Manual de ejercicios resueltos de Química Analítica Cuantitativa

Edición ampliada de ejercicios de Química Analítica Cuantitativa resueltos y explicados por el Prof. J.M. Fernández, originalmente revisados y maquetados por Í. Salinas e I. Guardado, donde la mayoría de los enunciados -lejos de ser originales- están tomados de los manuales clásicos de la materia

Cathodic stripping voltammetry of pyridine-2-thiol and some related compounds

The cathodic stripping voltammetric behaviour of pyridine-2-thiol and some related heterocyclic thiols has been studied at a static mercury drop electrode. The influence of substituents on the adsorption of these compounds on the mercury electrode, and the nature of the different thiolates responsible for the subsequent stripping signals have been investigated. Differential-pulse cathodic stripping voltammetry was used to establish linear calibration ranges for the compounds studied. The use of a pre-concentration time of 240 s in open circuit allowed a detection limit of 8.0 × 10–9M to be attained for pyridine-2-thiol

Distinct complexing trends of chitosan with toxic metals (PO1-24)

We have been able to prove that not only adsorption but also complexation of different metals (Pb, Cd, Mo, Cu, Zn and Cr) actually takes place in acetate buffer (pH=4) with Chitosans of different molecular weights and deacetylation degrees. Depending on the different electrochemical behaviour on mercury electrode of studied metals and the nature of the resulting complexes, diverse approaches have been used. Chitosan molecular weight and concentration had been seen to play a key role in the Chitosan binding activity with Zn, Pb and Cd, as reported elsewhere[1]. Length of Chitosan chains influences the degree of complexation with both Cr and Mo, while Cu binding capacity remains independent of the molecular weight of the assayed polymers. The larger the polymer chain length the higher the number of amino group available for the retention of both Cr and Mo within the tridimensional structure of the acting ligand. This is consistent with a predominant intra-chain linkage of both metal atoms. On the contrary, in the case of Cu, an inter-layer binding mechanism is proposed as the main retention factor by Chitosan

Obtaining of repair lime renders with microencapsulated phase change materials: optimization of the composition, application, mechanical and microstructural studies

Different batches of repair lime rendering mortars were designed by mixing microencapsulated Phase Change Materials (PCMs) and other additives. The final aim of these renders is to improve the thermal efficiency of the envelope of the Built Heritage, while allowing the practitioners to apply a render with positive final performance. The combinations of the PCMs in different weight percentages, a superplasticiser (to increase the fluidity of the render keeping constant the mixing water), an adhesion improver and a pozzolanic additive were studied. The adhesion of these renders onto bricks and limestone specimens and the shrinkage and cracking of the mortars were studied in detail. X-ray diffraction technique was used to study the composition and evolution of the carbonation process. Compressive strength measurements were studied in hardened specimens. In addition, the porous structure of the rendering mortars was studied by mercury intrusion porosimetry to assess the effect of the PCMs' addition. Samples underwent accelerated climatic ageing to study their durability and the preservation of the thermal efficiency. Results have shown that these thermally enhanced mortars are feasible materia Is for real-life application in the context of architectural heritage restoration and conservation

Enhancement of latent heat storage capacity of lime rendering mortars

Microencapsulated Phase Change Materials (PCMs) were included in air lime rendering mortars in order to improve the thermal comfort of the inhabitants and the energy efficiency of buildings of the Architectural Heritage under the premises of mínimum intervention and maximum compatibility. Three different PCMs were tested and directly added during the mixing process to fresh air lime mortars in three different percentages: 5, 10 and 20 wt. %. Some chemical additives were also incorporated to improve the final performance of the renders: a starch derivative as an adhesion booster; metakaolin as pozzolanic addition to shorten the setting time and to increase the final strength; anda polycarboxylated ether as a superplasticizer to adjust the fluidity of the fresh renders avoiding an excess of mixing water. The specific heat Cp, the enthalpy ti.H ascribed to the phase change and the melting temperature of the PCMs were determined by Differential Scanning Calorimetry (DSC). The capacity of the renders to store/release heat was demonstrated at a laboratory scale. The favourable results proved the effect of these PCMs with respect to the thermal performance of these rendering mortars, offering a promising way of enhancement of the thermal efficiency of building materia Is of the Cultural Heritage

A study of heavy metal complexation in wines

DPV was used to study complexation processes of Zn in must samples, at their natural pH. Titration curves allowed the calculation of ligand concentration and stability constants, following the suitable linearization methods

Effect of the TiO2 doped photocatalytic nano-additives on the hydration and microstructure of Portland and High Alumina Cements

Mortars with two different binders (Portland cement (PC) and high alumina cement (HAC)) were modified upon the bulk incorporation of nano-structured photocatalytic additives (bare TiO2, and TiO2 doped with either iron (Fe-TiO2) or vanadium (V-TiO2)). Plastic and hardened state properties of these mortars were assessed in order to study the influence of these nano-additives. Water demand was increased, slightly by bare TiO2 and Fe-TiO2, and strongly by V-TiO2, in agreement with the reduction of the particle size and the tendency to agglomerate. Isothermal calorimetry showed that hydration of the cementitious matrices was accelerated due to additional nucleation sites offered by the nano-additives. TiO2 and doped TiO2 did not show pozzolanic reactivity in the binding systems. Changes in the pore size distribution, mainly the filler effect of the nano-additives, accounted for the increase in compressive strengths measured for HAC mortars. A complex microstructure was seen in calcium aluminate cement mortars, strongly dependent on the curing conditions. Fe-TiO2 was found to be homogeneously distributed whereas the tendency of V-TiO2 to agglomerate was evidenced by elemental distribution maps. Water absorption capacity was not affected by the nano-additive incorporation in HAC mortars, which is a favourable feature for the application of these mortars

Combination of polymeric superplasticizers, water repellents and pozzolanic agents to improve air lime-based grouts for historic masonry repair

This paper presents the experimental procedure to develop air lime-based injection grouts including polymeric superplasticizers, a water repellent agent and pozzolanic agents as additives. Research focuses on the development of grouts to improve various characteristics simultaneously combining different additions and admixtures. Aiming to improve the injectability of the grouts, in this study different polymeric superplasticizers were added, namely polycarboxylated-ether derivative (PCE), polynaphthalene sulfonate (PNS) and condensate of melamine-formaldehyde sulfonate (SMFC). Sodium oleate was also used as a water repellent agent to reduce the water absorption. The enhancement of the strength and setting time was intended by using microsilica and metakaolin as pozzolanic mineral additions. Compatibility between the different admixtures and action mechanism of the different polymers were studied by means of zeta potential and adsorption isotherms measurements. Diverse grout mixtures were produced and investigated assessing their injectability, fluidity, stability, compressive strength, hydrophobicity and durability. This research leads to several suitable mixtures produced by using more than one component to enhance efficiency and to provide better performance of grouts. According to the results, the grout composed of air lime, metakaolin, sodium oleate and PCE was found the most effective composition improving the mechanical strength, injectability and hydrophobicity

Especiación del Pb en aguas de las Rías bajas Gallegas: puesta a punto de un método voltamperométrico y primeros resultados

El Pb no es un elemento esencial desde el punto de vista biológico, pero su estudio es importante debido a sus efectos tóxicos resultado de su entrada en los ecosistemas acuáticos principalmente por actividades antropogénicas, cuyo flujo se ha estimado en 1,38•108 kg a-1. La extensa costa gallega con 1720 km. de litoral y abundantes aportes de pequeños ríos es muy sensible a los efectos contaminantes de metales, que como el Pb, son transportados por vía atmosférico-fluvial. La necesidad de medidas en el medio acuático de las cabeceras de las rías se ha comenzado a abordar en trabajos como el presente que supone el primer estudio de especiación de Pb realizado en aguas de las Rías Bajas Gallegas utilizando la voltamperometría de redisolución anódica de pulso diferencial (DPASV). Esta es una técnica alternativa y complementaria a los métodos espectroscópicos. Ello es por su sensibilidad inherente y bajos límites de detección, por la precisión de los resultados y por su capacidad de abordar la especiación, a la vez que por su bajo coste y simplicidad de manejo. Se presentan a continuación los resultados del estudio de la complejación de Pb por ligandos orgánicos en dichas aguas mediante la aplicación del procedimiento de linealización propuesto por Ruzic y van den Berg

Estudio voltamétrico de los parámetros de complejación del zinc en aguas de las Rías Gallegas

El zinc se trata de un elemento biológicamente esencial en aguas marinas y estuáricas. Existen estudios [1] en los que se deduce que el zinc es un nutriente biolimitante para el fitoplancton. Por lo tanto, la complejación del zinc con ligandos orgánicos es crítica pues reduce drásticamente la concentración (o actividad) de los iones Zn+2 libres, que son los asimilables por el fitoplancton. A pesar de ello, elevadas concentraciones de Zn+2 (>10-8 M) pueden resultar tóxicas a ciertas diatomeas costeras [2]. Por lo tanto, la complejación orgánica del Zn+2 puede reducir su concentración y evitar su posible toxicidad a concentraciones altas. La posibilidad de contar con técnicas analíticas que permitan cuantificar la abundancia de los compleajos Zn-Ligandos Orgánicos y su constante condicional de estabilidad es, pues, de particular importancia. La técnica analítica utilizada, voltametría de redisolución anódica de pulso diferencial (DPASV), permite diferenciar la fracción de metal unido a ligandos orgánicos y la fracción inorgánica (metal libre + metal unido a ligandos inorgánicos). Una detallada descripción de esta técnica y del procedimiento de valoración de muestra se encuentra en la bibliografía [3, 4]. El objetivo de el presente trabajo es presentar un método para estudiar la complejación-especiación de el Zn+2 en aguas de las rías gallegas utilizando la técnica DPASV