv
NM Nitromethane 196 Merck P98%
BC Butylene carbonate 69 Merck
EMIOTf 3-Ethyl-1-methylimidazolium
triuoromethanesulfonate
10 Merck
TOMATFA Trioctylmethylammonium
triuoroacetate
48 Merck
MPN Methoxypropionitrile 275 Fluka P99%
DMSO-d Dimethylsulfoxide-d
6
Deutero P99.50%
w = mass fraction of water as determined by KarlFischer titration.
TABLE 2
Crystallisation points Tc and melting points Tm for the investigated substances
compared with their literature values
Material Tc/K Tm/K
This work Literature This work Literature
AN 229.27 0.03 229.30 0.05 [14],
229.30 0.003 [20],
229.312 [21]
229.07 0.2
BC 220.34 0.6 220 [22]
GBL 229.44 0.2 228.44 0.1 229.62 [23],
230.1 [24]
DEC 195.49 0.1 195.86 0.3 198.85 [3],
230.2 [25],
199.0 [24]
DME
a
204.06 0.07 203.41 0.1 215 [23],
204 [21]
DMC 277.61 0.06 277.76 0.1 [11] 277.06 0.3 277.8 [26]
DMSO 291.19 0.4 290.95 1 291.690 0.005
[27],
291.70 0.02
[28]
DMSO-d 293.72 0.04 293.40 0.1 293.97 0.02
[29]
DO 284.85 0.02 284.48 0.2 284.939 0.036
[30],
284.93 0.01
[31]
EC 308.83 0.2 309.50 0.1 [11], 308.53 0.1 309.75 [24]
EMC 218.80 0.2 218.14 0.2 220 [2],
216.7 [24]
EMIOTf 259.11 0.8 262.23 0.3 264 [32]
EP
a
199.71 0.03 199.3 [33]
MPN 210.85 0.9 209.53 0.2 216 [22]
NM 244.45 0.1 243.36 0.2 244.60 [34],
244.6 [25],
243.11 [35]
TOMATFA 285.62 0.1
a
From measurements with added carbon bres.
FIGURE 4. Plot of the amount of supercooling dT against the cooling rate v: (d) GBL,
(s) GBL with added carbon bres, (j) EMIOTf, and () EMIOTf with added carbon
bres.
P. Wachter et al. / J. Chem. Thermodynamics 40 (2008) 15421547 1545
stances with little tendency to supercooling, such as AN or DO. As
found for variation of cooling and heating rates, there is no clear
trend observable by addition of carbon bres either on the location
of crystallisation and melting points or on their standard devia-
tions. In most cases there is a small increase in temperature of
the crystallisation points by addition of carbon bres, but overall
the difference between the values obtained with or without addi-
tion of carbon bres remains very small, except for the crystallisa-
tion point of EMIOTf where a difference of more than 2 K was
observed, as shown in table 3.
The viscosities g at T 298 K of the investigated substances are
listed in table 4, since it was expected that the viscosity has an
inuence on supercooling and on reproducibility of crystallisation
and melting points determined.
The inuence of the viscosity on the magnitude of calculated
standard deviations for crystallisation and melting points is shown
in gure 5. As expected, the standard deviations for crystallisation
points increase slightly with increasing viscosity whereas the stan-
dard deviations for melting points stay nearly constant, apart from
one outlier, due the fact that the melting starts from a solid.
As noted above, the viscosity also has an important inuence on
supercooling, due to decreasing transport processes (in this case
the heat-transport) with increasing viscosity, which cannot be
completely equalised by mixing the sample. A second important
factor for the degree of supercooling is the different ability to form
crystals for different substances that depends strongly on molecu-
lar geometry, e.g. organic carbonates with a strong increase in the
magnitude of supercooling with a loss in symmetry from the
symmetric DMC via EMC to the asymmetric PC. These two different
TABLE 3
Crystallisation points Tc and melting points Tm for the investigated substances with and without added carbon bres
Substance Tc/K Tm/K
With carbon bres Without carbon bres With carbon bres Without carbon bres
AN 229.27 0.03 229.00 0.2 229.07 0.2 228.40 0.8
BC 220.34 0.6
GBL 229.44 0.2 229.68 0.07 228.44 0.1 228.87 0.2
DEC 195.49 0.1 195.9 0.3
DME 204.06 0.07 203.41 0.1
DMC 277.61 0.06 277.59 0.05 277.06 0.3 277.21 0.4
DMSO 291.19 0.4 291.33 0.3 289.95 1 290.54 0.6
DMSO-d 293.72 0.04 293.755 0.007 293.40 0.1 293.32 0.1
DO 284.85 0.02 284.50 0.2 284.48 0.2 283.75 0.3
EC 308.83 0.2 309.12 0.09 308.53 0.1 308.69 0.1
EMC 218.80 0.2 218.64 0.1 218.14 0.2 218.03 0.09
EMIOTf 259.11 0.8 261.24 0.2 262.23 0.3 262.59 0.2
EP 199.71 0.03
MPN 210.85 0.9 209.53 0.2
NM 244.45 0.1 244.54 0.06 243.36 0.2 243.57 0.2
TOMATFA 285.62 0.1 285.48 0.08
TABLE 4
Values of viscosities g at T 298 K for the investigated substances
Substance g/(mPa s)
AN 0.341 [23]
BC 3.1419 [25]
GBL 1.7315 [23]
DEC 0.753 [25]
DME 0.407 [23]
DMC 0.5902 [26]
DMSO 1.991 [36]
DMSO-d
DO 1.1964 [37]
EC 1.9
a
[23]
EMC 0.6478 [25]
EMIOTf 45
b
[32]
EP 0.5323
b
[24]
MPN 1.1 [22]
NM 0.6260 [38]
TOMATFA
a
At T 313 K.
b
At T 293 K.
FIGURE 5. Plot of the standard deviation rT of hc (j) and hm (N) against viscosity g
for several substances from table 4.
FIGURE 6. Plot of the amount of supercooling dT against viscosity g for several
substances from table 4 without (j) and with added carbon bres (N).
1546 P. Wachter et al. / J. Chem. Thermodynamics 40 (2008) 15421547
factors can reinforce or diminish each other, which leads to the
behaviour shown in gure 6.
In general, supercooling is strongly reduced by addition of car-
bon bres as crystallisation aids. A second observation is the in-
crease in supercooling with increasing viscosity for symmetric
molecules (AN, DMC, DO, and DMSO) as well as for asymmetric
molecules (EMC, NM, and GBL), for which the magnitude of
supercooling is several times larger than for symmetric molecules.
5. Conclusion
A new automatic computer-controlled device for fast and
simultaneous determination of phase transition points for up to
30 samples is presented. Its performance is illustrated and the reli-
ability of the determined phase transition points evaluated by
comparison with literature. The new equipment, which is able to
record temperaturetime functions of up to 30 samples at very
low heating and cooling rates down to 1.5 K h
1
, enabled a highly
accurate reproduction of well-known phase transition points, a
verication of only rarely given phase transition points and a
rst-time determination of so far unknown phase transition points.
Investigations of the inuence of cooling-rates, viscosity, and
application of crystallisation aids on the magnitude of the superco-
oling resulted in a decrease of supercooling with decreasing cool-
ing-rate, decreasing viscosity, and application of carbon bres as
crystallisation aids, respectively.
Acknowledgments
The authors thank the Bundesministerium fr Bildung und
Forschung (BMBF) under contract No. 01SF0304, the Deutsche
Forschungsgemeinschaft (DFG Priority Project Ionic Liquids SPP
1191) for funding and D. Moosbauer for editing our paper.
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