High-precision adiabatic calorimetry and the specific heat of cyclopentane at low temperature

We describe a fully automated adiabatic calorimeter designed for high-precision covering the temperature range 15 to 300 K. Initial measurements were performed on synthetic sapphire (20 g). The statistical error of the apparatus estimated from the scattering of theC _p data of sapphire is about 0.1% and the average absolute error of specific heat between 100 and 300 K was 0.7% compared to values given in the literature. The heat capacity and the three phase transitions of cyclopentane (C₅H₁₀) which is recommended as a standard for the temperature calibration of scanning calorimeters have also been measured. The transition temperatures were determined to be (literature values in parentheses): 122.23 K (122.39 K) 138.35 K (138.07 K) and 178.59 K (179.69 K), with an experimental error of ±40 mK.     

The standard molar enthalpies of formation of chromone-3-carboxylic acid, 6-methylchromone-2-carboxylic acid,and 6-methyl-4-chromanone determined by micro-combustion calorimetry

The energies of combustion of chromone-3-carboxylic acid (C3CA), 6-methylchromone-2-carboxylic acid (6MCC), and 6-methyl-4-chromanone (6M4C) were determined using an isoperibolic micro-combustion calorimeter. The calorimeter used in the present work has been assembled, calibrated, and tested in our laboratory with the desired results. Prior to the measurement of the energies of combustion, the purities, heat capacities (C _p), fusion temperatures (T _fus), and enthalpies of melting (Δ_fus H) for each compound were determined by differential scanning calorimetry. The values of the energies of combustion were used to derive standard molar enthalpies of combustion ( \( \Delta _{{\text{c}}} H_{{\text{m}}}^{\circ } \) ) and standard molar enthalpies of formation ( \( \Delta _{{\text{f}}} H_{{\text{m}}}^{\circ } \) ) in the crystalline phase at T = 298.15 K. The values found for the \( \Delta _{{\text{f}}} H_{{\text{m}}}^{\circ } \) of C3CA, 6MCC, and 6M4C were ?(619.5 ± 2.6), ?(656.2 ± 2.2), and ?(308.9 ± 3.0) kJ mol^?1, respectively.     

Construction,calibration and testing of a micro-combustion calorimeter

An isoperibolic micro-combustion calorimeter was designed, built and set up in our laboratory, taking as base a 1107 Parr combustion bomb of 22 cm³ of volume. Taken into account the geometrical form of the bomb, it was designed and constructed a vessel and a submarine chamber in brass. All of the pieces of the calorimeter were chromium-plated to reduce heat loss by radiation. The calorimeter was calibrated by using pellets of standard benzoic acid (mass approximate of 40 mg) leading to the energy equivalent of ε(calor) = (1283.8 ± 0.6) J · K⁻¹. In order to test the calorimeter, combustion experiments of salicylic acid were performed leading to a value of combustion energy of Δ_cu^∘ = −(21,888.8 ± 10.9) J · g⁻¹, which agrees with the reported literature values. The combustion of piperonylic acid was carried out as a further test leading to a value of combustion energy of Δ_cu^∘ = −(20,215.9 ± 10.4) J · g⁻¹ in accordance with the reported literature value. The uncertainty of the calibration and the combustion of salicylic acid and piperonylic acid was 0.05%.     

Pseudo-adiabatic calorimetry

A procedure is described for dealing with the error sources inherently present in any real calorimeter: work of powerP _s input from stirrer and possibly temperature sensor, and heat exchange at a rate ?G(T?T _e ) whereT andT _c are the temperatures of calorimeter and surroundings respectively. The constantsP _s andG are calculated from a period of thermal decay, and afterwards are used to correct the entire run. A calorimeter was designed with high thermal homogeneity and used in a test. The curve of calculated temperature exactly traces the heater energy, even after 5 h, with a standard deviation of about 1 mK. The relative error inC _p is less than 1/1000.     

Adsorption calorimetry

The efficiency of activated carbons prepared from corncob, to remove asphaltenes from toluene modeled solutions, has been studied in this work. The activating agent effect over carbonaceous solid preparation , and also temperature effect on the asphaltenes adsorption on the prepared activated carbons, was studied. The asphaltene adsorption isotherms were determined, and the experimental data were analyzed applying the Langmuir, Freundlich, Redlich–Peterson, Toth and Radke–Prausnitz and Sips models. Redlich–Peterson model described the asphaltenes isotherm on the activated carbons better. The asphaltenes adsorption capacities at 25° for activated carbons were: 1305 mg g^?1, 1654 mg g^?1 and 559.1 mg g^?1 for GACKOH, GACKP and GACH₃PO₄, respectively. Thermodynamic parameters such as ΔG°, ΔH°, and ΔS° were also evaluated from the adsorption isotherms in asphaltene solutions from toluene solutions, and it was found that the adsorption process was spontaneous and exothermic in nature. Kinetic parameters, reaction rate constant and equilibrium adsorption capacities were evaluated and correlated for each kinetic model. The results show that asphaltene adsorption is described by pseudo-second-order kinetics, suggesting that the adsorption process is chemisorption. The adsorption calorimetry was used to analyze the type of interaction between the asphaltenes and the activated carbons prepared in this work, and their values were compared with the enthalpic values obtained from the Clausius–Clapeyron equation.

     

Correlation analysis of cone calorimetry and microscale combustion calorimetry experiments

Flammability studies are conducted to evaluate the behavior of materials exposed to fire. In this study, microscale combustion calorimetry (MCC) and cone calorimetry methods were applied to acquire the flammability characteristics of red and grey extruded polystyrene (XPS) samples. To understand the effect of changes between parameters, Pearson’s correlation coefficient was used to examine their linear relationships. From the research, moderate and weak correlations were recorded between the total heat release rates from both methods for red and grey XPS, respectively. Plotting peak heat release rate against heat release temperature for MCC and ignition temperature for cone test showed that 25, 35 and 50 kW m^?2 incident heat fluxes of the cone test fall within 0.2 K s^?1 and 0.5 K s^?1 heating rates of MCC. Also, all the MCC parameters except char yield and total heat release presented good correlations with the cone calorimetry flammability characteristics. Hence, MCC could be used in conjunction with cone calorimetry to accurately and reliably assess the flammability of materials.

     

Learning about calorimetry

Calorimetry deals with the energetics of atoms, molecules, and phases and can be used to gather experimental details about one of the two roots of our knowledge about matter. The other root is structural science. Both are understood from the microscopic to the macroscopic scale, but the effort to learn about calorimetry has lagged behind structural science. Although equilibrium thermodynamics is well known, one has learned in the past little about metastable and unstable states. Similarly, Dalton made early progress to describe phases as aggregates of molecules. The existence of macromolecules that consist of as many atoms as are needed to establish a phase have led, however, to confusion between colloids (collections of microphases) and macromolecules which may participate in several micro- or nanophases. This fact that macromolecules can be as large or larger than phases was first established by Staudinger as late as 1920. Both fields, calorimetry and macromolecular science, found many solutions for the understanding of metastable and unstable states. The learning of modern solutions to the problems of materials characterization by calorimetry is the topic of this paper.This work was financially supported by the Div. of Materials Res., NSF, Polymers Program, Grant # DMR 90-00520 and Oak Ridge National Laboratory, managed by Lockheed Martin Energy Research Corp. for the U. S. Department of Energy, under contract number DE-AC05-96OR22464. Support for instrumentation came from TA Instruments, Inc. Research support was also given by ICI Paints, and Toray Industries, Inc.     

Orientation of anthracene molecules in naphthalene and tetracene molecules in anthracene single crystals

The orientation of isolated anthracene and tetracene molecules in naphthalene and anthracene single crystals, respectively, was determined using electron spin resonance. The result indicates only small deviations of less than 60° from that of a molecule in a substitutional position.     

Electrolysis in calorimetry

The procedure used by many electrochemists in calculating enthalpy in calorimetric measurements of electrolysis reactions is compared to a purely thermodynamic approach, using the data published by Fleischmannet al. [J. Electroanal. Chem., 287 (1990) 293.] as a case study.The set of excess values dH _ex/dt=dH _obs/dt -dH_calo/dt obtained with the former procedure was neither correlated to any of the experimental parameters nor to the set of values found using thermodynamics. The latter, smaller by factors of up to two orders of magnitude, are shown to follow an expression of the form dH _ex/dt=–kI exp (–E _a/RT) with an activation enthalpy of about 85 kJ·mol^–1. It is suggested that recombination of electrolysis gases may account for this.

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Zusammenfassung Das von vielen Elektrochemikern verwendete Verfahren zur Berechnung der Enthalpie in kalorimetrischen Messungen an Elektrolysereaktionen wurde unter Anwendung der von Fleischmann et.al. in einer Fallstudie [J. Electroanal. Chem., 287 (1990) 293.] veröffentlichten Angaben mit einer rein thermodynamischen Näherung verglichen.Eine Reihe von mit der ersten Methode erhaltenen überschu\werten dH _ex/dt=dH _obs/dt-dH _calc/dt korrelierte weder mit den experimentellen Parametern noch mit den entsprechenden, thermodynamisch gefundenen Werten. Letztere, um etwa zwei Grö\enordnungen kleinere Werte konnten durch die Gleichung dH _ex/dt= -kI exp (-E _a/RT) mit einer Aktivierungsenthalpie von etwa 85 kJ·mol^–1 beschrieben werden. Es wird deshalb nahegelegt, da\ dies einer Rekombinierung der Elektrolysegase zugeschrieben werden kann.

     

Heat capacity calorimetry

Experimental heat capacity measurements of α-ZrW₂O₈, and zeolitic polymorphs of SiO₂, BEA and MFI, have been made from 0.6 to 400 K. Measurements on β-ZrMo₂O₈ have been made from 8 to 400 K. Analysis of the results yields evidence for very low frequency modes in all four materials. These modes are responsible for negative thermal expansion behavior in α-ZrW₂O₈ and β-ZrMo₂O₈. Negative thermal expansion has been observed in some pure SiO₂ zeolites, but no studies have been made to look for it in BEA and MFI. The appearance of low frequency modes in these two zeolites suggests that temperature dependent structural investigations would be worthwhile. These modes are lower in energy than the Boson peak in vitreous silica. This revised version was published online in August 2006 with corrections to the Cover Date.     

High-sensitive heat-flow calorimetry

Heat production rates of chemical reactions or of biological cultures are a valuable signal, able to provide crucial information about the system under investigation. Commercially available bench-scale calorimeters reach a sensitivity of ≈100 mW/l. This sensitivity is usually sufficient for investigations in the field of reaction engineering or for safety studies. For the investigation of processes that exhibit only small exothermic or endothermic effects on the observation of the growth of biological material, the sensitivity of the calorimeter needs to be improved. This paper describes the modifications undertaken to reach a sensitivity of a few milliwatts per liter with an RC1 from Mettler-Toledo.     

New developments and applications in titration calorimetry and reaction calorimetry

Isothermal titration calorimetry (ITC) and reaction calorimetry (RC) have been used to construct the solid-liquid equilibrium line in ternary systems containing the solute to precipitate and an aqueous mixed solvent, and to study polymerization reactions under real process conditions, respectively. Phase diagrams have been established over the whole concentration range for some benzene substituted derivatives, including o-anisaldehyde, 1,3,5-trimethoxybenzene and vanillin, in {water + alcohol}mixtures at different temperatures. Acrylamide polymerization in aqueous solution using potassium permanganate/acid oxalic redox system as initiator was investigated on a homemade calorimeter, which works according to the isoperibolic mode. A Calvet type differential RC was used to illustrate the applicability of temperature oscillation calorimetry (TOC) for the evaluation of the heat transfer coefficient during the course of reaction.     

Pulsed bed calorimetry

Conventional calorimetry has always the difficulty of choosing between near to equilibrium working conditions and high thermal ramp rates. Thus, either the transport phenomena and sample homogeneities are good but the signals become weak due to thermal losses, or the signals are sharp, but strong gradients across the sample lead to chemical and thermal heterogeneities. The described pulsed fluidized bed technique, by strongly stirring the sample, allows good sample homogeneities even at high ramp rates. Moreover, the permanently regenerated cover gas allows as well a good heat transfer towards the thermocouples as a constant atmosphere composition leading to very precise onset temperatures.     

The art of calorimetry

An introduction to the various types of calorimeters is given. The requirements for precise temperature measurements with thermistors are derived. Methods and equations for accurate heat exchange corrections for isoperibol temperature-change calorimetry under various conditions are derived. The characteristics and design principles for constant temperature baths are discussed. The construction of devices for addition of reagents, of stirrers, and of calibration heaters is described.     

Photopyroelectric calorimetry of solids

An alternative photopyroelectric (PPE) technique that combines the front detection configuration (FPPE) with the thermal wave resonator cavity (TWRC) method is proposed. The theoretical analysis of the FPPE signal indicates that the configuration also offers information about both fluid sample and backing solid material. It is demonstrated that the normalized phase of the FPPE signal has an oscillating dependence as a function of the sample’s thickness. In the thermally thin regime for the sensor and liquid sample, the method can be used for direct measurement of backing thermal effusivity. This article presents experimental results on solid materials, with various values of thermal effusivity (Cu, brass, steel, glass, bakelite, and wood), used as backings in the detection cell. A study of the sensitivity of the technique for different liquid/backing effusivity ratios is performed. The main result of this article is the possibility of deriving the thermal effusivity of a solid sample (backing material) by monitoring the thickness of a fluid with well-known properties. In such a way, the so-called coupling fluid is not anymore a disturbing factor; however, its properties can be used to obtain the value of the thermal effusivity of a solid. The method proved to be suitable especially for thermal effusivity investigations of low thermal conductors. An application on polymer composites with different liquid/powder content is presented.     

Differential scanning calorimetry

This study was aimed to investigate the physicochemical changes induced in 200 nm extruded oligolamellar DPPC:DPPG (10:1) liposomes by freezing, followed by γ-irradiation, in the absence and presence of 5 mM stable cyclic nitroxide radicals, 2,2,6,6-tetramethylpiperidine-1-oxyl (Tempo) and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (Tempol). The characterization is based on the use of differential scanning calorimetry (DSC) and was aimed to differentiate the contribution of freezing and γ-irradiation in the presence and absence of nitroxides. Liposomal preparations of DPPC/DPPG which have sub-, pre- and main-phase transitions in the temperature range (0°C<T _m<50°C) were used. Our results show that: (1) freezing modified and induced fusion to MLV as well as fission to SUV, (2) freezing did not fully prevent the radiation-induced changes in the thermotropic characteristics of the liposomes, and (3) Tempo and Tempol did not prevent the changes in thermotropic behavior caused as a result of freezing of the liposomal dispersion. These results demonstrate that DSC is a powerful and sensitive tool in both physical and chemical studies of lipid assemblies. This work was supported in part by the Szold Foundation, Jerusalem, Israel and United State-Israel Binational Science Foundation (grant 95/318 to Y.B.).     

Analysis by calorimetry

The last years have seen the development of differential calorimetry into a scanning technique for routine analysis. In order of ease of determination heats of fusion, heats of reaction, phase diagrams, purity analysis, heat capacity and similar heat effects are added to the list of quickly measurable quantities. Accuracies of the order of 1–5% of heats of fusion and heat capacity are obtainable under favorable conditions. Special topics which have been discussed are instrumentation, transition temperatures, heat capacities, glass transitions, heats of transitions, and phase diagrams.     

Synthesis of anthracene ethers from anthracene methyl ethers via an acid-catalyzed exchange reaction

Selective synthesis of anthracene ethers was achieved under mild conditions via an acid-catalyzed ether-ether exchange reaction and its scope and limitations, as well as its potential in synthesizing anthracene-based crown ethers, tested.     

Polybenzimidazoles containing anthracene photodimer

Polybenzimidazoles that contained anthracene photodimer were prepared. The molecular weights of the polymers prepared by the photopolymerization of bis-anthrylbenzimidazoles were limited by the precipitation of the resulting polymers from the reaction organic solvents. Higher molecular weight polymers were obtained by the photopolymerization of bis-anthryl-Schiff's bases, followed by the oxidation of the resulting polymers. These polymers were soluble in acidic solvents such as formic and sulfuric acids but were insoluble in organic solvents.