Calculation of Heat of Reaction from Equilibrium Constants at Two Temperatures; Some New Heats of Ionization of Organic Acids.

1939 ◽  
Vol 43 (4) ◽  
pp. 431-438 ◽  
Author(s):  
A. W. Walde
1977 ◽  
Vol 47 (1) ◽  
pp. 44-51 ◽  
Author(s):  
H. Müller ◽  
V. Rossbach

The physicochemical principles of the dyeing of two polyamide-6 fibers modified with the monosodium salt of 5-sulphoisophthalic acid at pH 1.8 and 4.5 with an oxazonium dye (Astrazon Blue BG, C.I. 51004) and a thiazonium dye (Methylene Blue, C.I. 52015) are described. Measurements of the zeta potential by the flow-potential method have shown that the fibers have a very highly negatively-charged surface as compared with unmodified types. This decisively promotes the adsorption of the dyestuff cations on the fiber. The uptake of the dye can be described by means of the Langmuir adsorption isotherm as an ion-exchange reaction. It follows from the agreement of dyestuff saturation figures and comonomer contents that the dyestuff is bound stoichiometrically by the sulpho groups (pH 4.5; 80°C). Carboxyl groups probably take no part in the dyestuff binding at pH 1.8 and 4.5. The standard values of the heat of reaction have been determined from the temperature dependence of the equilibrium constants for reactions responsible for the dyestuff binding. They show that the dyestuff/fiber bond contains a covalent component, which is probably due to interactions between the sulphonate group and the dyestuff cation.


Soil Research ◽  
2000 ◽  
Vol 38 (4) ◽  
pp. 807 ◽  
Author(s):  
Sahta Ginting ◽  
Bruce B. Johnson ◽  
Sabine Wilkens

The effect of 5 organic anions (citrate, malate, malonate, oxalate, and tartrate) on the concentration of Al measured with 2 colorimetric reagents [pyrocatechol violet (PCV) and aluminon] was determined as a function of reaction time. The results are compared with concentrations of reactive Al [Al3+ + AlOH2+ + Al(OH)2+ ] predicted from stability constants. The PCV reagent was found to overestimate this fraction, i.e. to underestimate the extent of complexation by oxalate, malonate, and malate, even when the shortest reaction time of 30 s was applied. However, the aluminon reagent provided a good estimate of ‘reactive’ Al at the 30 s reaction time in the presence of all organic anions studied. At a citrate and tartrate to Al ratio of 1 : 2, the ‘reactive’ Al concentration, determined from stability constant data, underestimated the extent of Al complexation. These deviations could be modelled by the addition of a further complex, with the composition Al2 (OH)L2+ for citrate and Al2(OH)2L2+ for tartrate. Tentative equilibrium constants for these species are presented.


Author(s):  
Fabien Thomas ◽  
Armand Masion

Aluminum is the most abundant metal of the Earth’s crust, of which it represents approximately 8%, ranking after oxygen and silicon. It exists mainly as oxides. In terrestrial environments, aluminum commonly exists as secondary (authigenic) hydroxide or aluminosilicate minerals, mainly clays. These minerals are highly insoluble at neutral pH. However, aluminum occurs in detectable amounts in natural waters, due to leaching of the soil minerals in acidic conditions. Soil acidity may have a natural origin, such as an acidic (silicic) mother rock, melted snow, dissolved carbonic acid, or biologically generated organic acids. During the past two decades, it has been demonstrated that one of the major origins of increased aluminum mobilization and transport in forested soils is introduction of strong acid through atmospheric sulfur and nitrogen deposition. It has also been shown that aqueous aluminum is the biogeochemical link between atmospheric pollution and damage caused to tree roots and aquatic organisms such as plankton, crustaceans, insects, and fish. Biological studies have shown that the different aluminum species exhibit various toxicities: the most toxic are the monomeric and the polynuclear species; complexation with organic acids results in low toxicity. The significance of aluminum to human health has long been regarded as negligible. There is a possible link between high-level aluminum contamination by renal dialysis or hemodialysis, and neurodegenerative health disorders such as Parkinson’s or Alzheimer’s diseases, but the part played by aluminum is not clear. However, since aluminum salts are used on an industrial level as coagulants and flocculants in water treatment, the aluminum concentration and speciation in drinking water deserve careful monitoring. Because of the specific toxicity of the aluminum species, there has been considerable concern in the past two decades over the speciation of aqueous aluminum present in soils and aquatic systems. To this end, several techniques have been developed in order to partition the aluminum species. The most common among them are chromatographic separation and categorization methods such as timed ferron reaction, and computational methods derived from thermodynamic equilibrium constants. However, significant discrepancies between the results have been noticed, and attributed to the dramatic interference of organic and inorganic anions in the Al fractionation.


1967 ◽  
Vol 105 (2) ◽  
pp. 691-695 ◽  
Author(s):  
P. C. Engel ◽  
K. Dalziel

1. Equilibrium constants for the oxidation of glutamate by NAD+ and NADP+, catalysed by glutamate dehydrogenase, have been measured in phosphate buffers of different ionic strengths and at several temperatures. 2. The equilibrium constants for both systems vary markedly with ionic strength. Thermodynamic values for the two systems obtained by extrapolation to zero ionic strength differ significantly from one another. The standard free-energy change for NADP+ reduction has been calculated from that for NAD+ reduction. 3. The heat of reaction has been estimated and is the same with both coenzymes. 4. The thermodynamic data are discussed in relation to earlier data.


1948 ◽  
Vol 32 (2) ◽  
pp. 241-263 ◽  
Author(s):  
M. Kunitz

Crystalline soybean trypsin inhibitor protein undergoes denaturation on heating which is reversed on cooling. In the range of temperature of 35 to 50°C. a solution of the protein consists of a mixture of native and denatured forms in equilibrium with each other. The equilibrium is only slowly established and its final value at any temperature is the same whether a heated, denatured solution of the protein is cooled to the given temperature or whether a fresh solution is raised to that temperature. The kinetics of reversible denaturation of the soybean protein as well as the reversal of denaturation is that of a reversible unimolecular reaction, each process consisting at a given temperature of the same two simultaneous reactions acting in opposite directions. The experimental data on the effect of temperature on the velocity and the equilibrium constants of the opposing reaction were utilized in evaluating the reaction energies and activation energies. The reaction energies for denaturation were found to be as follows:— Change in total heat of reaction ΔH = 57,000 calories per mole Change in entropy of reaction ΔS = 180 calories per degree per mole The heat of activation ΔH1‡ for denaturation = 55,000 The heat of activation ΔH2‡ for the reversal of denaturation = –1900 The entropy ΔS1‡ for denaturation = 95 The entropy ΔS2‡ for reversal of denaturation = –84


2021 ◽  
Vol 2021 ◽  
pp. 1-9
Author(s):  
Xiaohui Song ◽  
Shuaiqi Sun ◽  
Lingzong Meng ◽  
Rongjian Ying ◽  
Yafei Guo ◽  
...  

The densities and pH values in the system NaBO2–Na2SO4–H2O at 298.15 K and 323.15 K were investigated. Combining the equilibrium constants for different boron species, the distributions of six boron species in the mixed solution were calculated with total boron concentration and pH values. The molar fractions of the six boron species are mainly affected by the total boron concentration and temperature, but rarely affected by the concentration of SO42–. The dominant boron species in the mixed solution at the two temperatures is B(OH)4‒. The mole fraction of B(OH)3, B5O6(OH)4‒, and B3O3(OH)4‒ can be neglected. The polyborate ions are easier to form as the temperature increases. The results of distribution for boron species in this study and those with the Pitzer model can both be used to describe the distribution of boron species in the mixed solution.


1965 ◽  
Vol 43 (8) ◽  
pp. 2387-2391 ◽  
Author(s):  
Hugh J. Anderson

The dilution of N-methylpyrrole by an inert solvent causes a change in the values of the proton chemical shifts which has been interpreted to support a "closed cyclic dimer" type of association between molecules. Equilibrium constants have been computed for the monomer–dimer system at two temperatures. The proton chemical shifts have been determined for the pure liquid at a series of temperatures covering a wide range. The effects of dilution in several different solvents have also been investigated.


1976 ◽  
Vol 54 (24) ◽  
pp. 3872-3875
Author(s):  
Harry Horlings ◽  
Donald S. Scott ◽  
John R. Wynnyckyj

Heat of reaction and free energy of formation at 25 °C were determined from experimental equilibrium yields for the reaction[Formula: see text]in an aqueous solution.The values are 5045 and 1927 cal/mol respectively. Equilibrium constants for the reaction were determined over a temperature range from 20 to 193 °C.


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