Pressure-temperature phase diagrams of smectogenic 4'-alkyl-4-cyanobiphenyls (9CB, 10CB, 11CB and 12CB)

The pressure-temperature ( p - T ) phase diagrams for four smectogenic members of the 4'-alkyl-4-cyanobiphenyl homologous series ( n CB, n =9, 10, 11 and 12) over the temperature range 320-410 K and pressure range 0.1-300 MPa (3 kbar) were constructed using DTA. At 1 atm 9CB exhibits nematic and smectic A d phases, while the other members show only the smectic A d phase. However, at elevated pressures the clearing line splits in the case of 10CB and 11CB which indicates the induction of a nematic phase. It was found that the triple point, where the isotropic, nematic and smectic phases coexist, is strongly shifted to higher pressures with increasing chain length. This was interpreted as being caused by a loss of the rod-like shape of the molecules containing longer alkyl tails which explore a range of conformations. The slope of the clearing line, d T /d p , depends strongly on the length of the alkyl chain for the n CB series, but does not show a step-wise change between the nematogenic and smectogenic members.     

Phase diagram and dielectric relaxation studies of n-octyl-isothiocyanato-biphenyl (8BT) in the crystalline E phase under high pressure

The pressure-temperature phase diagram of n-octyl-isothiocyanato-biphenyl (8BT) in the pressure range up to 250 MPa (2.5 kbar) and the temperature range 250-400 K was established with the aid of DTA. At 1 atm the substance exhibits exclusively CrE polymorphism. At pressures above 190 MPa, the clearing line splits showing an additional phase which is not yet identified. Dielectric relaxation measurements on the CrE phase of 8BT were performed in the pressure range 0.1-120 MPa and the temperature range 304-345 K. A Debye-type relaxation process was observed in the frequency range 100 Hz-1 MHz. The longitudinal relaxation time τ, characterizing the molecular reorientations around the short axis, was analysed with respect to the pressure and temperature, yielding the activation volume, Δ^# V = RT(? ln τ/?p)_T, and activation enthalpy, Δ^# H = R(? ln τ/? T^-1)_p, respectively. The results are compared with analogous data obtained recently for similar compounds having other liquid crystalline phases (N, SmA).     

Differential thermal analysis at high pressures— VIII: Phase behaviour of solid cyclopentanone,cyclopentanol, and cyclohexanone up to 3 KBAR

The phase behaviour of solid cyclopentanone, cyclopentanol, and cyclohexanone was investigated from 80 K to the melting temperature and up to 3 Kbar, using a low-temperature high-pressure differential thermal analysis apparatus. The melting temperature of cyclopentanone rises from 221.7 K at atmospheric pressure to 278 K at 2900 bar. No solid solid transition was observed. The melting temperature of cyclohexanone rises from 242.4 K at atmospheric pressure to 312 K at 2840 bar. Its well-known solid solid transition at atmospheric pressure (220.3 K) splits into two different solid solid transitions at elevated pressures. The melting temperature of cyclopentanol rises from 256 K at atmospheric pressure to 328 K at 2600 bar. Cyclopentanol exhibits two well-known solid solid transitions (236.4 K and 202.5 K at 1 atm), but an additional metastable form has been observed in the present work. the transition temperature being 195 K at 1 atm. Volume changes accompanying the phase transitions have been calculated using the Clausius Clapeyron equation.     

PVT data for liquid and solid cyclohexane,cyclohexanone and cyclopentanol up to 3000 bar

PVT data have been determined for cyclohexane (194–338 K), cyclohexanone (214–303 K), and Cyclopentanol (204–325 K) up to 3000 bars, as well as the volume changes accompanying the phase transitions. The volume changes allow the calculation of the corresponding enthalpy and entropy changes on using the Clausius-Clapeyron equation. The volume changes of melting decrease considerably with increasing pressure, whereas those due to solid-solid transitions exhibit much less of a pressure dependence. The PVT data of the liquid phases are described with the Tait equation.     

Dielectric studies of liquid crystals under high pressure. IV. Static permittivity and low frequency relaxation process in 4-n-hexyl-4'-cyanobiphenyl (6CB)

Dielectric studies of 4-n-hexyl-4'-cyanobiphenyl (6CB) were performed in the pressure range 0·1-150 MPa, the frequency range 1 kHz-13 MHz and the temperature range 290-327 K. The temperature and pressure dependencies of the static permittivity ε0| and the relaxation time τ| are analysed and compared with analogous data obtained recently for 5CB and 6CHBT (parts I-III of this series). It was shown that in the nematic phases of both 4-n-alkyl-4'-cyanobiphenyls the dipole-dipole correlations are broken by relatively low pressure.     

Bestimmung kleiner Wassergehalte in Methanol mittels Differentialthermoanalyse (DTA)

Zusammenfassung Eine Methode zur Bestimmung kleiner Wassergehalte in Methanol (0,02–1 Mol-%) mit Differentialthermoanalyse (DTA) wird beschrieben. Die Wirksamkeit verschiedener Trocknungsverfahren wird untersucht. Das Verfahren wird im Vergleich mit anderen Wasserbestimmungsmethoden in organischen Flüssigkeiten diskutiert.Die Deutsche Forschungsgemeinschaft und der Fonds der Chemischen Industrie unterstützten die Untersuchungen durch Sachmittel.     

PVT measurements on n -octyl-isothiocyanato-biphenyl (8BT) at elevated pressures

For the first time pressure-volume-temperature (PVT) measurements for the crystal-like smectic E phase have been performed. The phase diagram of 4′-n -octyl-4-isothiocyanatobiphenyl 8BT has been recently established using differential thermal analysis up to 250 MPa. 8BT exhibits a splitting of the clearing line above 170 MPa. PVT data have been measured in the same pressure range for temperatures between 313 and 393 K. Volume and enthalpy changes accompanying the clearing line of 8BT are also presented. The configurational part of the entropy change at the CrE-I transition of 8BT amounts to ≈ 60%. Using the PVT data and recently published dielectric relaxation results, the isochoric activation energy was calculated (giving ≈ 50% of the activation enthalpy); this is compared with analogous results for other liquid crystals.     

Dielectric studies of liquid crystals under high pressure II. Low frequency relaxation process in 4-n-pentyl-4′-cyanobiphenyl in relation to theories of the nematic state

Abstract

The results of high pressure dielectric studies of 4-n-pentyl-4′-cyanobiphenyl (5CB) are analysed in terms of theories of the nematic state. The retardation factor g∥ = τ∥/τ₀ and the effective, single-particle potential of mean torque were calculated at the nematic–isotropic transition temperature T _NI and along the isothermal, isobaric and isochoric paths within the nematic phase of 5CB. The potential of mean torque is compared with the order parameter known for the same conditions. The values of parameter γ relating the potential to the volume is discussed.     

Dielectric studies of liquid crystals under high pressure III. Low frequency relaxation process in 4-(trans-4′-n-hexylcyclohexyl)isothiocyanato benzene

Abstract

Dielectric studies of 4-(trans-4′-n-hexylcyclohexyl) isothiocyanatobenzene (6CHBT) were performed in the pressure range 0·1–150 MPa, the frequency range 1 kHz–13 MHz and the temperature range 295–325 K. The temperature and pressure dependencies of the static permittivity ?_0∥ and of the relaxation time τ_∥ are analysed and compared with the analogous data obtained recently for 4-n-pentyl-4′-cyanobiphenyl (5CB) (Parts I and II of this series). Marked differences in the dielectric properties of the nematic phases of the two substances are observed. They are interpreted as a result of varying degrees of molecular association in particular compounds. It is concluded that in the nematic phase of 6CHBT dipole–dipole correlations do not exist or are very weak, whereas for 5CB they are easily broken by a relatively low pressure.     

DTA,X-ray and dielectric relaxation studies of 14CB at atmospheric and elevated pressures

The pressure-temperature phase diagram of 4′-tetradecyl-4-cyanobiphenyl (14CB) up to 220 MPa (2.2 kbar) and between 320–400 K was established using DTA. The temperature range of the smectic A (SmA) phase slightly increases with pressure. The layer spacing d at 1 atm was determined as a function of temperature using X-ray diffraction. It was related to the molecular length l by the ratio d/l ? 1.4. The dielectric relaxation measurements in the isotropic and smectic A_d phases of 14CB at 1 atm were performed in the frequency range 10 kHz-3 GHz. Contributions from both principal rotational motions, i.e. around the short and long molecular axes, were separated. The relaxation measurements under high pressure in the SmA phase covered the low frequency process. The longitudinal relaxation time τ₁, characterizing the molecular reorientations around the short axis, was analysed with respect to the pressure and temperature dependences, giving activation volumes, Δ^# V = RT (? ln τ₁ / ?p)_T, and activation enthalpies, Δ^# H = RT(? ln τ₁ / ?T ^-1)_p, respectively. Surprisingly, all the activation quantities characterizing the rotational motions of 14CB molecules under different conditions are nearly the same as those determined recently for the much shorter homologue, 8CB. This indicates that the 14CB molecule is in fact relatively short due to conformational motions of the alkyl tail.