Low temperature heat capacity of (S)-ibuprofen

Molar heat capacities of ( S)-ibuprofen were precisely measured with a small sample precision automated adiabatic calorimeter over the temperature range from 80 to 370 K. Experimental heat capacities were fitted into a polynomial equation of heat capacities ( C-p,C- m) with reduced temperature ( X), [ X = f(T)]. The polynomial equations for ( S)-ibuprofen were C-p,C- m(s) = - 39.483 X-4 - 66. 649 X-3 + 95. 196 X-2 + 210. 84 X + 172. 98 in solid state and C-p,C- m(L) = 7. 191X(3) + 4. 2774 X-2 + 56. 365 X + 498. 5 in liquid state. The thermodynamic functions relative to the reference temperature of 298. 15 K, H-T - H-298.15 and S-T - S-298.15, were derived for the( S)-ibuprofen. A fusion transition at T-m = (324. 15 +/- 0. 02) K was found from the C-p - T curve. The molar enthalpy and entropy of the fusion transition were determined to be (18. 05 +/- 0. 31) kJ.mol(-1) and (55. 71 +/- 0. 95) J.mol(-1).K-1, respectively. The purity of the ( S)-ibuprofen was determined to be 99. 44% on the basis of the heat capacity measurement. Finally, the heat capacities of ( S)-ibuprofen and racemic ibuprofen were compared.

Measurements of the heat capacity of an azeotropic mixture of water and n-butanol from 78 to 320 K

Molar heat capacities of n-butanol and the azeotropic mixture in the binary system [water (x=0.716) plus n-butanol (x=0.284)] were measured with an adiabatic calorimeter in a temperature range from 78 to 320 K. The functions of the heat capacity with respect to thermodynamic temperature were established for the azeotropic mixture. A glass transition was observed at (111.9 +/- 1.1) K. The phase transitions took place at (179.26 +/- 0.77) and (269.69 +/- 0.14) K corresponding to the solid-liquid phase transitions of. n-butanol and water, respectively. The phase-transition enthalpy and entropy of water were calculated. A thermodynamic function of excess molar heat capacity with respect to temperature was established, which took account of physical mixing, destructions of self-association and cross-association for n-butanol and water, respectively. The thermodynamic functions and the excess thermodynamic ones of the binary systems relative to 298.15 K were derived based on the relationships of the thermodynamic functions and the function of the measured heat capacity and the calculated excess heat capacity with respect to temperature.

Heat capacity and thermodynamic properties of myclobutanil

The low-temperature heat capacities of myclobutanil (C15H17CIN4) were precisely measured with an automated adiabatic calorimeter over the temperature range from 78 to 368 K. The sample was observed to melt at (348.800 +/- 0.06) K. The molar enthalpy and entropy of the melting as well as the chemical purity of the substance were determined to be Delta(fus)H(m) = (30931 +/- 11) J.mol(-1), Delta(fus)S(m) = (88.47 +/- 0.02) J.mol(-1).K-1 and 99.41%, respectively. Further research of the melting process for this compound was carried out by means of DSC technique. The result was in agreement with that obtained from the measurements of heat capacities.

Heat capacity and enthalpy of fusion of fenoxycarb

Fenoxycarb was synthesized and its heat capacities were precisely measured with an automated adiabatic calorimeter over the temperature range from 79 to 360 K. The sample was observed to melt at (326.31 +/- 0.14) K. The molar enthalpy and entropy of fusion as well as the chemical purity of the compound were determined to be (26.98 +/- 0.04) kJ-mol(-1), (82.69 +/- 0.09) J-K-1-mol(-1) and 99.53% +/- 0.01%, respectively. The thermodynamic functions relative to the reference temperature (298.15 K) were calculated based on the heat capacity measurements in the temperature range between 80 and 360 K. The extrapolated melting temperature for the absolutely pure compound obtained from fractional melting experiments was (326.62 +/- 0.06) K. Further research on the melting process of this compound was carried out by means of differential scanning calorimetry technique. The result was in agreement with that obtained from the measurements of heat capacities.

Study of heat capacity measurement methods for small samples

Methods of measuring specific heats of small samples were studied. Three automated methods were explored, two of which have shown promising results. The adiabatic continuous heating method, has provided smooth well behaved data but further work is presently underway to improve on the results obtained so far . The decay method has been success fully implemented demonstrating reasonable agreement with accepted data for a copper test sample.

Time-dependent heat capacity of Mn12 clusters

In this paper we discuss both theoretical and experimental results on the time dependence of the heat capacity of oriented Mn12 magnetic clusters when a magnetic field is applied along their easy axis. Our calculations are based on the existence of two contributions. The first one is associated with the thermal populations of the 21 different Sz levels in the two potential wells of the magnetic uniaxial anisotropy and the second one is related to the transitions between the Sz levels. We compare our theoretical predictions with experimental data on the heat capacity for different resolution times at different fields and temperatures.

Density, heat capacity and thermal conductivity of liquid egg products

Density, heat capacity and thermal conductivity of liquid egg products, such as egg white, egg yolk, whole egg and various white and yolk blends, were determined as affected by temperature and water content ranging from 273 to 311 K and 51.8 to 88.2% (mass), respectively. Polynomial models fitted the experimental data very well, showing a linear relationship both for temperature and water content. (c) 2005 Published by Elsevier Ltd.

Temperature and concentration dependence of heat capacity of model aqueous solutions

Heat capacities of binary aqueous solutions of different concentrations of sucrose, glucose, fructose, citric acid, malic acid, and inorganic salts were measured with a differential scanning calorimeter in the temperature range from 5degreesC to 65degreesC. Heat capacity increased with increasing water content and increasing temperature. At low concentrations, heat capacity approached that of pure water, with a less pronounced effect of temperature, and similar abnormal behavior of pure water with a minimum around 30degreesC-40degreesC. Literature data, when available agreed relatively well with experimental values. A correction factor, based on the assumption of chemical equilibrium between liquid and gas phase in the Differential Scanning Calorimeter, was proposed to correct for the water evaporation due to temperature rise. Experimental data were fitted to predictive models. Excess molar heat capacity was calculated using the Redlich-Kister equation to represent the deviation from the additive ideal model.

Implementation of the Heated Pulsed Theory using actively heated fiber optics: measurements of soil volumetric water content and soil volumetric heat capacity

Existe una creciente necesidad de hacer el mejor uso del agua para regadío. Una alternativa eficiente consiste en la monitorización del contenido volumétrico de agua (θ), utilizando sensores de humedad. A pesar de existir una gran diversidad de sensores y tecnologías disponibles, actualmente ninguna de ellas permite obtener medidas distribuidas en perfiles verticales de un metro y en escalas laterales de 0.1-1,000 m. En este sentido, es necesario buscar tecnologías alternativas que sirvan de puente entre las medidas puntuales y las escalas intermedias. Esta tesis doctoral se basa en el uso de Fibra Óptica (FO) con sistema de medida de temperatura distribuida (DTS), una tecnología alternativa de reciente creación que ha levantado gran expectación en las últimas dos décadas. Específicamente utilizamos el método de fibra calentada, en inglés Actively Heated Fiber Optic (AHFO), en la cual los cables de Fibra Óptica se utilizan como sondas de calor mediante la aplicación de corriente eléctrica a través de la camisa de acero inoxidable, o de un conductor eléctrico simétricamente posicionado, envuelto, alrededor del haz de fibra óptica. El uso de fibra calentada se basa en la utilización de la teoría de los pulsos de calor, en inglés Heated Pulsed Theory (HPP), por la cual el conductor se aproxima a una fuente de calor lineal e infinitesimal que introduce calor en el suelo. Mediante el análisis del tiempo de ocurrencia y magnitud de la respuesta térmica ante un pulso de calor, es posible estimar algunas propiedades específicas del suelo, tales como el contenido de humedad, calor específico (C) y conductividad térmica. Estos parámetros pueden ser estimados utilizando un sensor de temperatura adyacente a la sonda de calor [método simple, en inglés single heated pulsed probes (SHPP)], ó a una distancia radial r [método doble, en inglés dual heated pulsed probes (DHPP)]. Esta tesis doctoral pretende probar la idoneidad de los sistemas de fibra óptica calentada para la aplicación de la teoría clásica de sondas calentadas. Para ello, se desarrollarán dos sistemas FO-DTS. El primero se sitúa en un campo agrícola de La Nava de Arévalo (Ávila, España), en el cual se aplica la teoría SHPP para estimar θ. El segundo sistema se desarrolla en laboratorio y emplea la teoría DHPP para medir tanto θ como C. La teoría SHPP puede ser implementada con fibra óptica calentada para obtener medidas distribuidas de θ, mediante la utilización de sistemas FO-DTS y el uso de curvas de calibración específicas para cada suelo. Sin embargo, la mayoría de aplicaciones AHFO se han desarrollado exclusivamente en laboratorio utilizando medios porosos homogéneos. En esta tesis se utiliza el programa Hydrus 2D/3D para definir tales curvas de calibración. El modelo propuesto es validado en un segmento de cable enterrado en una instalación de fibra óptica y es capaz de predecir la respuesta térmica del suelo en puntos concretos de la instalación una vez que las propiedades físicas y térmicas de éste son definidas. La exactitud de la metodología para predecir θ frente a medidas puntuales tomadas con sensores de humedad comerciales fue de 0.001 a 0.022 m3 m-3 La implementación de la teoría DHPP con AHFO para medir C y θ suponen una oportunidad sin precedentes para aplicaciones medioambientales. En esta tesis se emplean diferentes combinaciones de cables y fuentes emisoras de calor, que se colocan en paralelo y utilizan un rango variado de espaciamientos, todo ello en el laboratorio. La amplitud de la señal y el tiempo de llegada se han observado como funciones del calor específico del suelo. Medidas de C, utilizando esta metodología y ante un rango variado de contenidos de humedad, sugirieron la idoneidad del método, aunque también se observaron importantes errores en contenidos bajos de humedad de hasta un 22%. La mejora del método requerirá otros modelos más precisos que tengan en cuenta el diámetro del cable, así como la posible influencia térmica del mismo. ABSTRACT There is an increasing need to make the most efficient use of water for irrigation. A good approach to make irrigation as efficient as possible is to monitor soil water content (θ) using soil moisture sensors. Although, there is a broad range of different sensors and technologies, currently, none of them can practically and accurately provide vertical and lateral moisture profiles spanning 0-1 m depth and 0.1-1,000 m lateral scales. In this regard, further research to fulfill the intermediate scale and to bridge single-point measurement with the broaden scales is still needed. This dissertation is based on the use of Fiber Optics with Distributed Temperature Sensing (FO-DTS), a novel approach which has been receiving growing interest in the last two decades. Specifically, we employ the so called Actively Heated Fiber Optic (AHFO) method, in which FO cables are employed as heat probe conductors by applying electricity to the stainless steel armoring jacket or an added conductor symmetrically positioned (wrapped) about the FO cable. AHFO is based on the classic Heated Pulsed Theory (HPP) which usually employs a heat probe conductor that approximates to an infinite line heat source which injects heat into the soil. Observation of the timing and magnitude of the thermal response to the energy input provide enough information to derive certain specific soil thermal characteristics such as the soil heat capacity, soil thermal conductivity or soil water content. These parameters can be estimated by capturing the soil thermal response (using a thermal sensor) adjacent to the heat source (the heating and the thermal sources are mounted together in the so called single heated pulsed probe (SHPP)), or separated at a certain distance, r (dual heated pulsed method (DHPP) This dissertation aims to test the feasibility of heated fiber optics to implement the HPP theory. Specifically, we focus on measuring soil water content (θ) and soil heat capacity (C) by employing two types of FO-DTS systems. The first one is located in an agricultural field in La Nava de Arévalo (Ávila, Spain) and employ the SHPP theory to estimate θ. The second one is developed in the laboratory using the procedures described in the DHPP theory, and focuses on estimating both C and θ. The SHPP theory can be implemented with actively heated fiber optics (AHFO) to obtain distributed measurements of soil water content (θ) by using reported soil thermal responses in Distributed Temperature Sensing (DTS) and with a soil-specific calibration relationship. However, most reported AHFO applications have been calibrated under laboratory homogeneous soil conditions, while inexpensive efficient calibration procedures useful in heterogeneous soils are lacking. In this PhD thesis, we employ the Hydrus 2D/3D code to define these soil-specific calibration curves. The model is then validated at a selected FO transect of the DTS installation. The model was able to predict the soil thermal response at specific locations of the fiber optic cable once the surrounding soil hydraulic and thermal properties were known. Results using electromagnetic moisture sensors at the same specific locations demonstrate the feasibility of the model to detect θ within an accuracy of 0.001 to 0.022 m3 m-3. Implementation of the Dual Heated Pulsed Probe (DPHP) theory for measurement of volumetric heat capacity (C) and water content (θ) with Distributed Temperature Sensing (DTS) heated fiber optic (FO) systems presents an unprecedented opportunity for environmental monitoring. We test the method using different combinations of FO cables and heat sources at a range of spacings in a laboratory setting. The amplitude and phase-shift in the heat signal with distance was found to be a function of the soil volumetric heat capacity (referred, here, to as Cs). Estimations of Cs at a range of θ suggest feasibility via responsiveness to the changes in θ (we observed a linear relationship in all FO combinations), though observed bias with decreasing soil water contents (up to 22%) was also reported. Optimization will require further models to account for the finite radius and thermal influence of the FO cables, employed here as “needle probes”. Also, consideration of the range of soil conditions and cable spacing and jacket configurations, suggested here to be valuable subjects of further study and development.

Heated fiber optic distributed temperature sensing for measuring soil volumetric heat capacity and water content: A dual probe heat-pulse approach

The first feasibility study of using dual-probe heated fiber optics with distributed temperature sensing to measure soil volumetric heat capacity and soil water content is presented. Although results using different combinations of cables demonstrate feasibility, further work is needed to gain accuracy, including a model to account for the finite dimension and the thermal influence of the probes. Implementation of the dual-probe heat-pulse (DPHP) approach for measurement of volumetric heat capacity (C) and water content (θ) with distributed temperature sensing heated fiber optic (FO) systems presents an unprecedented opportunity for environmental monitoring (e.g., simultaneous measurement at thousands of points). We applied uniform heat pulses along a FO cable and monitored the thermal response at adjacent cables. We tested the DPHP method in the laboratory using multiple FO cables at a range of spacings. The amplitude and phase shift in the heat signal with distance was found to be a function of the soil volumetric heat capacity. Estimations of C at a range of moisture contents (θ = 0.09– 0.34 m3 m−3) suggest the feasibility of measurement via responsiveness to the changes in θ, although we observed error with decreasing soil water contents (up to 26% at θ = 0.09 m3 m−3). Optimization will require further models to account for the finite radius and thermal influence of the FO cables. Although the results indicate that the method shows great promise, further study is needed to quantify the effects of soil type, cable spacing, and jacket configurations on accuracy.

An annotated bibliography of compiled thermodynamic data sources for biochemical and aqueous systems (1930 to 1975) : equilibrium, enthalpy, heat capacity, and entropy data /

101 selected references to books and journal articles. Also includes some foreign-language titles. Alphabetical arrangement by primary authors. Each entry gives bibliographical information and annotation. Author, subject indexes.

The enthalpy and heat capacity of uranium monocarbide to 1200C /

"Contract AT(30-1)-2789."

Estimating the specific heat capacity of starch-water-glycerol systems as a function of temperature and compositions

Increasing interests in the use of starch as biodegradable plastic materials demand, amongst others, accurate information on thermal properties of starch systems particularly in the processing of thermoplastic starch (TPS), where plasticisers (water and glycerol) are added. The specific heat capacity of starch-water-glycerol mixtures was determined within a temperature range of 40-120degreesC. A modulated temperature differential scanning calorimeter (MTDSC) was employed and regression equations were obtained to predict the specific heat capacity as a function of temperature, water and glycerol content for four maize starches of differing amylose content (0 - 85%). Generally, temperature and water content are directly proportional to the specific heat capacity of the systems, but the influence of glycerol content on the thermal property varied according to the starch type.