Differential Thermal Analysis and PVT Measurements on 2,2,2-Trichloro-ethanol Under High Pressure

1997 ◽  
Vol 52 (6-7) ◽  
pp. 493-501 ◽  
Author(s):  
M. Jenau ◽  
M. Sandmann ◽  
A. Würflinger ◽  
J. Ll. Tamarit
Keyword(s):  
Thermal Analysis ◽  
Differential Thermal Analysis ◽  
Atmospheric Pressure ◽  
Solid Phase ◽  
Melting Curve ◽  
Phase Behaviour ◽  
Enthalpy Changes ◽  
Pvt Measurements ◽  
Plastic Phase ◽  
Lower Temperature

Abstract The phase behaviour, the calorimetric and volumetric properties of 2,2,2-trichloro-ethanol (TCE) have been studied with differential thermal analysis (DTA) and pVT measurements in the pressure range 1 atm to 300 MPa and temperatures between 250 K to 355 K. TCE displays a metastable plastic phase (solid I') and a non-plastic solid phase II at atmospheric pressure. At least two pressure-induced solid phases have been detected: a stable plastic phase (solid I') and a non-plastic phase (solid III). There are two sets of triple points: a) 123 MPa and 308 K with the phases solid I, solid II and the liquid, b) 243 MPa and 316 K for solid I, II, III. Furthermore a metastable low-temperature brittle form (solid II') has been found, which transforms to solid I at a considerably lower temperature than solid II. The melting curve of solid I' can be pursued to higher pressures up to 260 MPa. On the other hand, the melting curve of the stable plastic phase solid I can be extrapolated beyond the triple point to pressures below 123 MPa. Volume and enthalpy changes are reported for all phase transitions.

1H NMR and Thermal Studies of CH3NH3Br in a Metastable Solid Phase Newly Found above 483 K

1989 ◽  
Vol 44 (8) ◽  
pp. 738-740 ◽  
Author(s):  
Masataka Tansho ◽  
Daiyu Nakamura ◽  
Ryuichi Ikeda
Keyword(s):  
Thermal Analysis ◽  
Differential Thermal Analysis ◽  
Solid Phase ◽  
Thermal Studies ◽  
Stable Phase ◽  
Self Diffusion ◽  
H Nmr ◽  
Plastic Phase ◽  
Metastable Solid Phase ◽  
Absorption Measurements

Abstract By differential thermal analysis a new high-temperature solid phase of methylammonium bromide was found between 483 K and its “melting point” (510 K). 1H NMR absorption measurements revealed the presence of rapid 3D translational self-diffusion and overall rotation of methylammonium cations in this phase. These cationic motions are quite analogous to those of methylammonium iodide in its ionic plastic phase. Surprisingly, this plastic-like phase is metastable, the stable phase in the same temperature range being liquid.

Structural Phase Transitions in Solid tert-Butylammonium Nitrate as Studied by Differential Thermal Analysis and 1H-NMR

1989 ◽  
Vol 44 (1) ◽  
pp. 71-74
Author(s):  
Hiroyuki Ishida ◽  
Tadashi Iwachido ◽  
Naomi Hayama ◽  
Ryuichi Ikeda ◽  
Miyuki Hashimoto ◽  
...  
Keyword(s):  
Thermal Analysis ◽  
Differential Thermal Analysis ◽  
Solid Phase ◽  
Structural Phase ◽  
Structural Phase Transitions ◽  
Self Diffusion ◽  
H Nmr ◽  
Nmr Techniques ◽  
Plastic Phase ◽  
Solid Phases

Abstract Seven solid phases including three metastable phases of (CH3)3CNH3NO3 were revealed by differential thermal analysis in the temperature range between 80 K and the melting point (418 K), and cationic dynamics in each phase was studied by use of 1H-NMR techniques. The highesttemperature solid phase obtainable above 412 K was found to be an ionic plastic phase, where the cations perform rapid translational self-diffusion and overall rotation about their center of gravity.

PVT and DTA Measurements on trans-4-n-Hexyl- (4'-Cyanophenyl)-Cyclohexane (6PCH) up to 300 MPa

1999 ◽  
Vol 54 (5) ◽  
pp. 281-286 ◽  
Author(s):  
M. Sandmann ◽  
F. Hamann ◽  
A. Würflinger
Keyword(s):  
Thermal Analysis ◽  
Phase Diagram ◽  
High Pressure ◽  
Differential Thermal Analysis ◽  
Phase Transitions ◽  
Melting Curve ◽  
Enthalpy Changes ◽  
Volume Entropy ◽  
Solid Phases ◽  
Specific Volumes

The phase diagram of trans-4-n-hexyl-(4'-cyanophenyl)-cyclohexane, (6PCH) has been established by high-pressure differential thermal analysis. Specific volumes are presented for temperatures between 300 and 370 K up to 300 MPa. The p,Vm ,T data have been determined for the nematic, isotropic, and (partly, in the neighbourhood to the melting curve) solid phases. Volume and enthalpy changes along the phase transitions have also been calculated. As previously, the p,Vm,T data were used to calculate the volume entropy for the nematic-isotropic transition. The molar volumes along the clearing line TNI (p) enabled us to calculate the molecular field parameter γ = ∂ln TNI/∂In VNI , being 4.1.

PVT Measurements on 4-n-Pentyl-4´-Cyano-Biphenyl (5CB) and trans-4-(4´-Octyl-Cyclohexyl)-Benzonitrile (8PCH) up to 300 MPa

1997 ◽  
Vol 52 (10) ◽  
pp. 739-747 ◽  
Author(s):  
M. Sandmann ◽  
F. Hamann ◽  
A. Würflinger
Keyword(s):  
Liquid Crystalline ◽  
Solid Phase ◽  
Melting Curve ◽  
Entropy Change ◽  
Isotropic Phase ◽  
Enthalpy Changes ◽  
Metastable Form ◽  
Pvt Measurements ◽  
Crystal Phases ◽  
Specific Volumes

Abstract Specific volumes are presented for 4-n-pentyl-4´-cyanobiphenyl (5CB) and trans-4-(4´-octyl-cyclo-hexyl)-benzonitrile (8PCH) for temperatures between 300 and 370 K up to 300 MPa. The p,Vm ,T data were determined for the liquid crystalline and isotropic phases, and partly also for the solid phase adjacent to the melting curve. Stable and metastable crystal phases can be distinguished. The density and melting temperature of the metastable form are lower than for the stable one. Volume and enthalpy changes accompanying the phase transitions are reported as well. The p,Vm ,T data allow to calculate the entropy change for a hypothetical transition at constant volume. The molar volumes along the nematic-isotropic phase transition TNI (p) allow to determine the molecular field parameter γ = ∂In TNI /∂ In VNI.

Differential Thermal Analysis and Dielectric Studies on Neopentanol under Pressure

1992 ◽  
Vol 47 (11) ◽  
pp. 1127-1134 ◽  
Author(s):  
H. G. Kreul ◽  
R. Waldinger ◽  
A. Würflinger
Keyword(s):  
Thermal Analysis ◽  
Differential Thermal Analysis ◽  
Relaxation Time ◽  
Phase Transitions ◽  
Dielectric Relaxation ◽  
Pressure Dependence ◽  
Dielectric Relaxation Time ◽  
Dielectric Studies ◽  
Dielectric Measurements ◽  
Plastic Phase

Abstract Differential thermal analysis (DTA) and dielectric measurements have been performed on 2,2-dimethyl- 1-propanol (neopentanol) up to 200 MPa. Neopentanol exhibits at least one orientationally disordered (ODIC) phase (solid I) that transforms at lower temperatures to a non-plastic phase (solid II). There is evidence of a further ODIC phase denoted as solid I'. The pressure dependence of the phase transitions and the dielectric behaviour up to frequencies of 13 MHz are described. Activation enthalpies and volumes are derived from the dielectric relaxation time and compared with results for other alcohols

Solid phase precipitates in (Zr,Th)-OH-(oxalate, malonate) ternary aqueous system

2009 ◽  
Vol 97 (4-5) ◽  
Author(s):  
Taishi Kobayashi ◽  
Takayuki Sasaki ◽  
I. Takagi ◽  
Hirotake Moriyama
Keyword(s):  
Thermal Analysis ◽  
Differential Thermal Analysis ◽  
Solid Phase ◽  
Aqueous System ◽  
Carboxylate Ligand ◽  
X Ray Diffraction ◽  
Large Excess ◽  
X Ray ◽  
Acidic Conditions ◽  
Solid Phases

AbstractThe solubility-limiting solid phases in the ternary aqueous systems of Zr(IV)/OH/oxalate, Zr(IV)/OH/malonate, Th(IV)/OH/oxalate and Th(IV)/OH/malonate were characterized by elemental analysis, X-ray diffraction, thermogravimetric analysis and differential thermal analysis. The ternary solid phase of M(IV)/OH/carboxylate was observed to form, even under acidic conditions, depending on the pH and the concentration of carboxylate ligand. In the presence of a large excess of carboxylic acid, however; the binary M(IV)-carboxylate solid phase formed.

Differential Thermal Analysis and Dielectric Studies on 2-Methyl-2-Nitro-Propane under High Pressure

1995 ◽  
Vol 50 (4-5) ◽  
pp. 502-504 ◽  
Author(s):  
D. Büsing ◽  
M. Jenau ◽  
J. Reuter ◽  
A. Würflinger ◽  
J. Li. Tamarit
Keyword(s):  
Thermal Analysis ◽  
Differential Thermal Analysis ◽  
Temperature Phase ◽  
Dielectric Studies ◽  
Static Permittivity ◽  
Coexistence Region ◽  
Disordered Phase ◽  
Plastic Phase ◽  
Related Compounds ◽  
Low Temperature Phase

Abstract Differential thermal analysis and dielectric studies under pressures up to 300 MPa and temperatures of about 200 to 350 K have been performed on 2-methyl-2-nitro-propane (TBN). TBN displays an orientationally disordered phase (ODIC), solid I, and two non-plastic phases, solids II and III. The coexistence region of the plastic phase I increases with increasing pressure, whereas the low-temperature phase II apparently vanishes at a triple point I, II, III, above 300 MPa. The static permittivity increases on freezing, characterizing the solid I as an ODIC phase. In the frame of the Kirkwood-Onsager-Fröhlich theory the g-factor is about unity, discounting specific dielectric correlations. The dielectric behaviour of TBN is similar to previously studied related compounds, such as 2-chloro-2-methyl-propane or 2-brome- 2-methyl-propane

PVT Measurements on 4′-n-Octyl-Biphenyl-4-Carbonitrile (8CB) up to 300 MPa

1998 ◽  
Vol 53 (9) ◽  
pp. 787-792
Author(s):  
M. Sandmann ◽  
A. Würflinger
Keyword(s):  
Volume Change ◽  
Atmospheric Pressure ◽  
Volume Changes ◽  
First Order ◽  
Smectic A ◽  
Enthalpy Changes ◽  
Second Order Transition ◽  
Clearing Temperature ◽  
Pvt Measurements ◽  
Period Of Oscillation

Abstract P, Vm , Tdata have been measured for the smectic, nematic and isotropic phases of 4'-n-octyl-biphen-yl-4-carbonitrile (8CB) in the temperature range 300-370 K and pressures up to 300 MPa. At atmospheric pressure all phase transitions appear to be of first order due to a discontinuity in the density. The volume change at the smectic A -nematic transition is only a tenth of the volume change at the clearing temperature. At moderate pressures below 80 MPa the SA -N transition could be detected as a discontinuity in the period of oscillation in measurements with a high-pressure vibrating tube densimeter. At higher pressures the discontinuity seems to die away, possibly indicating a change from first order to second order transition. From the volume changes and the slopes of the transition lines we calculate the enthalpy changes at the phase transition. The p, Vm , T data enable us to calculate the volume part of the entropy and the molecular field parameter γ=δln TNI/δln VNI .

pVT Measurements and Related Studies on the Binary System nC16H34 -nC17H36 and on nC18H38 at High Pressures

2001 ◽  
Vol 56 (9-10) ◽  
pp. 626-634 ◽  
Author(s):  
Albert Würflinger ◽  
Denise Mondieig ◽  
Fazil Rajabalee ◽  
Miquel Angel Cuevas-Diarte
Keyword(s):  
Binary System ◽  
Specific Volume ◽  
Transition Point ◽  
Binary Systems ◽  
High Pressures ◽  
Ambient Pressure ◽  
Melting Curve ◽  
Enthalpy Changes ◽  
Rotator Phase ◽  
Pvt Measurements

Abstract The phase diagram of the binary system nC16H34 -nC17H36 has been established at ambient pressure using DSC and crystallographic measurements. At low temperatures below the rotator phase RI there exist two crystal forms Op (about x(C17) = 0.25) and Mdci (about x(C17) = 0.67) which are different from the crystal structures of the pure compounds (Tp for C16 and Oi for C17). Furthermore two compositions: (a) C16/C17 = 3:1 and (b) = 1:2, which correspond to the coexistence range of Op and Mdci, were chosen for high pressure DTA and pVT measurements, yielding the following findings: The specific volume of the rotator phase of C17 is distinctly lower than those of the binary systems at the same state point. Assuming the existence of a metastable rotator phase for C16, an excess volume of Δ VE/V ≈ 0.01 can be estimated. Due to the very enlarged coexistence range of RI, the mixtures reach their lower transition point at considerably lower temperatures (in isobaric measurements) or higher pressures (in isothermal measurements), where the specific volume is lower than that of C17 at its transition point. Furthermore, the volume and enthalpy changes of the Φord -RI transition is distinctly smaller for the binary systems than for pure C17. Thus the specific volumes of the phases Op and Mdci are appreciably larger than ν(spec.) of C17. Op and Mdci have practically the same specific volume in accordance with the crystallographic results. Enthalpy values are obtained with the aid of the Clausius-Clapeyron equation which agree well with enthalpies derived from the DSC measurements. Furthermore, pVT data have been established for the liquid and solid phases of nC18H38 in the neighbourhood of the melting curve, allowing to determine volume and enthalpy changes of melting as a function of pressure.

Thermal Behavior of the Gypsum Binder in Dental Casting Investments

1986 ◽  
Vol 65 (6) ◽  
pp. 877-884 ◽  
Author(s):  
T. Mori
Keyword(s):  
Phase Transition ◽  
Thermal Analysis ◽  
Differential Thermal Analysis ◽  
Sodium Chloride ◽  
Thermal Behavior ◽  
Boric Acid ◽  
Atmospheric Pressure ◽  
Calcium Sulfate ◽  
Calcium Sulfate Dihydrate ◽  
Initial Stage

This study examined the thermal behavior of cast gypsum specimens, with and without additives, by means of simultaneous differential thermal analysis-thermogravimetry (DTA-TG) and dilatometry. Specimens were prepared from wet-calcined hemihydrates (Hydrocal and Den-site). The additives studied were boric acid (H3BO 3) and sodium chloride (NaCl), and these were added to the hemihydrate powders in concentrations of 2 wt% (in the case of H3BO3) and 0.5 wt% (in the case of NaCl). A large shrinkage was observed in the range of 300 to 500°C, and this was greatly reduced when either H3BO3 or NaCl was present. The dehydration of gypsum (calcium sulfate dihydrate) was not completed until the initial stage of this large shrinkage was reached, but the phase transition of calcium sulfate anhydrite (III-CaSO4 to II-CaSO4) was the major cause for the large shrinkage. This phase transition occurred over a much wider temperature range than that suggested by the DTA-TG results. Dehydration conditions similar to those employed in wet calcination of gypsum appeared to be produced under atmospheric pressure when NaCl was present.

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