A calorimetric study of acrylate photopolymerization

The kinetics of the photoinitiated polymerization of lauryl acrylate (LA), 1,6-hexanedioldiacrylate (HDDA) and pentaerythritol tetraacrylate (PET₄A) have been investigated using differential scanning calorimetry (DSC). An autoacceleration phenomenon is observed with the multifunctional acrylates, but not with lauryl acrylate. The empirical dependences of reaction rate on such parameters as incident light intensity, initiator concentration, and temperature have been established and are in general found to vary with monomer conversion. Apparent activation energies for the photopolymerizations have been determined from rate versus temperature data. The multifunctional acrylates show an increasing activation energy with monomer conversion, whereas the apparent activation energy for lauryl acrylate not only decreases with conversion, but becomes negative at conversions greater than about 30%. The ratio k_p/k is calculated from rate versus conversion data under constant illumination and the (independently determined) initiation rate. Analysis of rate versus time data under nonsteady-state conditions (light turned off) yields the ratio k_t/k_p. With these two ratios the rate constants for propagation (k_p) and termination (k_t) may be separated and their respective values calculated. Both k_p and k_t are found to decrease substantially with monomer conversion, indicating a significant change in the rates of both the propagation and termination steps as the polymerization advances. These observations are explained in terms of a radical isolation phenomenon and diffusion control of the propagation step.     

A calorimetric study of egg white proteins

Egg white is of great interest for many culinary and industrial applications. Egg white is used for coating, gluing, thickening and so on in pasta, desserts, etc. There is thus a great interest from the industrial point of view to better know this raw material, used in very large amounts in the dessert production for example, and to obtain egg white fractions with different functional properties.Various egg white fractions prepared by selected procedures were analyzed by differential scanning calorimetry (DSC). The products resulting from a given fractionation procedure can thus be described by the thermal denaturation parameters (temperatures and enthalpies) of the egg white proteins.This work demonstrates the interest of the DSC technique and proves that the fractionation procedures selected here give the expected protein fractions.     

A calorimetric study of three long-chain ionic surfactants

Differential enthalpies of solution in water of crystalline sodium dodecyl sulphate (SDS), sodium p-octylbenzenesulphonate (SOBS), and hexadecyltrimethylammonium bromide (CTAB) have been measured as a function of concentration at temperatures between 25 and 50 °C. The concentration change was small in the experiments and the results give a good approximation to the partial molar enthalpy content of the surfactant in the monomer and micellar states relative to the crystalline state. The enthalpies of dissolution to give monomers showed a strong, linear increase with temperature for SDS and SOBS and a nearly linear increase for CTAB, while the enthalpy of dissolution to give micelles was constant between 25 and 50 °C for the first two surfactants and only slowly increased for CTAB. Partial molar heat capacities were derived for monomeric and micellar SDS and SOBS. The large positive partial molar heat capacities of the monomeric surfactants are characteristic for hydrophobic solutes and the large heat capacity change for micelle formation arises from the loss of hydrophobic hydration in the formation of micelles.Results of microtitration experiments at 25 ° C show that the micelle formation of CTAB is not a simple aggregation process, but indicate a secondary process taking place closely after the critical micelle concentration (CMC).     

A differential scanning calorimetric study of some phenol derivatives

Differential scanning calorimetry has been applied to derive the fusion enthalpies and entropies of series of mono and dimethylphenols, mono and dichlorophenols, and mono and dinitrophenols.

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Zusammenfassung DSC wurde verwendet zur Ermittlung der Schmelzenthalpie und Entropie der Reihen von Mono- und Dimethylphenolen, Mono- und Dichlorphenolen, Mono- und Dinitrophenolen.

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A differential scanning calorimetric study of cysteine hydrochloride monohydrate

An irreversible phase change, ΔH (transition) = 5.44 ± 0.11 kcal mol^?1 at 337.1 ± 0.3 K has been confirmed in L-(+)-cysteine hydrochloride monohydrate. Phase transitions resulting from thermal pretreatment are also reported and discussed.     

A calorimetric study of the thermodynamic properties of potassium molybdate

The low-temperature heat capacity of K₂MoO₄ was measured by adiabatic calorimetry. The smoothed heat capacity values, entropies, reduced Gibbs energies, and enthalpies were calculated over the temperature range 0–330 K. The standard thermodynamic functions determined at 298.15 K were C _p ^° (298.15 K) = 143.1 ± 0.2 J/(mol K), S°(298.15 K) = 199.3 ± 0.4 J/(mol K), H°(298.15 K)-H°(0) = 28.41 ± 0.03 kJ/mol, and Φ°(298.15 K) = 104.0 ± 0.4 J/(mol K). The thermal behavior of potassium molybdate at elevated temperatures was studied by differential scanning calorimetry. The parameters of polymorphic transitions and fusion of potassium molybdate were determined.     

A calorimetric study of the glass transition kinetics in polyisoprene

The connection between the dielectric and calorimetric relaxation behaviours of synthetic polyisoprene Cariflex IR 305 is studied. A similar comparison of dielectric and dilatometric results was described in [1]. The heat capacity was measured during heating of samples prepared with different thermal history. Experimental results were compared with the heat capacity curves calculated for a model based on the multiparameter theory of Kovacs et al. [4]. The model considers the relaxation system as being composed of a set of subsystems characterized by different relaxation times. The distribution of relaxation times and their temperature dependence were taken from the diclectric measurement. The relaxation time of a subsystem from posed to depend, not only on the actual, temperature of the sample, but also on the deviation of this subsystem from equilibrium, or alternatively, on the deviation of the system as a whole. The comparison between the measured and modeled curves shows that both influences must be taken into account in order to explain the experimental results.Dedicated to Prof. Dr. W. Pechhold on the occasion of his 60th birthday.     

A calorimetric study of the ultrasound-stimulated hydrolysis of solventless TEOS-water mixtures

The kinetics of ultrasound-stimulated and HCl-catalyzed hydrolysis of solventless TEOS-water mixtures was studied as a function of temperature ranging from 10°C up to 65°C by means of flux calorimetry measurements. A specially designed device was utilized for this purpose. The exothermic peak arising few minutes after sonication began has been attributed mainly to the hydrolysis reaction. The overall hydrolysis process, which was measured through the irradiation time up to the hydrolysis peak, was found to be thermally activated, with an apparent activation energy E=36.4 kJ/mol. The alcohol produced at the early hydrolysis due to sonication seems to further enhance the reaction, via a parallel autocatalytic path, which is controlled by a faster pseudo second order rate constant (k). Our modeling yielded k=6.3×10^–2M^–1min^–1 at 20°C, which is in a reasonable agreement with the literature, and an activation energy E=40.4 kJ/mol for the specific process of hydrolysis in presence of alcohol.     

Interface influenced phase transitions of alkylcyanobiphenyl liquid crystals A calorimetric study

Abstract

Using an AC-calorimetry technique, we report measurements of the heat capacity and the phase shift between the applied heating power and the resulting thermal oscillations on the thermotropic liquid crystal series of alkylcyanobiphenyl (nCB) above the tricritical point. Specifically, we studied the first order phase transition smectic A to isotropic as a function of substrate, under atmospheric pressure. Different combinations of sapphire, Kapton type 200H polyimide film and air, are used to vary systematically the interfaces encountered by a liquid crystal. The calorimeter uses a sapphire disk, 10 mm in diameter and 0·13 mm thick, above which the samples are placed. A second sapphire disk, or a disk-shaped Kapton film, are used to sandwich the liquid crystal. Air interface samples are droplets allowed to spread naturally on the chosen substrate. The chosen geometry is such that interface effects appear to be maximized. Striking features found in the heat capacity and the phase shift studies with 10CB and 12CB will be presented for the different interfaces.     

A differential scanning calorimetric study on phase transformations of HgI2

A quantitative study of the different factors that influence the- transformation of mercuric iodide was carried out with differential scanning calorimetry. The transformation temperature and the peak width during the heating of the material were followed. An attempt was made to explain the experimental results.

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Zusammenfassung Mittels Differential-Scanning-Kalorimetrie wurde der Einfluss verschiedener Faktoren auf die- Umwandlung von Quecksilberjodid quantitativ untersucht. Dabei wurde die Umwandlungstemperatur und die Signalbreite beim Erhitzen der Substanz beobachtet. Es wurde ein Versuch unternommen, die experimentellen Ergebnisse zu erklären.

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Solvation of small hydrophobic molecules in formamide: A calorimetric study

The solubility and enthalpy of solution of benzene, cyclohexane, hexane, and heptane in formanide have been determined from titration microcalorimetric experiments at 25°C. The solution enthalpies are significantly more endothermic than in water but still the solubility is much higher. The entropy changes in formamide are small and positive and do not vary significantly with size. The enthalpies of solution of some 1-alkanols, 1-chloro- and 1,5-dichloropentane and pentane-1,5-diol were measured as functions of concentration. The solution enthalpies for 1-alkanols from methanol to decanol increase linearly with chain length. The enthalpic interaction coefficients h_xx are small and negative in formamide while they are large and positive in water. The partial molar heat capacities C _p,2 ^o for 1-propanol, 1-pentanol, benzene and cyclohexane in formamide were determined at 25°C from drop heat capacity measurements. Values of C _p,2 ^o are only slightly larger than the molar heat capacities of the liquid solutes.     

A calorimetric study of the temperature effect on Calcium Phosphate precipitation

The precipitation of calcium phosphate was studied using a heat flow twin calorimeter (C80, Setaram, France). The process was carried out using two identical membrane vessels. In the lower parts of both vessels 2 mL of a supersaturated solution (solution A) containing Ca(H₂PO₄)·2H₂O (0.054 M) and CaCl₂·H₂O (0.125 M) with a molar ratio Ca/P = 1.67 were added. Then 0.05 mL of an ammonium solution (25% w/w) (solution B) and 0.05 mL of distilled water were transferred in the upper parts of sample and reference vessels, respectively. After temperature had been maintained at 303, 313, 323 and 333 K the membranes of both sample and reference vessels were broken simultaneously. The precipitation process also repeated with the same conditions for periods of 15, 60 and 120 min in a bath. The first two calorimetric curves (303, 313 K) show a single exothermic step during the process as a sharp peak in the initial stage. On the contrary at the experimental temperature of 323 K except of the sharp peak in the initial stage, a steadily exothermic tendency appears after 100 min time. In higher temperature (333 K) the sharp peak appears in the initial stage followed by a broad exothermic step between 75 and 320 min time. The XRD analyses show that the solids in the initial experimental stages are mainly consisted of dicalcium phosphate dihydrate (DCPD) for the lower temperature and a biphasic or triphasic system consisted of hydroxyapatite (HA), dicalcium phosphate anhydrous (DCPA) and octacalcium phosphate (OCP) for the rest temperatures. The XRD analyses show also that during the solution aging the initial products are transformed into the more stable thermal forms of HA and octacalcium phosphate (OCP).     

A differential scanning calorimetric study on phase transformations of HgI2

The influence of stoichiometry on the mercuric iodide to transformation temperature was studied in a limited region around the exact stoichiometry. It is concluded that although this influence is small, the transformation temperature has its highest value at the exact stoichiometry composition.

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Zusammenfassung In einem begrenzten Intervall in der Nähe der exakten Stöchiometrie von Quecksilberjodid wurde der Einfluß der Stöchiometrie auf die/ß Umwandlungstemperatur untersucht. Es konnte festgestellt werden, daß dieser Einfluß zwar gering ist, die Umwandlungstemperatur ihren größten Wert jedoch bei der exakten Stöchiometrie erreicht.

     

A calorimetric contribution to the study of polymorphism in tetramethylammonium chloride

The heat capacity of tetramethylammonium chloride has been measured from 115 to 498 K, both for the thermodynamically stable modifications and for the form II, which is metastable below 407 K. The entropy gains at the IV → III λ-transition and at the III → II first-order transition are estimated to be 1.19 J K⁻¹ mol⁻¹ and 4.16 J K⁻¹ mol⁻¹, respectively. At 125 K, the entropy of the metastable phase II exceeds that of the stable modification IV by only 1.76 J K⁻¹ mol⁻¹. If, as has been suggested, each cation in phase II has two possible orientations, it would seem that at 125 K this disorder in phase II is largely, if not wholly, suppressed, without the appearance of any transition or thermal anomaly.Results are also recorded of test measurements of the heat capacity of the NBS sample of synthetic sapphire (α-Al₂O₃) from 138 to 515 K.     

A differential scanning calorimetric study of phase transitions in polysubstitutedn-alkylammonium halides

A DSC investigation of severaln-alkylammonium salts is reported. The results of this investigation can be used to help decide which of several crystalline forms should be studied by X-ray diffraction for the best correlation between the liquid and solid states.

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Zusammenfassung Es wird über eine DSC-Untersuchung verschiedenern-Alkylammoniumsalze berichtet. Die Ergebnisse dieser Untersuchung können zur Entscheidung beitragen, welche von mehreren Kristallformen durch Röntgendiffraktion untersucht werden sollten um die beste Korrelation zwischen den flüssigen und festen Zuständen zu erzielen.

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Résumé On communique les résultats d'une étude par analyse calorimétrique différentielle (DSC) de divers sels den-alkylammonium. Les résultats de cette étude donnent des indications pour le choix des formes cristallines qui nécessitent d'être étudiées par diffraction des rayons X afin d'obtenir la meilleure corrélation entre les états liquides et solides.

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Visiting Professor of Chemistry, 1973–1974, Hebrew University, Jerusalem, Israel.

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This investigation was partially supported by the National Science Foundation. The hospitality of the Department of Inorganic and Analytical Chemistry of the Hebrew University is gratefully acknowledged. The authors thank Prof. I. Mayer and A. S. Kertes of the Hebrew University for suggesting this problem and for kindly furnishing samples of then-alkylammonium halides.     

A differential scanning calorimetric study on the irreversible thermal unfolding of concanavalin A

A differential scanning calorimetry study on the thermal denaturation of concanavalin A at pH 5.2 where it exists in the dimeric form was carried out. The calorimetric transitions were observed to be irreversible and the transition temperature of the protein increased with increasing scan rate, indicating that the thermal denaturation process is under kinetic control. The thermal unfolding, and its scan rate dependence could be explained according to the kinetic scheme with k as first-order kinetic constant whose change with temperature is given by the Arrhenius equation. Using this model, rate constant as a function of temperature and activation energy of the process have been calculated. The average activation energy of the kinetic process using different approaches is 129±10 kJ mol⁻¹. The differential scanning calorimetric results on transition temperatures and calorimetric enthalpies supported by intrinsic fluorescence indicate that the irreversibility in the calorimetric transitions of concanavalin A includes a combination of post-transition aggregation, chain separation and loss of cofactor.     

A theoretical study on growth patterns of Ni-doped germanium clusters

Ni-doped germanium clusters have been systematically investigated by using the density functional approach. The growth-pattern behaviors, stabilities, charge transfer, and polarities of these clusters are discussed in detail. Obviously different growth patterns appear between small-sized Ni-doped germanium clusters and middle- or larger-sized Ni-doped germanium clusters. The Ni-convex or substituted Ge(n) frames for small-sized clusters as well as Ni-concaved or encapsulated Ge(n) frames for middle- or large-sized clusters are dominant growth patterns. The calculated fragmentation energies manifest that the magic numbers of stabilities are 5, 8, 10, and 13 for Ni-doped germanium clusters; the obtained relative stabilities exhibit that the Ni-encapsulated Ge(10) cluster is the most stable species of all different-sized clusters, which is in good agreement with available experimental observations of CoGe(10)(-). Natural population analysis shows that different charge-transfer phenomena depend on the sizes of the Ni-doped Ge(n) clusters. Additionally, the properties of frontier orbitals and the polarities of Ni-doped Ge(n) clusters are also discussed.     

Differential calorimetric study of polycyclic aromatic hydrocarbons

The temperature, enthalpy, entropy of melting and crystal transitions of 21 polycyclic aromatic hydrocarbons, containing from 2 to 6 unsubstituted condensed rings, were determined by differential scanning calorimetry. The temperature and the molar entropy of melting generally increase with increasing degree of symmetry and molecular size of the hydrocarbon. Apparent deviations from this trend are discussed in terms of molecular distorsion due to steric interaction between neighbouring hydrogens.