Basicity calorimetry

Calorimetry is the basic experimental method employed in thennochemistry and thennal physics which enables the measurement of the difference in the energy U or enthalpy //of a system as a result of some process being done on the system. The instrument that is used to measure this energy or enthalpy difference (At/ or AH) is called a calorimeter. In the first section the relationships between the thennodynamic fiinctions and calorunetry are established. The second section gives a general classification of calorimeters in tenns of the principle of operation. The third section describes selected calorimeters used to measure thennodynamic properties such as heat capacity, enthalpies of phase change, reaction, solution and adsorption. 

A calorimeter Is a device used to measure heat flows that accompany chemical processes. The basic features of a calorimeter include an Insulated container and a thermometer that monitors the temperature of the calorimeter. A block diagram of a calorimeter appears in Figure 6-15. In a calorimetry experiment, a chemical reaction takes place within the calorimeter, resulting in a heat flow between the chemicals and the calorimeter. The temperature of the calorimeter rises or falls in response to this heat flow. 

Several collaborating laboratories (usually five participating laboratories) test the proposed substance using a variety of techniques. The relative reactivity or relative absorbance of the impurities present in a substance must be checked when a nonspecific assay method is employed, e.g. by colorimetry or ultraviolet spectrophotometry. It is particularly important to quantify the impurities when a selective assay is employed. In such a case, it is best to examine the proposed substance by as many methods as practicable, including, where possible, absolute methods. For acidic and basic substances, titration with alkali or acid is simple but other reactions which are known to be stoichiometric may be used. Phase solubility analysis and differential scanning calorimetry may also be employed in certain cases. 

Calorimetry investigations of zinc ions with functionalized pyridines have been carried out in both dimethylformamide and acetonitrile. The pyridines used were pyridine, 3-methylpyridine, and 4-methylpyridine. In DMF, for all three pyridines, four- and six-coordinate species formed and their formation constants, reaction enthalpies and entropies were determined. The stability increases linearly with increasing basicity of the pyridine derivative. The formation of the 3-methylpyridine complex is enthalpically less favorable and entropically more favorable than... 

The basic principle of heat-flow calorimetry is certainly to be found in the linear equations of Onsager which relate the temperature or potential gradients across the thermoelements to the resulting flux of heat or electricity (16). Experimental verifications have been made (89-41) and they have shown that the Calvet microcalorimeter, for instance, behaves, within 0.2%, as a linear system at 25°C (41)-A. heat-flow calorimeter may be therefore considered as a transducer which produces the linear transformation of any function of time f(t), the input, i.e., the thermal phenomenon under investigation]] into another function of time ig(t), the response, i.e., the thermogram]. The problem is evidently to define the corresponding linear operator. 

The development of the theory of heat-flow calorimetry (Section VI) has demonstrated that the response of a calorimeter of this type is, because of the thermal inertia of the instrument, a distorted representation of the time-dependence of the evolution of heat produced, in the calorimeter cell, by the phenomenon under investigation. This is evidently the basic feature of heat-flow calorimetry. It is therefore particularly important to profit from this characteristic and to correct the calorimetric data in order to gain information on the thermokinetics of the process taking place in a heat-flow calorimeter. 

The basic principle of solution calorimetry is simple. In one experiment the enthalpy of solution of, for example, LaA103(s) [32] is measured in a particular solvent. In order to convert this enthalpy of solution to an enthalpy of formation, a thermodynamic cycle, which gives the formation reaction... 

Bromine trifluoride calorimetry has considerable development potential both with respect to improved accuracy and with respect to the range of materials which can be examined. Thus the more insoluble or refractory materials could be reacted in "acid or "basic solutions in BrF3 or even in molten acids or bases at higher temperatures. (The, 80/180 ratio in rocks can be measured on the oxygen released by dissolving minerals in such melts.)... 

Many methods have been developed to detect the Lewis acidity/basicity and Bronsted acid-ity/basicity. Liquid- or gas-phase titration, UV spectroscopy, and calorimetry are some of the non-spectroscopic methods of detecting acidity and basicity of an oxide material.26 However, we shall confine our discussion to the spectroscopic methods of detecting the acidity and basicity of an oxide material. IR, Raman, and NMR are the common spectroscopic techniques used to quantify the acidity or basicity of an oxide material. 

Be familiar with the basic measurements required for the experiments. For example, in a calorimetry experiment you do not measure the change in temperature, you calculate it. You measure the initial and final temperatures. 

Fluorine bomb calorimetry is in many aspects similar to oxygen bomb calorimetry. The experiments are carried out in isoperibol instruments, which, except for the bomb, are basically identical to those described in sections 7.1 and 7.2. The procedure used to calculate Acf/°(298.15 K) from the experimental results is also analogous to that discussed for oxygen bomb calorimetry in section 7.1. Thus, a temperature-time curve, such as the one in figure 7.2, is first acquired, and the corresponding adiabatic temperature rise, A Tad, is derived. 

S. Sunner. Basic Principles of Combustion Calorimetry. In Experimental Chemical Thermodynamics, vol. 1 Combustion Calorimetry S. Sunner, M. Mansson, Eds. IUPAC-Pergamon Press Oxford, 1979 chapter 2. 

Microcalorimetry has gained importance as one of the most reliable method for the study of gas-solid interactions due to the development of commercial instrumentation able to measure small heat quantities and also the adsorbed amounts. There are basically three types of calorimeters sensitive enough (i.e., microcalorimeters) to measure differential heats of adsorption of simple gas molecules on powdered solids isoperibol calorimeters [131,132], constant temperature calorimeters [133], and heat-flow calorimeters [134,135]. During the early days of adsorption calorimetry, the most widely used calorimeters were of the isoperibol type [136-138] and their use in heterogeneous catalysis has been discussed in [134]. Many of these calorimeters consist of an inner vessel that is imperfectly insulated from its surroundings, the latter usually maintained at a constant temperature. These calorimeters usually do not have high resolution or accuracy. 

Extensive studies of the acidity and basicity of zeolites by adsorption calorimetry have been carried out over the past decades, and many reviews have been published [62,64,103,118,120,121,145,146,153,154]. For a given zeolite, different factors can modify its acidity and acid strength the size and strength of the probe molecule, the adsorption temperature, the morphology and crystallinity, the synthesis mode, the effect of pretreatment, the effect of the proton exchange level, the Si/Al ratio and dealumination, the isomorphous substitution, chemical modifications, aging, and coke deposits. 

It was proven that microcalorimetry technique is quite well developed and very useful in providing information on the strength and distribution of acidic and basic sites of catalysts. When interpreting calorimetric data, caution needs to be exercised. In general, one must be careful to determine if the experiments are conducted under such conditions that equilibration between the probe molecules and the adsorption sites can be attained. By itself, calorimetry only provides heats of interaction. It does not provide any information about the molecular nature of the species involved. Therefore, other complementary techniques should be used to help interpreting the calorimetric data. For example, IR spectroscopy needs to be used to determine whether a basic probe molecule adsorbs on a Brpnsted or Lewis acid site. 

A basic method for determining the energy change involved with many chemical processes is calorimetry. A calorimeter is an insulated container used to carry out a chemical process. A thermometer is used to measure temperature changes that take place during the process. A simple constant-pressure calorimeter is shown in Figure 10.3. This type of calorimeter derives its name from the fact that it is open to the atmosphere and the pressure remains constant during the process. Constant-pressure... 

From potentiometry, calorimetry (Table 16) and ESR spectroscopy,463 65 there is agreement about the species in moderately acidic solutions. On the other hand, the nature of species present in neutral or basic solutions is still controversial. 

A rather different study of the kinetics of decomposition of solid complexes of [VO(dbm)2(L)] (dbm = dibenzoylmethanato, L = py and several methyl-, dimethyl- and amino-pyridines) used differential scanning calorimetry (DSC).531 Using the temperature that corresponds to the loss of the molecule L in equation (37), a linear relationship was found between it and the basicity of L, except for 4-amino- and 4-methyl-pyridine. 

The enthalpy and entropy of complex formation between Zn11 and picolinate and dipicolinate anions in aqueous solution have been determined by calorimetry and from formation constant data. The greater stability of the dipicolinate complex compared to the picolinate complex reflects an entropy effect, and Ais actually less favourable. These anions are well known to have a low basicity to H+ compared to their complexing ability to metals. In the present case, this probably reflects the coplanarity of the carboxylate anions and the pyridine ring, so that the oxygen atoms are in a favourable position to coordinate.800... 

A study has been reported of the complexation of ZnBr2 by Br- (as LiBr) in solvents of low basicity but different dielectric permittivities (propylene carbonate, (MeO)2CO and EtOAc) using Raman spectroscopy and calorimetry.1012 Both the [ZnBr3] and [ZnBr4]2 anions are observed, except in the case of EtOAc, where only the 1 1 complex is formed. The dielectric permittivity has no effect on the AHf of the complexes. 

An important hypothesis related to interface energetics is that of Nyilas, who said that the free energy of adsorption basically drives conformational change 132>. He probed this approach by measuring the enthalpy of adsorption using micro calorimetry and attempted to relate surfaces with low heats of protein adsorption with increased blood compatibility. 

As pointed out in Section 8.2, most physical and chemical processes, not just the chemical transformation of reactants into products, are accompanied by heat effects. Thus, if calorimetry is used as an analytical tool and such additional processes take place before, during, or after a chemical reaction, it is necessary to separate their effects from that of the chemical reaction in the measured heat-flow signals. In the following, we illustrate the basic principles involved in applying calorimetry combined with IR-ATR spectroscopy to the determination of kinetic and thermodynamic parameters of chemical reactions. We shall show how the combination of the two techniques provides extra information that helps in identifying processes additional to the chemical reaction which is the primary focus of the investigation. The hydrolysis of acetic anhydride is shown in Scheme 8.1, and the postulated pseudo-first-order kinetic model for the reaction carried out in 0.1 M aqueous hydrochloric acid is shown in Equation 8.22 ... 

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