Computational Studies of POSS Based Materials
Effetto del polimero polipropilenglicole sulla dinamica della reazione di Belousov-Zabotinsky
Rate-retarding effects of mixed anionic/non-ionic micelles on the alkaline hydrolysis of the chloropentamminocobalt(III) complex
Abstract Rate data for the alkaline hydrolysis of the chloropentaamminecobalt(III) cation in the presence of mixed micelles composed of (i) anionic sodium decylsulphate (SDeS) and non-ionic dodecylpenta(oxyethylene glycol) monoether (C 12 E 5 ) surfactants and (ii) anionic sodium perfluorooctanoate (SPFO) and non-ionic C 12 E 5 surfactants has been obtained at T 298 K and constant electrolyte concentration 0.08 mol dm −3 ([NaOH] = 0.01 mol dm −3 , [NaClO 4 ] = 0.07 mol dm −3 ) over a wide range of total surfactant concentration ( C t ) and anionic mole fraction ( χ ). The critical micelle concentrations (c.m.c.s) of the mixed micelles have been determined over the entire χ range by means of…
L'Avventura delle Scienze - Tomo B
Amphiphilic derivatives of a polyaspartamide: their aggregation and solubilization ability
Abstract The self-aggregation and solubilization capability of a series of amphiphilic copolymers obtained by derivatisation of polymeric chain of α,β-poly(N-2-hydroxyethyl)- dl -aspartamide (PHEA) with polyethylene glycols (PEG, being different molecular weight 2000 or 5000 Da, PEG2000 and PEG5000, respectively) and/or hexadecylamine alkyl chain (C16), namely PHEA–PEG2000, PHEA–PEG5000, PHEA–C16, PHEA–PEG2000–C16 and PHEA–PEG5000–C16, have been evidenced by performing systematic tensiometric and spectrophotometric studies. All measurements have been performed at 25.0 °C over a wide copolymer concentration range. The tensiometric results have shown that, for all copolymers studied, the surf…
Mesoscopic structural organization in fluorinated room temperature ionic liquids
The presence of fluorous tails in room-temperature ionic liquids imparts new properties to their already rich spectrum of appealing features. The interest towards this class of compounds that are of ionic nature with melting point less than 25 degrees C is accordingly growing; in particular, compounds bearing relatively long fluorous tails have begun to be considered. In this invited presentation, we show recent results arising from the systematic study of structural properties of a series of fluorinated room temperature ionic liquids, with growing fluorous chain length. At odd with the current understanding of this class of compounds, we show experimentally that they are characterized by t…
The apparently anomalous effects of surfactants on interfacial tension in the IBA/water system near its upper critical solution temperature
We studied the effect of anionic, cationic, and nonionic surfactants on the interfacial tension between the two phases of the isobutyric acid/water system using spinning drop tensiometry. It has been found that interfacial tension decreases with increasing concentration of the surfactant in the case of sodium dodecyl sulfate (SDS) and of dodecyltrimethylammonium chloride (DTAC). However, in the case of Triton X-100 an increase of surfactant concentration leads to an increase of the interfacial tension. Such results are consistent with the upper critical solution temperature (UCST) in the presence of these surfactants: the UCST decreases with increasing SDS and DTAC concentrations while it i…
Measurement of the Effective Interfacial Tension in a Miscible System (1-Butanol-Water) by Spinning Drop Tensiometry
Effects of non-ionic micelles on transient chaos in an unstirred Belousov-Zhabotinsky reaction.
The behaviour of the Ce(IV)-catalyzed Belousov-Zhabotinsky (BZ) system has been monitored at 20.0 degrees C in unstirred batch conditions in the absence and presence of different amounts of the non-ionic micelle-forming surfactants hexaethylene glycol monodecyl ether (C10E6) and hexaethylene glycol monotetradecyl ether (C14E6). The influence of the non-ionic surfactants on both the kinetics of the oxidation of malonic acid (MA) by Ce(IV) species and the behaviour of the BZ reaction in stirred batch conditions has also been studied over a wide surfactant concentration range. The experimental results have shown that, in unstirred batch conditions, at surfactant concentrations below the critic…
Thermodynamic Behavior of Non-Ionic Tri-block Copolymers in Water at Three Temperatures
Apparent molar volumes (V Φ) of aqueous solutions of some copolymers, based on ethylene oxide (EO) and propylene oxide (PO) units, were determined as functions of concentration at three temperatures. Viscosity measurements were also carried out on some of these systems. The effects studied include how the molecular architecture and the molecular weight affect the aggregation of the copolymer, keeping constant the EO/PO ratio. Modeling of the volumetric data yielded the partial molar volume of the copolymer in the standard (V°) and the aggregated (V M) states, as well as the equilibrium constant for micellization and the aggregation number. Analysis of the viscosity data supported the insigh…
Chimica dalla H alla Z. Edizione BLU - Volume BLU Dai fenomeni alle soluzioni, 1° Biennio
L'Energia al centro
Un corso concepito, progettato e scritto specificamente per gli Istituti Tecnici e non derivato da edizioni dello scientifico. Il programma è strutturato nel pieno rispetto delle indicazioni nazionali, ma con attenzione alla prassi didattica e l’approccio a ogni singolo argomento è calibrato e declinato per il target di studenti che si iscrivono a questo tipo di scuole. Il corso si sviluppa in cinque temi e il concetto di energia come portante di tutta la disciplina viene accostato a tutti i concetti fondamentali della fisica, a mano a mano che essi vengono presentati. Tre grandi infografiche aprono il libro legano i concetti presentati nel corso di fisica alla vita quotidiana. La teoria è …
Dynamic evolution of the oscillatory Belousov-Zhabotinsky reaction upon addition of a non-ionic polymer
Abstract The dynamic evolution of the oscillatory Belousov–Zhabotinsky reaction upon addition of increasing amount of the non-ionic polymer polypropylene glycol with molecular weight 425 g mol−1 (PPG-425) was investigated in a stirred-batch reactor by monitoring the Ce(IV) absorbance changes. The oscillatory parameters are significantly altered by the presence of the polymer. The findings obtained in the present work revealed that the PPG-425 is not only more effective, than other polymer previously [R. Lombardo, C. Sbriziolo, M.L. Turco Liveri, K. Pelle, M. Wittmann, Z. Noszticzius, in: J.A. Pojman, Q. Tran-Cong-Miyata (Eds.), Nonlinear Dynamics in Polymeric Systems, American Chemical Soci…
L'Avventura delle Scienze - Tomo C
Dielectric Characterization of Fruit Nectars at Low RF Frequencies
Dielectric properties of apple, apricot, peach, and pear nectars were studied in the frequency range from 15 kHz to 30 MHz and the temperature range from 25 to 60 degrees C. Both the relative dielectric constants and the dielectric loss factors decreased by increasing frequency and increased linearly with increasing temperature with values in the order 10(4)-10(2) and 10(5)-10(2), respectively. The power dissipation densities and the power penetration depths were found to increase linearly with temperature. Power dissipation densities remained essentially constant for all the samples while power penetration depths decreased significantly on increasing frequency. The dependence of each of th…
CO evolution rate during the reaction between Ce(IV) ions and bromomalonic acid in acidic medium
L'Energia al Centro - Volume 2
ART AND TECHNIQUE: ARTISTIC REPRODUCTION OF THE ANCIENT BRONZE IL GUERRIERO DA PETRALIA SOTTANA
The reproduction of artistic objects is useful for museological, teaching, and commercial purposes. In some cases, the reproduction is carried out to replace the originals located in outdoor environments and to prevent the deterioration due to weathering or pollution. This article describes the different phases that led to the reproduction of the Il Guerriero da Petralia Sottana. The observation of stylistic characteristics and the physical-chemical investigation were carried out in order to obtain information about the composition of the alloy and the technological properties of the artifact by using Optical Microscopy and X- ray Fluorescence. The reproduction in wax was performed by using…
Perturbation of the BZ system with non ionic polymers: effect of components concentration
Aggregation of Poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) Copolymers in Water at Some Temperatures. Volumetric and viscosimetric studies
A multi-analytical non-invasive and micro-invasive approach to canvas oil paintings. General considerations from a specific case
Abstract The investigation of artwork to understand story, state of conservation and to know about the composing materials is an issue that is getting growing attention in specialized literature. From a methodological point of view the scientific community is trying to reach a common proposal that could contribute to define a Standard Operating Procedure (SOP) for the application of portable non-invasive and microinvasive techniques for in-situ analyses. In this paper the oil painting on canvas “St. Girolamo nello studio” by Nicolo Buttafoco was investigated to known the materials and techniques used by the artist as well as to evaluate its preservation status. The survey has been conducted…
The effect of rotational acceleration on diffusion between miscible fluids
Noi e La Chimica - Dalle biomolecole al metabolismo
Behaviour of the Belousov-Zhabotinsky oscillator in the presence of carboxymethyl-celulose
Mechanistic Investigations of the BZ Reaction with Oxalic Acid Substrate. I. The Oscillatory Parameter Region and Rate Constants Measured for the Reactions of HOBr, HBrO2, and Acidic BrO3- with Oxalic Acid
This paper is the first part of a study reinvestigating the mechanism of the Belousov-Zhabotinsky (BZ) reaction of oxalic acid, which is the simplest organic substrate for a BZ oscillator. New experiments are performed to find the oscillatory region in 1 M sulfuric acid at 20 °C. The removal rate of the end product bromine by an inert gas stream is a critical parameter here: oscillations can be observed only in a window of that parameter. The “rate constant” for the physical removal of bromine is measured as a function of the gas flow rate and reactor volume; furthermore, the rate constants of three component reactions important in this system are also determined. These are oxygen atom tran…
Spectrophotometric evidence for the solubilization site of betalain pigments in membrane biomimetic systems.
The solubilization site of two betalain pigments, namely, betanin and indicaxantin, into l-alpha-dipalmitoyl-phosphatidylcholine (DPPC) and dimyristoylphosphatidylcholine (DMPC) vesicles was investigated by a spectrophotometric study. Pigment absorbance was monitored by varying phospholipid concentration, at a constant temperature that was varied in a range including the main phase transition temperature (Tm) of the relevant phospholipid bilayer. Maximum betanin absorption increased with the increase of DPPC concentration within the entire temperature range, reaching a plateau. The binding constant (Kb) of the pigment, calculated according to a pseudo-two-phase model, varied with the temper…
La Scoperta delle Scienze - 3
Kinetic evidence for the solubilization of pyridine-2-azo-p-dimethylaniline in alkanediyl-α,ω-bis(dimethylcetylammonium nitrate) surfactants. Role of the spacer chain length
The incorporation of the bidentate ligand pyridine-2-azo-p-dimethylaniline (PADA) into micellar aggregates of the dimeric cationic surfactants propanediyl-, hexanediyl- and dodecanediyl-alpha,omega-bis(dimethylcetylammonium nitrate) (16-3-16,2NO(3)(-), 16-6-16,2NO(3)(-) and 16-12-16,2NO(3)(-), respectively) has been studied at 25 degreesC by examining the kinetics of the complexation reaction of the Ni(II) ion with this ligand. For comparison, cetyltrimethylammonium nitrate ( CTAN), which can be considered as the "monomeric'' surfactant of 16-3-16,2NO(3)(-), has also been used. The kinetic data have shown that, for 16-3-16,2NO(3)(-) and CTAN, at a surfactant concentration below the critical…
La scoperta delle scienze - 2
Mechanistic investigations on the BZ reaction with oxalic acid I. The oscillatory parameter region and rate constants measured for the reactions of HOBr, HBrO2 and acidic BrO3- with oxalic acid
L'avventura delle Scienze - Tomo D
Evidence for the Existence of an Effective Interfacial Tension between Miscible Fluids: Isobutyric Acid-Water and 1-Butanol-Water in a Spinning-Drop Tensiometer
We report definitive evidence for an effective interfacial tension between two types of miscible fluids using spinning-drop tensiometry (SDT). Isobutyric acid (IBA) and water have an upper critical solution temperature (UCST) of 26.3 degrees C. We created a drop of the IBA-rich phase in the water-rich phase below the UCST and then increased the temperature above it. Long after the fluids have reached thermal equilibrium, the drop persists. By plotting the inverse of the drop radius cubed (r(-)(3)) vs the rotation rate squared (omega(2)), we confirmed that an interfacial tension exists and estimated its value. The transition between the miscible fluids remained sharp instead of becoming more…
L'avventura delle Scienze - Tomo A
Synthesis of yttrium aluminum garnet nanoparticles in confined environment, and their characterization
Abstract Nanopowders of yttrium aluminum garnet (YAG, Y3Al5O12) have been prepared by thermal treatment of hydroxides obtained by synthesis in a confined environment constituted by water/Cetyltrimethylammonium bromide (CTAB)/1-butanol/n-heptane. The phase behavior of the above system has been investigated on varying the water/CTAB molar ratio (R) at constant 1-butanol/CTAB and heptane/CTAB molar ratio. The dispersed aqueous phases were constituted by solutions of ammonia and of yttrium and aluminum nitrates, respectively. Measures of Kinematic Viscosity, Electrical Conductivity and Small Angle X-ray Scattering have been carried out. It was found that, on increasing the ammonia solution cont…
Adsorption of triblock copolymers and their homopolymers at laponite clay/solution interface. Role played by the copolymer nature
The adsorption thermodynamics of copolymers, based on ethylene oxide (EO) and propylene oxide ( PO) units, at the laponite (RD) clay/liquid interface was determined at 298 K. The copolymer nature was tuned at molecular level by changing the hydrophilicity, the architecture and the molecular weight (Mw) keeping constant the EO/PO ratio. Polyethylene (PEGs) and polypropylene (PPGs) glycols with varying Mw and their mixture were also investigated to discriminate the role of the EO and the PO segments in the adsorption process. Enthalpies of transfer of RD, at fixed concentration, from water to the aqueous macromolecule solutions as functions of the macromolecule molality were determined. They …
Una comunità di pari?
Spatio-temporal perturbation of the dynamics of the ferroin catalyzed Belousov-Zhabotinsky reaction in a batch reactor caused by sodium dodecyl sulfate micelles.
The effects of the anionic surfactant sodium dodecyl sulfate (SDS) on the spatio-temporal and temporal dynamics of the ferroin-catalyzed Belousov-Zhabotinsky (BZ) reaction have been studied over a wide surfactant concentration range. For the first time, investigations were performed also for unstirred systems. The presence of SDS in the reaction mixture influences the oscillatory parameters to an extent that significantly depends on the surfactant concentration. The trend of the wave speed v upon the increasing amount of SDS was found to have a maximum at [SDS] = 0.075 mol dm (-3) ( v = 0.071 mm s (-1)), after which the speed decreased to 0.043 mm s (-1) at [SDS] = 0.5 mol dm (-3), which is…
Oscillations, waves and patterns in SDS micellar systems
Rate-retarding effects of mixed anionic/non-ionic micelles on the alkaline hydrolysis of the chloropentamminocobalt(III) complex - Role of the anionic surfactant chain nature
Rate data for the alkaline hydrolysis of the chloropentaamminecobalt(III) cation in the presence of mixed micelles composed of (i) anionic sodium decylsulphate (SDeS) and non-ionic dodecylpenta(oxyethylene glycol) monoether (C12E5) surfactants and (ii) anionic sodium perfluorooctanoate (SPFO) and non-ionic C12E5 surfactants has been obtained at T 298K and constant electrolyte concentration 0.08 mol dm−3 ([NaOH] = 0.01 mol dm−3, [NaClO4] = 0.07 mol dm−3) over a wide range of total surfactant concentration (Ct) and anionic mole fraction (χ). The critical micelle concentrations (c.m.c.s) of the mixed micelles have been determined over the entire χ range by means of surface tension measurements…
Chimica in Cucina
Elementi di Chimica Fisica
New way to produce smart materials: emulsion polimerization coupled to oscillating reaction
Temporal and spatio-temporal behaviour of the BZ reaction in the presence of SDS aggregates
Stationary Patterns and Segmented/Big Waves in a Belousov-Zabotinsky/Micelles System
Effect of pseudo-gravitational acceleration on the dissolution rate of miscible drops
The effect of pseudo-gravitational acceleration on the dissolution process of two phase miscible systems has been investigated at high acceleration values using a spinning drop tensiometer with three systems: 1-butanol/water, isobutyric acid/water, and triethylamine/water. We concluded that the dissolution process involves at least three different transport phenomena: diffusion, barodiffusion, and gravitational (buoyancy-driven) convection. The last two phenomena are significantly affected by the centrifugal acceleration acting at the interface between the two fluids, and the coupling with the geometry of the dissolving drop leads to a change of the mass flux during the course of the dissol…
Noi e la chimica - Dalla biochimica alle nanotecnologie
La Scoperta delle Scienze - 1
BZ reaction with oxalic acid mechanism investigations: I. oscillatory parameter region and rate constant measuments
Volumetric and viscosimetric studies to probing the structure of nano-organized systems based on nonionic block copolymers at some temperatures
Amphiphilic derivatives of a polyaspartamide: their aggregation and solubilization ability.Tensiometric and spectrophotometric studies
The self-aggregation and solubilization capability of a series of amphiphilic copolymers obtained by derivatisation of polymeric chain of α,β-poly(N-2-hydroxyethyl)-dl-aspartamide (PHEA) with polyethylene glycols (PEG, being different molecular weight 2000 or 5000 Da, PEG2000 and PEG5000, respectively) and/or hexadecylamine alkyl chain (C16), namely PHEA–PEG2000, PHEA–PEG5000, PHEA–C16, PHEA–PEG2000–C16 and PHEA–PEG5000–C16, have been evidenced by performing systematic tensiometric and spectrophotometric studies. All measurements have been performed at 25.0 °C over a wide copolymer concentration range. The tensiometric results have shown that, for all copolymers studied, the surface tension…
Nonlinear response of a batch BZ oscillator to the addition of the anionic surfactant sodium dodecyl sulfate.
The response of the Belousov-Zhabotinsy (BZ) system to the addition of increasing amounts of the anionic surfactant sodium dodecyl sulfate (SDS) was monitored at 25.0 degrees C in stirred batch conditions. The presence of SDS in the reaction mixture influences the oscillatory parameters, i.e., induction period and oscillation period, to an extent that depends on the surfactant concentration. The experimental results have shown that the induction period increases slightly on increasing surfactant concentration and, then, a further increase in the [SDS] leads to an enhancement while the oscillation period increases monotonously on increasing SDS concentration. It has been proposed that the re…
POLY 496-Behavior of the Belousov-Zhabotinsky oscillator in the presence of carboxymethyl-cellulose
Perturbation of the oscillatory Belousov-Zhabotinsky reaction with polyethylene glycol
The effects of the water soluble non-ionic polymers poly(ethylene glycol) (PEG-400, PEG-900 and PEG-2000) and poly(ethylene glycol dimethylether) (MPEG-2000) on the dynamics of the cerium ion catalyzed oscillatory Belousov-Zhabotinsky (BZ) reaction were investigated in a stirred batch reactor by measuring CO2 evolution rate and Ce(IV) absorbance changes. Addition of increasing amounts of additives strongly influences all the oscillatory parameters (induction period, time period and amplitude) to an extent that depends on the type of the additive used. The polymer perturbation effects are compared with those previously obtained with methanol and ethylene glycol (1). All these experimental ob…