Low-temperature properties of monoalcohol glasses and crystals
We review and jointly discuss both earlier and recent experiments conducted by us on simple aliphatic glass-forming monoalcohols at low temperatures, including specific heat, thermal conductivity, Brillouin scattering and x-ray diffraction experiments. The family of simple monoalcohols constitutes a...
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Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України
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nasplib_isofts_kiev_ua-123456789-1184592025-02-10T01:01:46Z Low-temperature properties of monoalcohol glasses and crystals Ramos, M.A. Hassaine, M. Kabtoul, B. Jiménez-Riobóo, R.J. Shmyt’ko, I.M. Krivchikov, A.I. Sharapova, I.V. Korolyuk, O.A. 9th International Conference on Cryocrystals and Quantum Crystals We review and jointly discuss both earlier and recent experiments conducted by us on simple aliphatic glass-forming monoalcohols at low temperatures, including specific heat, thermal conductivity, Brillouin scattering and x-ray diffraction experiments. The family of simple monoalcohols constitutes an interesting model system to explore different relevant issues concerning molecular glass-forming liquids, low-temperature universal proper-ties of glasses, and even the glass transition phenomenon itself. More specifically, we discuss the role played by the molecular aspect ratio in vitrification/crystallization kinetics, the reported appearance of particular cases of polymorphism (in ethanol) and polyamorphism (in butanol), and especially the influence of position isomerism and the location of the hydrogen bond on the lattice dynamics and hence on the low-temperature universal prop-erties of glasses. The Laboratorio de Bajas Temperaturas (UAM) is an associated unit with the ICMM-CSIC. This work was par-tially supported by the Spanish MINECO (FIS2011-23488 and Consolider Ingenio Molecular Nanoscience CSD2007-00010 program) and by the Comunidad de Madrid through program Nanobiomagnet (S2009/MAT-1726). 2013 Article Low-temperature properties of monoalcohol glasses and crystals / M.A. Ramos, M. Hassaine, B. Kabtoul, R.J. Jiménez-Riobóo, I.M. Shmyt’ko, A.I. Krivchikov, I.V. Sharapova, O.A. Korolyuk // Физика низких температур. — 2013. — Т. 39, № 5. — С. 600–605. — Бібліогр.: 29 назв. — англ. 0132-6414 PACS: 65.60.+a, 65.40.Ba, 66.70.Hk, 63.50.–x https://nasplib.isofts.kiev.ua/handle/123456789/118459 en Физика низких температур application/pdf Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України |
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9th International Conference on Cryocrystals and Quantum Crystals 9th International Conference on Cryocrystals and Quantum Crystals |
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9th International Conference on Cryocrystals and Quantum Crystals 9th International Conference on Cryocrystals and Quantum Crystals Ramos, M.A. Hassaine, M. Kabtoul, B. Jiménez-Riobóo, R.J. Shmyt’ko, I.M. Krivchikov, A.I. Sharapova, I.V. Korolyuk, O.A. Low-temperature properties of monoalcohol glasses and crystals Физика низких температур |
| description |
We review and jointly discuss both earlier and recent experiments conducted by us on simple aliphatic glass-forming monoalcohols at low temperatures, including specific heat, thermal conductivity, Brillouin scattering and x-ray diffraction experiments. The family of simple monoalcohols constitutes an interesting model system to explore different relevant issues concerning molecular glass-forming liquids, low-temperature universal proper-ties of glasses, and even the glass transition phenomenon itself. More specifically, we discuss the role played by the molecular aspect ratio in vitrification/crystallization kinetics, the reported appearance of particular cases of polymorphism (in ethanol) and polyamorphism (in butanol), and especially the influence of position isomerism and the location of the hydrogen bond on the lattice dynamics and hence on the low-temperature universal prop-erties of glasses. |
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Article |
| author |
Ramos, M.A. Hassaine, M. Kabtoul, B. Jiménez-Riobóo, R.J. Shmyt’ko, I.M. Krivchikov, A.I. Sharapova, I.V. Korolyuk, O.A. |
| author_facet |
Ramos, M.A. Hassaine, M. Kabtoul, B. Jiménez-Riobóo, R.J. Shmyt’ko, I.M. Krivchikov, A.I. Sharapova, I.V. Korolyuk, O.A. |
| author_sort |
Ramos, M.A. |
| title |
Low-temperature properties of monoalcohol glasses and crystals |
| title_short |
Low-temperature properties of monoalcohol glasses and crystals |
| title_full |
Low-temperature properties of monoalcohol glasses and crystals |
| title_fullStr |
Low-temperature properties of monoalcohol glasses and crystals |
| title_full_unstemmed |
Low-temperature properties of monoalcohol glasses and crystals |
| title_sort |
low-temperature properties of monoalcohol glasses and crystals |
| publisher |
Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України |
| publishDate |
2013 |
| topic_facet |
9th International Conference on Cryocrystals and Quantum Crystals |
| url |
https://nasplib.isofts.kiev.ua/handle/123456789/118459 |
| citation_txt |
Low-temperature properties of monoalcohol glasses and crystals / M.A. Ramos, M. Hassaine, B. Kabtoul, R.J. Jiménez-Riobóo, I.M. Shmyt’ko, A.I. Krivchikov, I.V. Sharapova, O.A. Korolyuk // Физика низких температур. — 2013. — Т. 39, № 5. — С. 600–605. — Бібліогр.: 29 назв. — англ. |
| series |
Физика низких температур |
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© M.A. Ramos, M. Hassaine, B. Kabtoul, R.J. Jiménez-Riobóo, I.M. Shmyt’ko, A.I. Krivchikov, I.V. Sharapova, and O.A. Korolyuk, 2013
Low Temperature Physics/Fizika Nizkikh Temperatur, 2013, v. 39, No. 5, pp. 600–605
Low-temperature properties of monoalcohol glasses
and crystals
M.A. Ramos, M. Hassaine, and B. Kabtoul
Laboratorio de Bajas Temperaturas, Departamento de Física de la Materia Condensada, and Instituto de Ciencia
de Materiales “Nicolás Cabrera”, Universidad Autónoma de Madrid, Cantoblanco, Madrid E-28049, Spain
E-mail: miguel.ramos@uam.es
R.J. Jiménez-Riobóo
Instituto de Ciencia de Materiales de Madrid (ICMM-CSIC), Cantoblanco, Madrid E-28049, Spain
I.M. Shmyt’ko
Institute of Solid State Physics of Russian Academy of Sciences, Chernogolovka 142432, Moscow dist., Russia
A.I. Krivchikov, I.V. Sharapova, and O.A. Korolyuk
B. Verkin Institute for Low Temperature Physics and Engineering of the National Academy of Sciences of Ukraine
47 Lenin Ave., Kharkov 61103, Ukraine
Received September 24, 2012
We review and jointly discuss both earlier and recent experiments conducted by us on simple aliphatic glass-
forming monoalcohols at low temperatures, including specific heat, thermal conductivity, Brillouin scattering
and x-ray diffraction experiments. The family of simple monoalcohols constitutes an interesting model system to
explore different relevant issues concerning molecular glass-forming liquids, low-temperature universal proper-
ties of glasses, and even the glass transition phenomenon itself. More specifically, we discuss the role played by
the molecular aspect ratio in vitrification/crystallization kinetics, the reported appearance of particular cases of
polymorphism (in ethanol) and polyamorphism (in butanol), and especially the influence of position isomerism
and the location of the hydrogen bond on the lattice dynamics and hence on the low-temperature universal prop-
erties of glasses.
PACS: 65.60.+a Thermal properties of amorphous solids and glasses: heat capacity, thermal expansion, etc.;
65.40.Ba Heat capacity;
66.70.Hk Glasses and polymers;
63.50.–x Vibrational states in disordered systems.
Keywords: glass transition, monohydroxy alcohols, low-temperature thermal properties of glasses, specific heat,
polymorphism, molecular glasses.
1. Introduction
The very nature of glasses (and of disordered con-
densed matter, in general), as well as glass-transition re-
lated phenomena, still represents an open challenge in con-
densed-matter physics [1] and chemical physics. Also, the
universal properties (thermal, vibrational, acoustic, dielec-
tric, etc.) exhibited by glasses or amorphous solids at low
temperatures or low frequencies [2] continue to be a major
controversial issue.
On the other hand, much interest has been recently paid
to molecular glass-forming liquids. One practical reason
for such an interest is that these liquids usually solidify
either into crystal or glassy states at temperatures between
liquid-nitrogen and room temperatures, therefore providing
easy access to the different states of the substance for ma-
ny experimental techniques. They often also include ma-
nifestations of polymorphism and even polyamorphism [3]
(i.e., the apparent existence of first-order transitions be-
tween two liquid states of a single-component substance
Low-temperature properties of monoalcohol glasses and crystals
Low Temperature Physics/Fizika Nizkikh Temperatur, 2013, v. 39, No. 5 601
or, more generally, between two distinct amorphous states
of that substance), that makes them even more interesting
to be studied.
In this paper, we briefly review and discuss the main
calorimetric and thermodynamic results found in the fa-
mily of aliphatic monohydroxy alcohols–or monoalcohols–
H(CH2)nOH for n = 1, 2, 3, 4, both from our own experi-
ments and from the literature. First, we will discuss how
the gradual elongation of the molecule with increasing
number of ethyl groups affects the vitrification vs crystalli-
zation kinetics for primary monoalcohols (that is, when the
hydrogen bond is fixed at the end of the molecule). We
will also address briefly the reported presence of crystal-
line polymorphism in ethanol and polyamorphism in bu-
tanol. Then, we will show the noticeable changes that oc-
cur in the lattice dynamics and hence in the low-tem-
perature properties of both glass and crystal states when
chemical (position) isomers are introduced, namely by
comparing 1-propanol vs 2-propanol and the different iso-
mers of butanol.
2. Experimental techniques
The experiments discussed in the present work include
calorimetric and specific-heat measurements, performed
either at liquid nitrogen or at liquid helium temperatures
and using different calorimetric methods, low-temperature
thermal conductivity measurements in the range 2 120 K,
Brillouin-scattering experiments in the range 10 300 K,
and x-ray diffraction experiments between liquid-nitrogen
and room temperatures.
As described in more detail elsewhere [4], we have im-
plemented a quasiadiabatic continuous calorimetric system
for glass-forming liquids that allows in situ preparation and
calorimetric characterization of the different phases of the
substance (typically using liquid nitrogen as thermal sink),
followed by accurate heat-capacity measurements at low
temperatures [5], where the liquid nitrogen bath is readily
replaced by liquid helium, and using then two alternative
thermal relaxation methods [4].
The thermal conductivity of the different samples was
measured under equilibrium vapor pressure in an experi-
mental set-up already described [6], using the steady-state
potentiometric method.
High-resolution Brillouin-scattering measurements of
both longitudinal and transverse sound velocities of the
different samples in their glass state at low temperature
were conducted by using an Ar
+
ion laser (wavelength =
= 514.5 nm) and a Sandercock-type 3+3 tandem Fabry-
Pérot interferometer [7]. In order to obtain direct informa-
tion of the sound propagation velocities, the 90A scattering
geometry was used.
The structure of the liquid and solid states of the different
monoalcohols was investigated by means of x-ray diffrac-
tion experiments. An x-ray diffractometer D-500 (Siemens)
with a secondary graphite monochromator and Cu-K ra-
diation was used in transmission geometry. As described in
more detail in Ref. 8, the liquid sample was inserted into a
disk-like sample holder with beryllium disks of ~ 20 mm
in diameter as windows. The thickness of the beryllium
disks is ~ 0.1 mm and the distance between windows is
~ 1.0 mm.
3. Experimental results
3.1. Methanol
The first primary monoalcohol of the series (n = 1) is
methanol or methyl alcohol, CH3OH, which presents a
small, “quasi-spherical” molecule and readily crystallizes.
Hence it is very difficult to obtain pure methanol as bulk
glass for standard conditions and cooling rates in typical
calorimetric experiments [9]. The structure of both the liq-
uid and the two low-temperature crystal phases found at
ambient pressure consists of linear chains of alternating
hydrogen bonded molecules [10]. Some researchers have
studied methanol with a few molar percent of water as to
avoid crystallization, but that is certainly another sub-
stance. Therefore, we have not measured the thermal prop-
erties of methanol.
3.2. Ethanol
Whereas pure methanol readily crystallizes and cannot
be obtained in the glass state for standard conditions and
cooling rates, ethanol exhibits a very rich polymorphism
presenting four different solid states. Thus, ethanol or ethyl
alcohol, CH3CH2OH (i.e., n = 2), is not an excellent glass-
former but at least the glass state can be readily obtained
by supercooling the liquid at 30 K/min [11], or even at
slower cooling rates above 6 K/min [12 15], since the crit-
ical cooling rate for ethanol has been found to depend on
several factors such as minor water impurity, mechanical
or geometrical details of the experimental cell driving hete-
rogeneous crystallization and even on the previous thermal
history of the liquid [16].
As said above, pure ethanol (see Fig. 1) exhibits a very
rich polymorphism presenting four different solid states
[11 13]: the ordinary amorphous solid or glass state ob-
tained when the liquid is cooled sufficiently fast, a body-
centred cubic plastic crystal (PC) with rotational disorder
which by quenching becomes an orientationally-disordered
crystal (ODC), and a fully-ordered (monoclinic) crystal
state with 4 atoms per unit cell [17], which in turn exists in
four distinct phases [14], depending on temperature and
thermal history. Therefore, a relatively simple and easily
available chemical substance as ethanol offers an extreme-
ly useful benchmark to study the glass transition phenome-
non and the very nature of glasses and amorphous solids,
since one can choose and discriminate the roles played by
translational, rotational and orientational disorder.
Very interestingly, both the standard glass transition
(amorphous solid supercooled liquid) and that dynami-
M.A. Ramos et al.
602 Low Temperature Physics/Fizika Nizkikh Temperatur, 2013, v. 39, No. 5
cal freezing of the PC into the ODC were found to occur at
the same temperature ( 97 K)g gT T and with compa-
rable discontinuities in the specific heat [11,13,16], as
shown in Fig. 2(a). Furthermore, the ODC state also exhi-
bits, qualitatively and almost quantitatively, the same uni-
versal glassy properties at low temperatures such as tunne-
ling states [5], the plateau in the thermal conductivity [18]
or the boson peak [13,15], as the truly amorphous, struc-
tural glass state, and in clear contrast to the stable (monoc-
linic) crystal (see Fig. 3(a)). For those reasons, such ODCs
are sometimes also named “glassy crystals” or “orienta-
tional glasses”.
3.3. Propanol
By putting a third carbon atom (i.e., adding another
ethyl group) to the monoalcohol chain, one gets for n = 3
the best glass-forming substance of the series: 1-propanol
or n-propanol. This fact is evidenced by a narrower tem-
perature range for the supercooled liquid than in ethanol.
The glass transition temperatures are essentially the same,
Tg 98 K for 1-propanol, but the melting point is now
11 K lower: Tm = 148 K. Indeed complete crystallization of
1-propanol requires annealing over several hours at tem-
peratures within a narrow range about 135 K [19,20]. Its
isomer 2-propanol is also a rather good glass-former, with
higher transition temperatures, Tg 115 K and Tm = 185 K,
but a similar discontinuity of Cp(Tg) 45 J/(mol·K) (see
the inset in Fig. 1 of Ref. 19). Surprisingly, 2-propanol was
found [19] to exhibit a much higher boson peak (the broad
maximum in Cp/T
3
) than 1-propanol. This was attributed
to a correspondingly higher density of Debye-like acoustic
excitations, since the cubic Debye coefficients of the cor-
responding crystals presented a similar ratio (see Fig. 3(b)).
3.4. Butanol
By further elongating the molecule (n = 4), the glass-
forming tendency begins to reverse: 1-butanol (n-butanol)
glass can be easily obtained when cooling the liquid at a
moderately slow rate, but it crystallizes when heating the
glass or if the supercooled liquid is kept at certain tempera-
tures long enough. Interestingly, a metastable phase (be-
tween the glass and crystal ones) was found in 1-butanol
[21], very similar to that previously found in triphenyl
phosphite (TPP) [22,23]. In both cases, a new solid phase
denoted as glacial phase or glacial state [22], obtained by a
first-order, exothermic transformation from the super-
cooled liquid state was observed. Among other interpreta-
tions, this controversial “glacial phase” was firstly attri-
buted in TPP to a defect-ordered phase within the theory of
frustration-limited domains [22], and later was considered
(both for TPP and 1-butanol) as a manifestation of liquid-
liquid transitions between two distinct liquid (with their
corresponding amorphous solid) states [23]. A brief review
Fig. 1. Schematic Gibbs-energy phase diagram for ethanol.
When the supercooled liquid (SCL) below the melting point
(Tm = 159 K) is quenched fast enough, the glass state is obtained
at Tg 97 K. By heating the glass above Tg or by cooling the
SCL more slowly, a plastic crystal (PC) is obtained, which be-
comes an orientationally-disordered crystal (ODC) below a glass-
like transition also at gT 97 K.
Fig. 2. Specific heat measured around the corresponding glass
transitions for ethanol: solid circles show the glass–supercooled
liquid (SCL) transition at Tg 97 K, open circles show the ana-
logous transition from the orientationally-disordered crystal
(ODC) to the plastic crystal (PC), and crosses are data for the
stable crystal (a); butanol: the symbols for the three position iso-
mers with glass states are indicated in the legend, and the similar
glass-transition temperatures are labelled in the plot (b).
Low-temperature properties of monoalcohol glasses and crystals
Low Temperature Physics/Fizika Nizkikh Temperatur, 2013, v. 39, No. 5 603
about polyamorphism with special emphasis on the case of
TPP can be found in Ref. 3.
Nonetheless, Hédoux et al. [24] have perfomed several
experiments on TPP, and have shown that the atypical
transformation kinetics found can be understood as a con-
sequence of a time lag of nucleation, inducing a high nuc-
leation rate which frustrates the crystallization and leads to
the so-called “glacial state”. By using Raman-scattering,
the origin of the frustration of the crystallization in 1-bu-
tanol has also been explained [25] from the consideration
that the rearrangement of the hydrogen-bonded molecules
is unavoidably prevented by the very low molecular mobil-
ity of the system only a few degrees above Tg. The “glacia-
tion” process would be an abortive crystallization driven
by the formation of a layered, two-dimensional hydrogen-
bond network. This particular transformation kinetics can
nonetheless be described [24,25] by a classical nucleation-
growth law. In fact, the temporal evolution of the trans-
formation degree in 1-butanol at two different temperatures
above Tg
were found [25] to follow a clear Avrami sig-
moidal shape, indicative of a first-order character for the
isothermal transformation. The authors estimated degrees
of crystallinity at the end of the transformation processes
typically around 70 80% [25]. Our recent experiments
[7,8,26] fully support this view that the “glacial phase”
of 1-butanol is just a mixture of many nanocrystallites em-
bedded in a disordered matrix, presumably due to an ab-
orted crystallization originated by a high nucleation rate in
a temperature range where the crystal growth is low. In
addition, the stable crystalline state was found to present
triclinic symmetry with 6 atoms per unit cell [8].
Finally, we have concurrently studied [27] the low-
temperature thermal properties of the different position
isomers of butanol (n-, sec-, tert- and iso-butanol), though
only in three of them we were able to obtain the glass state:
in tertbutanol only crystalline phases were observed. In
Fig. 2(b) we show the obtained specific-heat data around
the glass transition for n-butanol (= 1-butanol), sec-butanol
(= 2-butanol) and iso-butanol. Also, in three out of the four
cases, we were able to obtain the fully crystalline state and
measured their specific heat as a useful reference. Bril-
louin-scattering measurements at low temperatures of lon-
gitudinal and transverse sound velocities for the different
glasses provided us with the Debye phonon-like contribu-
tion to their specific-heat curves. Complementary thermal-
conductivity measurements for those butanol glasses, per-
formed between 2 K and the glass transition temperatures
allowed us to carry out an exhaustive study [27] for differ-
ent glasses of the same substance, i.e., butanol, in order to
assess the effects of changing the spatial arrangement of
atoms and the position of hydrogen bonds in the lattice on
the low-temperature thermal and elastoacoustic properties
around the universal boson peak feature in glasses. In brief,
we found that the main thermal properties of butanol
glasses at low temperatures strongly vary among its differ-
ent position isomers, when the hydrogen bond of the hy-
droxyl group (OH) locates in a different position of the
butanol molecule, in clear contrast with the elastic Debye
contributions, since both the Debye specific heat of the
reference crystals and that of glasses obtained from Bril-
louin experiments remain essentially constant for the dif-
Fig. 3. Reduced specific-heat Cp/T
3
plots for glasses and crystal-
line phases of: pure ethanol, including the orientationally-
disordered crystal (ODC) (a); 1-propanol and 2-propanol (b);
different position isomers of butanol, as indicated in the legend.
In all cases, the obtained Debye levels for the crystals are shown
with dashed lines (c).
M.A. Ramos et al.
604 Low Temperature Physics/Fizika Nizkikh Temperatur, 2013, v. 39, No. 5
ferent isomers (see Fig. 3(c)). Moreover, we want to stress
that a consistent analysis of all low-temperature thermal
properties of butanol glasses using the soft-potential mo-
del [28] was possible [27].
4. Discussion
We will firstly focus on the primary monoalcohols. As
shown above, by gradually increasing the “length” of the
molecule, one modifies the balance between crystallization
kinetics and glass-forming ability. Whereas pure methanol
(a small, “quasi-spherical” molecule) readily crystallizes
and we were not able to obtain it in the glass state for stan-
dard conditions and cooling rates, ethanol seems to possess
a “critical” aspect ratio for its molecule, with competing
interactions and driving forces which are likely at the ori-
gin of its interesting and rich polymorphism, depicted in
Fig. 1. By adding another ethyl group to the hydrocarbon
backbone and hence further elongating the “ellipsoidal”
molecule, the best glass-forming primary monoalcohol is
observed: 1-propanol. Propanol molecules seem to be long
enough as to seriously hinder the crystallization arrange-
ment. With the next in the series, the glass-forming ten-
dency begins to reverse: 1-butanol glass can be easily ob-
tained when cooling the liquid at a moderately slow rate,
but it readily crystallizes when heating the glass, though
often in a two-step process that could be wrongly taken as
a polyamorphic transition. Interestingly, this glass-forming
tendency found in primary monohydroxy alcohols is exact-
ly the same previously observed for the first four members
of the alkyl-cyclohexanes family [29]. It suggests therefore
that when the hydrocarbon molecules are long enough,
they begin to find easier to align themselves and crystall-
ize, and this crossover typically occurs when passing from
3 to 4 carbon atoms in the linear chain.
In Table 1, we summarize the main calorimetric and
thermodynamic data of all studied monoalcohols. We in-
clude the value of the specific-heat discontinuity at the
glass transition in units of the gas constant, Cp(Tg)/R, as a
measure of the number of degrees of freedom that are re-
leased at the glass transition. It is noteworthy that Cp
(Tg)/R does not increase more or less linearly with the size
of the molecule (i.e., with n), but it remains rather constant.
Also, the position and height of the boson peak in the dif-
ferent glasses (including the “glassy crystal” of ethanol,
ODC) is compared to the Debye contribution found in the
corresponding crystals. No clear correlation between them
is found. In this case, however, the amount of low-
temperature glassy excitations per mol roughly increases
with the size of the molecule.
5. Conclusions
We have discussed how either the gradual elongation of
the monoalcohol molecule with increasing number of ethyl
groups or the hydrogen-bonding location have a strong
influence on the glass-forming ability, as well as on low-
frequency dynamics and low-temperature properties of
molecular solids. The competition between crystallization
rate and glass-forming ability seems to depend mainly on
the aspect ratio of the molecules, ranging from the easiest
crystal former methanol to the best glass former propanol.
Intermediate glass formers as ethanol or butanol has been
argued to present the added value of a rich polymor-
phism the former and the possibility of comparing dif-
ferent chemical isomers –the latter . However, the claimed
polyamorphism reported to exist in n-butanol ascribed to a
new glacial state was found to be just a mixture of nano-
crystallites embedded in a glassy matrix, presumably due to
an aborted crystallization originated by a high nucleation
rate in a temperature range where the crystal growth is low.
On the other hand, it was found that the low-energy
glassy excitations (tunneling states, boson peak…) of the
structural (amorphous) and orientational (ODC) glasses of
ethanol were very similar, whereas those of secondary al-
cohols were unexpectedly larger than those of their corres-
ponding primary alcohols. Nonetheless, in the case of pro-
Table 1. Calorimetric and thermodynamic data of several monohydroxy alcohols. Tg is the glass-transition temperature and Cp(Tg)
its specific-heat discontinuity; R is the gas constant; Tm is the melting temperature; CD, crystal is the Debye cubic coefficient obtained
from the crystal specific heat; Tmax,BP is the temperature of the maximum in Cp/T
3
(boson peak) and (Cp/T
3
) BP its height.
Substance
Tg,
K
Cp (Tg),
J·mol
–1·K–1
Cp /R
Tm,
K
CD, crystal,
mJ·mol
–1·K–4
Tmax,BP,
K
(Cp/T
3
) BP,
mJ·mol
–1·K–4
Refs.
methanol 103 30 3.6 176 – – – 9
ethanol (glass) 97 35.3 4.2 159 0.766 6.1 2.4 15,16
ethanol (ODC) 97 22.8 2.7 127.5 0.766 6.8 2.2 15,16
1-propanol 98 45 5.4 148 1.10 6.7 2.7 15,19
2-propanol 115 46 5.5 185 1.55 5.0 3.6 15,19
(1-) n-butanol 111 48 5.8 184 1.40 5.4 3.1 8,27
(2-) sec-butanol 118 40 4.8 185 – 4.8 4.6 27
tert-butanol – – – 293 1.28 – 27
isobutanol 113 40 4.8 168 1.28 4.8 5.7 27
Low-temperature properties of monoalcohol glasses and crystals
Low Temperature Physics/Fizika Nizkikh Temperatur, 2013, v. 39, No. 5 605
panol, 2-propanol crystal exhibits a correspondingly larger
Debye coefficient than 1-propanol crystal. In contrast, 2-bu-
tanol glass also exhibits a significantly higher low-tem-
perature specific heat than that of 1-butanol, but the Debye
specific heats of all butanol crystals are practically identic-
al. Therefore, no universal correlation between the boson
peak of glasses and the Debye-like elastic properties can be
drawn.
Acknowledgments
The Laboratorio de Bajas Temperaturas (UAM) is an
associated unit with the ICMM-CSIC. This work was par-
tially supported by the Spanish MINECO (FIS2011-23488
and Consolider Ingenio Molecular Nanoscience CSD2007-
00010 program) and by the Comunidad de Madrid through
program Nanobiomagnet (S2009/MAT-1726).
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