A theoretical method of researching ion-molecule reactions in solution

A method has been devised for researching the mechanisms of ion-molecule reactions in aqueous solutions, which involves deriving an approximate reaction path by means of a model Hamiltonian, in which the medium is described by a set of point Langevin dipoles. At the stationary points on the PES derived in that way, the solvation may be simulated by means of a more accurate scheme for the medium, namely by direct optimization of the potential energy for the solvate shell. The method has been tested on the reaction CO₂+OH^–HCO₃ ^–. The model Hamiltonian has been constructed by MINDO/3. Good agreement with experiment is obtained.Translated from Teoreticheskaya i Éxperimental'naya Khimiya, Vol. 23, No. 3, pp. 281–288, May–June, 1987.     

Isothermal calorimeter for studies of polymer solution processes

A simple differential, isothermal calorimeter has been built to study the thermodynamics of interactions associated with a variety of polymer solution processes. The calorimeter is readily operated at temperatures ranging from ambient to about 200°C., temperature adjustments are rapid, and the apparatus is rugged enough to permit application to commercial process studies. Though less sensitive than microcalorimeters, it represents an attractive combination of satisfactory accuracy, speed, and flexibility of operation. The operation of the calorimeter is demonstrated by measurements of the heat of solution of sodium chloride in water and the heats of solution of various polyolefins in Tetralin and α-chloronaphthalene. The latter tend to confirm the presence of polymer aggregates in chloronaphthalene solutions below the thermodynamic melting temperature of the polymer.     

Characteristic parameter method for studying kinetics of opposing reactions in calorimeter

According to the theoretical basis of thermokinetics, the integral and differential thermokinetic equations of opposing reactions have been derived, and a novel thermokinetic research method, the characteristic parameter method for opposing reactions which taking place in a batch conduction calorimeter under isothermal condition, has been proposed in this paper. Only needing the characteristic thermoanalytical data corresponding to t_m and 2t_m from the same curve, the rate constants of forward and backward reactions and equilibrium constant can be calculated simultaneously with this method. In order to test the validity of this method, the proton-transfer reactions of nitroethane with ammonia at 15 and 25°C, and with trihydroxymethyl aminomethane (Tris) at 15 and 30°C have been studied, respectively. The results of rate constants and equilibrium constants calculated with this method are in agreement with those in the literature. Therefore, the characteristic parameter method for opposing reaction is believed to be correct.This revised version was published online in November 2005 with corrections to the Cover Date.     

Conditions for calibration of an isothermal titration calorimeter using chemical reactions

The reaction of protonation of 2-amino-2-(hydroxymethyl)-1,3-propanediol (TRIS) is a suitable one for the calibration of isothermal titration calorimeter (ITC), providing that experimental conditions are appropriately chosen. The conditions and methods for handling experimental data from a nanowatt-ITC are discussed. Also, the binding of Ba²⁺ to 18-Crown-6 is successfully used to check the accuracy and precision of the chemical calibration performed with TRIS. This latter reaction has the additional advantage that the data can also be used for a check on the determination of the value of a binding constant. The anomaly of the first injection in ITC is analyzed and, by combining calorimetric and spectroscopic measurements, it is shown that it mainly results from a backlash effect of the syringe plunger rather than from a diffusion effect.     

Fitting isoperibolic calorimeter data for reactions with pseudo-first order chemical kinetics

The non-linear least squares fitting of the chemical heat flow and the reactor temperature are compared for reactions with pseudo-first order chemical kinetics carried out in an isoperibolic calorimeter operating quasi-isothermally. Both methods give very similar results for the reaction rate constant and enthalpy of reaction but fitting the reactor temperature appears to have some advantages especially when there is an enthalpy of mixing of the reagents.     

New possibilities of recently constructed high-temperature solution calorimeter

The calorimeter presented in this paper is constructed under supervision of authors. The most substantial innovation of construction of the device was introduction of intermediate container with ten sockets. As a result the calorimeter is used for determination of enthalpy of formation for alloys in a wide range of temperature (up to 1,400 K). As an example results from alloys from the Ni–Al–Cr system are presented, they are aimed to determine directly γ′ / γ′ + γ / γ phase boundaries with use of this “in situ” calorimetric method. Precise indication of phase boundaries is crucial for determination of phase diagrams.     

Application of an adiabatic precision calorimeter in the field of organic reactions

Adiabatic calorimetry is a suitable method for investigations of reactions because the generated heat remains completely in the reactor. For the investigation of organic reactions, the adiabatic precision calorimeter ACTRON 5 is used. The alcoholyses of phenyl isocyanate and 1,2-butyleneoxide were investigated. The temperature-time course was estimated by means of the nonlinear program TA-kin. Inclusion of the concentration-time course in the estimation procedure led to an increase in the reliability of the parameters. Probes were taken during isoperibolic measurements and were analysed by means of HPLC.     

Which calorimeter is best? A guide for choosing the best calorimeter for a given task

Most scientists are not knowledgeable about calorimetry. The purpose of this paper is to assist the novice in calorimetry to select the best calorimeter commercially available for their task. The primary literature is a poor guide for instrument selection. Instrument developments in calorimetry are usually not reported in primary literature and calorimetric measurements are usually done with the calorimeter that is available, not the best instrument for the measurement. A procedure for choosing the best calorimeter for a given task is described.     

A calorimetric unit for measurements of the thermal effects of reactions in solution

A calorimetric unit for measurements of the thermal effects of reactions in solution was created. The unit was designed following the classic scheme of a hermetic liquid calorimeter working under isoperibolic conditions, it had a thermometric sensitivity of 10⁻⁴ K and a calorimetric sensitivity of 10⁻² J. The accuracy of calorimeter operation was checked against the heats of solution of potassium chloride. The molar integral enthalpies of solution of glycine in water at 298 K were determined.     

A new micro-fluid chip calorimeter for biochemical applications

Based on a new thermopile heat power sensor, which was developed in MEMS technology, a miniaturized flow-through calorimeter was constructed. The heat power sensor consists of a silicon chip with a thin film BiSb/Sb thermopile and a PMMA reaction chamber. To ensure high signal resolution the heat power sensor is mounted inside a high-precision thermostat, which has a temperature stability of less than 100 μK. The heat power sensitivity of the calorimeter is 4-7 V W⁻¹ depending on the thermal conductivity of the liquid, the height of the chosen reaction chamber and the volume flow rate. A limit of detection of less than 50 nW can be obtained for volume flows lower than 5 μl min⁻¹. An important advantage is the low sample consumption of the calorimeter. For special applications the sample need for one measurement pulse does not exceed 20 μl.     

A device for sample agitation in an accelerating rate calorimeter

A stirring bar type agitation system has been designed and characterized for the accelerating rate calorimeter (ARC). The device allows stirring of the contents of a standard ARC sample container at stirring rates of up to 500 rev. min^?1, depending on sample viscosity. Experiments on a well-characterized thermal decomposition reaction, such as that of di-t-butyl peroxide, indicate that the device does not degrade the measurement of the energy of reaction, ΔE_v, the Arrhenius activation energy, E_a, or the pre-exponential factor, A.The utility of this stirring apparatus is demonstrated by examining the runaway data of a suspension polymerization. The results indicate that a polymerization “kill” agent can be successfully used for that particular reaction.     

Rate constants for reactions of iodine atoms in solution

Laser flash photolysis (at 248 or 308 nm) or aryl iodides in water or water/methanol solutions produces iodine atoms and phenyl radicals. Iodine atoms react rapidly with added I^? to form I₂^? but do not react rapidly with O₂ (k ? 10⁷ L mol^?1 s^?1). Iodine atoms oxidize phenols to phenoxyl radicals, with rate constants that vary from 1.6 × 10⁷ L mol^?1 s^?1 for phenol to about 6 × 10⁹ L mol^?1 s^?1 for 4-methoxyphenol and hydroquinone. Ascorbate and a Vitamin E analogue are also oxidized very rapidly. N-Methylindole is oxidized by I atoms to its radical cation with a diffusion-controlled rate constant, 1.9 × 10¹⁰ L mol^?1 s^?1. Iodine atoms also oxidize sulfite and ferrocyanide ions rapidly but do not add to double bonds. The phenyl radicals, produced along with the I atoms, react with O₂ to give phenylperoxyl radicals, which react with phenols much more slowly than I atoms. © 1995 John Wiley & Sons, Inc.     

A direct isoperibol aneroid calorimeter

An aneroid isoperibol calorimetric apparatus is described which is particularly suitable for measurement of the reaction heat among solids. Such an apparatus contains four calorimeters and allows to carry out differential measurements. Each calorimeter includes two small electric furnaces employed for heating the solid mixture until the reaction begins and for the successive electric calibrations, respectively. The temperature trend of each calorimeter is followed by 80 thermocouples in series. The instrument characteristics are briefly discussed. Examples of its employment in the alloy thermochemistry are given.     

A new magnetically recoverable heterogeneous palladium catalyst for phosphonation reactions in aqueous micellar solution

A new heterogeneous palladium complex of 2‐aminothiophenol supported on nanomagnetic γ‐Fe₂O₃ was synthesized and characterized using various methods. The catalyst was used as a magnetically recoverable heterogeneous palladium catalyst for phosphonation reactions via C ? P bond formation. Using this method, a wide range of electrophilic benzenes was coupled successfully with phosphite esters (triethyl/tri‐isopropyl/triphenylphosphite and diethyl/di‐isopropyl/diphenylphosphite) in aqueous micellar solution to generate the corresponding arylphosphonates in good to high yields. The catalyst was separated using an external magnet and reused for six consecutive cycles without any significant loss of its reactivity. Copyright © 2015 John Wiley & Sons, Ltd.     

Enthalpy of solution of carbohydrates using a modified differential scanning calorimeter

A differential scanning calorimeter (DSC) was modified for the determination of enthalpies of solution. The measurements were performed on aqueous solutions of the deoxy- and fluoro-deoxy derivatives of D-glucopyranose (Glu) where the OH group on the C1, C2, C3, and C6 is replaced by H (1HGlu, 2HGlu, 3HGlu, and 6HGlu) and by F (1FGlu, 2FGlu, 3FGlu, and 6FGlu), 4-deoxy 4-fluoro--D-glucopyranoside (4FGlu), 1-methoxy--D-glucopyranoside (MeOGlu), 1-phenoxy--D-glucopyranoside (PheOGlu), D-mannopyranose (Man), and 3-methoxy--D-glucopyranoside (3MeOGlu), at 15.1, 25.0, 35.0, and 45.1°C. The enthalpies of solution _sH⁰(T) ranged from 1.00±0.25 kJ-mol^–1 for 6HGlu at 15.1°C to 20.4±1.4 for PhOGlu at 45.1°C and were in good agreement with literature values for Man, Glu, MeOGlu, and 3MeOGlu at 25.0 and 35.0°C and for MeOMan and 2HGlu at 35.0°C. _sH⁰(T) for the derivatives were then extrapolated up to the melting temperature T_m and compared with their enthalpies of fusion, _fH also determined from DSC measurements. If the agreement between _sH⁰(T_m) and _fH was within the 95% confidence level, then it was concluded that intermolecular interactions between the carbohydrate molecules in the liquid phase were the same as between the carbohydrate and water molecules in the solution phase. This agreement was observed for aqueous solutions of Man, Glu, MeOGlu, 3HGlu, 3FGlu, and 6FGlu.     

A new micro reaction calorimeter

Traditional reaction calorimeters require highly trained operators and the use of a large sample size (10 ml to 1000 ml) which is incompatible with highly reactive substances. A new calorimeter with a 2 ml or less sample size lends itself to the determination of reactivity of materials for process safety and to the determination of safety of materials shipped in compartment tank cars. The TC-100 Titration Calorimeter meets these requirements. A cost effective instrumentation of a differential cell design provides high sensitivity heat flow measurements. Automatic liquid injection and continuous mixing provides information on the heat of reaction and its rate. A portable instrument with small sample size allows for rapid temperature equilibration and safe handling of very reactive materials.     

Quantum aspects of self-organized periodic chemical reactions

It is a remarkable empirical fact, known for a long time, that in certain self-organized periodic chemical reactions, such as Liesegang's or Belousov-Zhabotinsky's reactions, the product of molecular weight of precipitate, precipitation length period, and speed of precipitation is of the order of universal Planck's quantum of action h. Based on the fact that the classical and quantum diffusions are processes, which are indistinguishable in the configuration space, a quantum criterion in terms of diffusion constants has been established. This criterion enables one to find out conditions under which the quantum behavior of self-organized periodic reactions can be observed.     

Extended batch calorimetry on periodic chemical reactions

Three small setups for a batch microcalorimeter are described which allow for simultaneous determinations of the rate of heat production and of light absorbance, electrode potential or gas production. The setups are tested with fast chemical reactions and the time constants of the calorimetric signal have been determined thereby. Finally, examples are presented showing the usefulness of the device for investigations of periodic chemical reactions.     

A constant heat-flux calorimeter for measuring heat transfer data

A new isothermal calorimeter, designed especially for simultaneously measuring the heat of reaction and the heat transfer data in a reaction solution, is described. The system, called a Constant Heat-Flux Calorimeter, is similar to a differential scanning calorimeter in terms of direct calorimetric measurement of the energies of reaction, but differs from the conventional calorimeters described in the literature. With this device, one recorded output in a temperature control circuit is a linear function of change in energies of reaction, and second in a differential temperature control circuit is found to be proportional to a resistance to heat transfer in a solution. The performance of the calorimeter was evaluated on the basis of some results on heat transfer data of aqueous solution of polyethylene glycol and on solution polymerization of styrene at constant temperatures.