Chemical speciation effects on the volumetric properties of aqueous sulfuric acid solutions

Densities of fifteen aqueous solutions of sulfuric acid (H2SO4) have been measured by vibrating-tube densimetry at solute molalities (m) from (0.01 to 3.0) mol·kg−1 over the temperature range 293.15 ≤ T/K ≤ 343.15. These data have been used to calculate the corresponding apparent molar volumes Vϕ(H2SO4,aq), which represent a significant expansion of the volumetric database for this industrially-important acid. At 298.15 K the present results agree well with literature data, notably with the century-old values given in the 1926 International Critical Tables. At other temperatures, where comparisons are possible agreement with the present Vϕ values is also very satisfactory. Consistent with earlier studies, Vϕ(H2SO4,aq) was found to exhibit an abnormally-large decrease at low concentrations (m ≤ 0.1 mol·kg−1). This effect is consistent with a change in the chemical speciation of H2SO4(aq), from an essentially 1:1 electrolyte (H+(aq) + HSO4− (aq)) at higher concentrations to a predominantly 1:2 electrolyte (2H+(aq) + SO42− (aq)) in dilute solutions. The Vϕ values were modelled using variants of Young’s rule and the Pitzer formalism. Combination of these results with literature values for the standard volume V°(SO42−,aq) enabled estimation of V°(HSO4−,aq) and the standard volume change, ΔrV°, for the first protonation of the sulfate ion (H+(aq) + SO42−(aq) → HSO4−(aq)) as functions of temperature. It is shown that V°(HSO4−,aq) is sensitive to the value of the first protonation constant and probably cannot be determined to better than ± 0.3 cm3·mol−1 at present

Chemical speciation effects on the volumetric properties of aqueous sulfuric acid solutions

Densities of fifteen aqueous solutions of sulfuric acid (H2SO4) have been measured by vibrating-tube densimetry at solute molalities (m) from (0.01 to 3.0) mol·kg−1 over the temperature range 293.15 ≤ T/K ≤ 343.15. These data have been used to calculate the corresponding apparent molar volumes Vϕ(H2SO4,aq), which represent a significant expansion of the volumetric database for this industrially-important acid. At 298.15 K the present results agree well with literature data, notably with the century-old values given in the 1926 International Critical Tables. At other temperatures, where comparisons are possible agreement with the present Vϕ values is also very satisfactory. Consistent with earlier studies, Vϕ(H2SO4,aq) was found to exhibit an abnormally-large decrease at low concentrations (m ≤ 0.1 mol·kg−1). This effect is consistent with a change in the chemical speciation of H2SO4(aq), from an essentially 1:1 electrolyte (H+(aq) + HSO4− (aq)) at higher concentrations to a predominantly 1:2 electrolyte (2H+(aq) + SO42− (aq)) in dilute solutions. The Vϕ values were modelled using variants of Young’s rule and the Pitzer formalism. Combination of these results with literature values for the standard volume V°(SO42−,aq) enabled estimation of V°(HSO4−,aq) and the standard volume change, ΔrV°, for the first protonation of the sulfate ion (H+(aq) + SO42−(aq) → HSO4−(aq)) as functions of temperature. It is shown that V°(HSO4−,aq) is sensitive to the value of the first protonation constant and probably cannot be determined to better than ± 0.3 cm3·mol−1 at present

Chemical data evaluation: General considerations and approaches for IUPAC projects and the chemistry community (IUPAC Technical Report)

The International Union of Pure and Applied Chemistry has a long tradition of supporting the compilation of chemical data and their evaluation through direct projects, nomenclature and terminology work, and partnerships with international scientific bodies, government agencies, and other organizations. The IUPAC Interdivisional Subcommittee on Critical Evaluation of Data has been established to provide guidance on issues related to the evaluation of chemical data. In this first report, we define the general principles of the evaluation of scientific data and describe best practices and approaches to data evaluation in chemistryinfo:eu-repo/semantics/publishedVersio

Observation of electron transfer mediated decay in aqueous solution

Photoionization is at the heart of X ray photoelectron spectroscopy XPS , which gives access to important information on a sample s local chemical environment. Local and non local electronic decay after photoionization in which the refilling of core holes results in electron emission from either the initially ionized species or a neighbour, respectively have been well studied. However, electron transfer mediated decay ETMD , which involves the refilling of a core hole by an electron from a neighbouring species, has not yet been observed in condensed phase. Here we report the experimental observation of ETMD in an aqueous LiCl solution by detecting characteristic secondary low energy electrons using liquid microjet soft XPS. Experimental results are interpreted using molecular dynamics and high level ab initio calculations. We show that both solvent molecules and counterions participate in the ETMD processes, and different ion associations have distinctive spectral fingerprints. Furthermore, ETMD spectra are sensitive to coordination numbers, ion solvent distances and solvent arrangemen

Preservice Elementary Science Teachers' Argumentation Competence: Impact of a Training Programme

The recent literature has shown the importance of Preservice Elementary Science Teachers (PESTs) having a deep understanding of argumentation, as this factor may affect the nature of the class activities that are taught and what students learn. A lack of understanding of this factor may represent an obstacle in the development of science education programmes in line with the development of scientific competences. This paper presents the results of the design and implementation of a training programme of 6 sessions (12 hours of class participation plus 8 hours of personal homework) on argumentation. The programme was carried out by 57 Spanish PESTs from Malaga, Spain. The training programme incorporates the innovative use of certain strategies to improve competence in argumentation, such as teaching PESTs to identify the elements of arguments in order to design assessment rubrics or by including peer assessment during evaluation with and without rubrics. The results obtained on implementing the training programme were evaluated based on the development of PESTs’ argumentation competence using Toulmin’s argumentative model. Data collection methods involved two tasks carried out at the beginning and the end of the programme, i.e., pre-test and post-test, respectively. The conclusion of the study is that students made significant progress in their argumentation competence on completing the course. In addition, PESTs who followed the training programme achieved statistically better results at the end than those in the control group (n = 41), who followed a traditional teaching programme. A 6-month transfer task showed a slight improvement for the PESTs of the experimental group in relation to the control group in their ability to transfer argumentation to practice, especially to the extent to which they mentioned argumentation in their practice portfolios.This work is part of the “I+D Excelencia” project “Development and evaluation of scientific competences through context based and modelling teaching approaches” case studies (EDU2013-41952-P), funded by the Spanish Ministry of Economy and Finance through its 2013 research call

Role of urea and methylamines in buoyancy of elasmobranchs

The possible role of urea and trimethylamine oxide (TMAO) in providing positive buoyancy has been examined for elasmobranch fishes. TMAO has a considerably lower density than an equimolar solution of urea, and solutions of both TMAO and urea are considerably less dense than equimolar solutions of most other body fluid solutes. The body fluid composition of three elasmobranchs, the whiskery shark Furgaleus ventralis, the black whaler shark Carcharhinus obscurus and the shovelnosed ray Aptychotremata vincentiana, is typical for marine elasmobranchs, with plasma concentrations of about 260 mmol l-1 Na+, 250 mmol l-1 Cl-, 340 mmol l-1 urea and 70 mmol l-1 trimethylamine oxide. A plasma density of 1.015 was calculated for the whaler shark (from the concentrations, relative molecular masses and absolute molal volumes of plasma solutes), which would contribute a positive lift of 8.45 g l-1. There is a large positive contribution to buoyancy by urea (3.7 g l-1), trimethylamine oxide (1.8 g l-1) and Cl- (4.0 g l-1), whereas slight negative buoyancy is conferred by Na+ (-0.8 g l-1). Divalent cations (Ca2+, Mg2+) contribute minimal negative buoyancy (about -0.1 g l-1 each) despite their rather negative partial molal volumes, because of their low concentrations. Muscle fluids contain about 40 mmol l-1 Cl-, 365 mmol l-1 urea, 160 mmol l-1 trimethylamine oxide, 16 mmol l-1 betaine and 69 mmol l-1 sarcosine. The organic solutes contribute about 12.1 g l-1 lift. Although urea and TMAO act as balancing osmolytes, and TMAO as a counteracting solute, a positive buoyancy role must be considered as a further adaptive function of urea and TMAO accumulation in chondrichthyean fishes

Chemical speciation of environmentally significant metals with inorganic ligands Part 2: The Cu2+-OH-, Cl-, CO32-, SO42-, and PO43- systems

Complex formation between CuII and the common environmental ligands Cl-, OH-, CO32-, SO42-, and PO43- can have a significant effect on CuII speciation in natural waters with low concentrations of organic matter. Copper(II) complexes are labile, so the CuII distribution amongst these inorganic ligands can be estimated by numerical modeling if reliable values for the relevant stability (formation) constants are available. This paper provides a critical review of such constants and related thermodynamic data. It recommends values of log10βp,q,r° valid at Im = 0 mol kg-1 and 25 °C (298.15 K), along with the equations and specific ion interaction coefficients required to calculate log10βp,q,r values at higher ionic strengths. Some values for reaction enthalpies, ΔrHm, are also reported where available. In weakly acidic fresh water systems, in the absence of organic ligands, CuII speciation is dominated by the species Cu2+(aq), with CuSO4(aq) as a minor species. In seawater, it is dominated by CuCO3(aq), with Cu(OH)+, Cu2+(aq), CuCl+, Cu(CO3)OH-, Cu(OH)2(aq), and Cu(CO3)22- as minor species. In weakly acidic saline systems, it is dominated by Cu2+(aq) and CuCl+, with CuSO4(aq) and CuCl2(aq) as minor species

Sulfate protonation in sodium chloride and sodium perchlorate media

The equilibrium (association) constant, KA, for the first protonation of the sulfate ion in aqueous solution: [H+(aq) + SO2−4(aq) ⇌ HSO−4(aq)] has been measured at 298.15 K in NaCl and NaClO4 media using glass-electrode potentiometry at five ionic strengths in the range 0.5 ≤ I/(mol·dm−3) ≤ 5.0. The present KA values vary smoothly with I and are in good agreement with reliable literature data but indicate that the previously reported value of KA at I = 5 mol·dm−3 in NaClO4 media is in error

A chemical view of the most ancient metazoa - biomarker chemotaxonomy of hexactinellid sponges

Hexactinellid sponges are often considered to be the most ancient metazoans. Lipid biomarkers from 23 species were studied for information on their phylogenetic properties, particularly their disputed relation to the two other sponge classes (Demospongiae, Calcarea). The most prominent lipid compounds in the Hexactinellida comprise C28 to C32 polyenoic fatty acids. Their structures parallel the unique patterns found in demosponge membrane fatty acids (demospongic acids) and strongly support a close phylogenetic association of the Demospongiae and the Hexactinellida. Both taxa also show unusual mid-chain methylated fatty acids (C15 C25 ) and irregular C25- and C40-isoprenoid hydrocarbons, tracers for specific eubacteria and Archaea, respectively. These biomarkers indicate a similar, highly conservative symbiont community, although some shift in the abundance of the associated microbiota was observed. The lack of these features in calcareous sponges further contradicts the still common view that Calcarea and Demospongiae are more closely related to each other than either is to the Hexactinellida