Towards a Non Empirical Kinetic Model for the Lifetime Prediction of Polyethylene Pipes Transporting Drinking Water

A kinetic model has been elaborated to predict the lifetime of polyethylene pipes transporting slightly pressurized (3–12 bars) drinking water disinfected by free radical reagents. This model is composed of three levels: i) A system of differential equations, derived from a mechanistic scheme for radical chain oxidation in the presence of free radical reagents, giving access to the spatial distribution (in the pipe wall) of oxidation products and stabilizer concentration; ii) Equations allowing to predict the profiles of average molar masses from the spatial distribution of chain scissions and crosslinking events; iii) An empirical creep equation and a failure criterion derived from regression curves obtained in pure water (without disinfectant). It is assumed that the chemical degradation modifies only the time to transition between ductile and brittle regimes of failure, and that this time is linked to the weight average molar mass according to the classical power law. By superimposing these three levels, it is possible to predict the time to failure under the coupled effects of pressure and chemical degradation. This model is successfully applied to the case of chlorine dioxide.     

Combined kinetic analysis of thermal degradation of polymeric materials under any thermal pathway

Combined kinetic analysis has been applied for the first time to the thermal degradation of polymeric materials. The combined kinetic analysis allows the determination of the kinetic parameters from the simultaneous analysis of a set of experimental curves recorded under any thermal schedule. The method does not make any assumptions about the kinetic model or activation energy and allows analysis even when the process does not follow one of the ideal kinetic models already proposed in the literature. In the present paper the kinetics of the thermal degradation of both polytetrafluoroethylene (PTFE) and polyethylene (PE) have been analysed. It has been concluded, without previous assumptions on the kinetic model, that the thermal degradation of PTFE obeys a first order kinetic law, while the thermal degradation of PE follows a diffusion-controlled kinetic model.     

Kinetic model for the radical degradation of tri-halonitromethane disinfection byproducts in water

The halonitromethanes (HNMs) are byproducts of the ozonation and chlorine/chloramine treatment of drinking waters. Although typically occurring at low concentrations HNMs have high cytotoxicity and mutagenicity, and may therefore represent a significant human health hazard. In this study, we have investigated the radical based mineralization of fully-halogenated HNMs in water using the congeners bromodichloronitromethane and chlorodibromonitromethane. We have combined absolute reaction rate constants for their reactions with the hydroxyl radical and the hydrated electron as measured by electron pulse radiolysis and analytical measurements of stable product concentrations obtained by ⁶⁰Co steady-state radiolysis with a kinetic computer model that includes water radiolysis reactions and halide/nitrogen oxide radical chemistry to fully elucidate the reaction pathways of these HNMs. These results are compared to our previous similar study of the fully chlorinated HNM chloropicrin. The full optimized computer model, suitable for predicting the behavior of this class of compounds in irradiated drinking water, is provided.     

Kinetics and mechanism of the chlorine dioxide-trithionate reaction

The trithionate-chlorine dioxide reaction has been studied spectrophotometrically in a slightly acidic medium at 25.0 ± 0.1 °C in acetate/acetic acid buffer monitoring the decay of chlorine dioxide at constant ionic strength (I = 0.5 M) adjusted by sodium perchlorate. We found that under our experimental conditions two limiting stoichiometries exist and the pH, the concentration of the reactants, and even the concentration of chloride ion affects the actual stoichiometry of the reaction that can be augmented by an appropriate linear combination of these limiting processes. It is also shown that although the formal kinetic order of trithionate is strictly one that of chlorine dioxide varies between 1 and 2, depending on the actual chlorine dioxide excess and the pH. Moreover, the otherwise sluggish chloride ion, which is also a product of the reaction, slightly accelerates the initial rate of chlorine dioxide consumption and may therefore act as an autocatalyst. In addition to that, overshoot-undershoot behavior is also observed in the [(·)ClO(2)]-time curves in the presence of chloride ion at chlorine dioxide excess. On the basis of the experiments, a 13-step kinetic model with 6 fitted kinetic parameter is proposed by nonlinear parameter estimation.     

Kinetic Parameters of Polyethylene Degradation by the Natural Zeolite Chabazite

High-density polyethylene (PE) was subjected to thermal degradation alone and in the presence of an ammonium-exchanged zeolite chabazite (CHA/PE). The processes were carried out in a reactor connected online to a gas chromatograph/mass spectrometer in order to analyse the evolved products. Polymer degradation was also evaluated by thermogravimetry, from room temperature up to 800°C, under a dynamic nitrogen atmosphere, with multiple heating rates. From the TG curves, the activation energy relating to the degradation process was calculated by using the Flynn and Wall multiple heating rate kinetic model for pure PE and for CHA/PE. The exchanged chabazite exhibited good selectivity for the catalytic degradation of PE to low molecular mass hydrocarbons. This revised version was published online in August 2006 with corrections to the Cover Date.     

Liquid chromatography/time-of-flight mass spectrometric analyses for the elucidation of the photodegradation products of triclosan in wastewater samples

Liquid chromatography coupled with time-of-flight mass spectrometry (LC/TOFMS) was applied for the identification of four new photodegradation products of triclosan, a major antimicrobial agent used in personal care products. Wastewater samples, spiked at 7 microg/mL with triclosan, were irradiated with natural sunlight in order to generate the photodegradation products. Aliquots of the spiked water samples were taken at different times of irradiation and compounds were isolated from the water samples by solid-phase extraction. Separation and detection of the compounds and degradation products were accomplished by LC/TOFMS, which provided highly selective information about elemental compositions. Accurate mass measurements for the four degradation products permitted postulation of proposed empirical formulae in this study. Replacement of chlorine atoms by hydroxyl groups and chlorine losses are the major degradation pathways proposed. The degradation products were formed also under environmental conditions in wastewater matrices, thus suggesting their presence in real wastewater treatment processes.     

Aqueous chlorination of sulfamethazine and sulfamethoxypyridazine: Kinetics and transformation products identification

Sulfonamides (SNs) are synthetic antimicrobial agents. These substances are continually introduced into the environment, and they may spread and maintain bacterial resistance in the different compartments. The chlorination of 2 SNs, namely, sulfamethazine (SMT) and sulfamethoxypyridazine (SMP), was investigated to study their reactivity with chlorine at typical concentrations for water treatment conditions. Experiments conducted in purified water show an acceleration of SMT and SMP degradation of a factor 1.5 by comparison to drinking water matrix. This difference is due to pH variation and competitive reactions between SNs and mineral and organic compounds, with chlorine in drinking water. In the presence of an excess of chlorine (6.7 μmol·L⁻¹) in ultrapure water at pH 7.2, second‐order degradation rate constants were equal to 4.5 × 10²M⁻¹·s⁻¹ and 5.2 × 10²M⁻¹·s⁻¹ for SMT and SMP, respectively. The structures of transformation products were investigated by liquid chromatography tandem mass spectrometry analyses with equimolar concentrations between chlorine and SNs. SO₂ elimination, cyclization, and electrophilic substitutions were the main pathways of by‐products formation. Moreover, the toxicity of the proposed structures was predicted by using toxicity estimation software tool program. The results indicated that most by‐products may present developmental toxicity.     

Deterioration of polyethylene pipes exposed to water containing chlorine dioxide

Chlorine species used as disinfectants in tap water have a deteriorating effect on many materials including polyethylene. There are only very few scientific reports on the effect on polyethylene pipes of water containing chlorine dioxide. Medium-density polyethylene pipes stabilized with hindered phenol and phosphite antioxidants were pressure tested with water containing 4 ppm chlorine dioxide at 90 °C and pH = 6.8 as internal medium. The stabilizers were rapidly consumed towards the inner pipe wall; the rate of consumption was four times greater than in chlorinated water (4 ppm, pH = 6.8) at the same temperature. The depletion of stabilizer occurred far into the pipe wall. A supplementary study on a polymer analogue (squalane) containing the same stabilizer package showed that the consumption of the phenolic antioxidant was 2.5 times faster when exposed water containing chlorine dioxide than on exposure to chlorinated water. The subsequent polymer degradation was an immediate surface reaction. It was confirmed by differential scanning calorimetry, infrared spectroscopy and size exclusion chromatography that in the surface layer which came into contact with the oxidising medium, the amorphous component of the polymer was heavily oxidized leaving a highly crystalline powder with many carboxylic acid chain ends in extended and once-folded chains. Scanning electron microscopy showed that propagation of cracks through the pipe wall was assisted by polymer degradation.     

Studying the photochemical fate of methyl parathion in natural waters under tropical conditions

This article discusses the degradation of methyl parathion (MP) in natural and sterilized waters. Experiments were prepared using natural waters gathered in two aquatic systems (Rio de Janeiro State, Brazil), ultra-pure water and humic water solution under different conditions (i.e. in the presence/absence of light, sterilized/no sterilize solutions). The exposition to sunlight was carried out using experimental bottles without headspace immersed in a swimming pool for temperature control. Natural waters results showed that the degradation kinetic of MP is of first order and the half-lives for lake water experiments, under direct sunlight and shade, were 4.41 and 6.89 days, respectively. The kinetic curve for MP degradation in river waters showed that there are no differences when samples were sterilized and placed (or not) under shade conditions, and the half-lives ranged from 5.37 to 2.75 days for sterilized river water/absence of sunlight and natural/presence of sunlight, respectively. Therefore, our results showed that photolysis plays, in addition to bio- and chemical degradation, an important role in the decomposition of MP in aquatic environments.     

Closed form numerical approach for a kinetic interpretation of high-cis polybutadiene rubber vulcanization with sulphur

A novel mathematical approach to predict the vulcanization degree of high-cis polybutadiene rubber vulcanized with sulphur is presented. The model has kinetic base, it is constituted by four reactions occurring in series and parallel and takes contemporarily into consideration, within a simplified but reliable scheme, the actual reactions occurring during polybutadiene sulphur curing, namely primary crosslinking and possible de-vulcanization. The first order differential equation system obtained is suitably rearranged and a closed form expression for the vulcanization degree is derived, depending the four kinetic constants characterizing the chemistry describing reactions. Instead of using classic least-squares optimization routines to characterize kinetic constants on experimental data, a simplified but reliable approach is proposed, where a system of four non-linear equations is solved with a recursive strategy, allowing estimating kinetic constants that proved to fit well normalized experimental data. The procedure is fast and its reliability is tested on a number of experimental data available, relying into a high-cis polybutadiene rubber cured under different temperatures and accelerators concentrations. Very good approximations of experimental data are obtained, also in comparison with a heuristic numerical approach where optimization is obtained interactively.     

Studies on Kinetics of Chlorination Reaction of Polyethylene

Through kinetic method, the reaction mechanism and the rate equations of chlorination of polyethylene are suggested in this paper. The rate of chlorination is second order with respect to the concentration of methylene remained and chlorine, respectively. Apparent changes in crystallinity during chlorination processes were determinated by differential scanning calorimetry(DSC). The mathematical model relating crystallinety with kinetic parameters and function of sequence length distribution are derived.     

微囊藻毒素在单波长紫外光照射下的光降解动态研究

研究了两种微囊藻毒素在两种紫外光照射下的光降解行为,研究结果表明:UV-C是降解微囊藻毒素较好的光源;光照强度是影响毒素降解重要的因素,其次是温度和酸度;在UV-C的照射下,水体腐殖质对光降解具有抑制作用;微囊藻毒素的光解反应符合准一级动力学模型.同时本工作还按实际环境水体中毒素的含量水平进行了模拟研究,发现紫外光UV-C对环境水体中低含量的微囊藻毒素具有很强的去除能力.为今后发展无毒、高效、经济实用的饮用水处理技术做了有益的探索.     

Pneumatoamperometric determination of chlorine in water

Free chlorine in water can be determined by acidifying the water sample, purging it with nitrogen and determining the chlorine present in the nitrogen stream with a gold porous electrode. The current response of gold porous electrode is related to the concentration of free chlorine by using a calibration curve. This pneumatoamperometric method gives results fully comparable to the standard o-toluidine photometric method used for water supplies. It is uninfluenced by the presence of other dissolved oxidants and requires only one milliliter of sample.     

Reaction of β-blockers and β-agonist pharmaceuticals with aqueous chlorine. Investigation of kinetics and by-products by liquid chromatography quadrupole time-of-flight mass spectrometry

The degradation of two β-blockers (atenolol and propranolol) and one β-receptor agonist (salbutamol) during water chlorination was investigated by liquid chromatography-mass spectrometry (LC-MS). An accurate-mass quadrupole time-of-flight system (QTOF) was used to follow the time course of the pharmaceuticals and also used in the identification of the by-products. The degradation kinetics of these drugs was investigated at different concentrations of chlorine, bromide and sample pH by means of a Box-Behnken experimental design. Depending on these factors, dissipation half-lives varied in the ranges 68-145 h for atenolol, 1.3-33 min for salbutamol and 42-8362 min for propranolol. Normally, an increase in chlorine dosage and pH resulted in faster degradation of these pharmaceuticals. Moreover, the presence of bromide in water samples also resulted in a faster transformation of atenolol at low chlorine doses. The use of an accurate-mass high-resolution LC-QTOF-MS system permitted the identification of a total of 14 by-products. The transformation pathway of β-blockers/agonists consisted mainly of halogenations, hydroxylations and dealkylations. Also, many of these by-products are stable, depending on the chlorination operational parameters employed.     

Effective closed form starting point determination for kinetic model interpreting NR vulcanized with sulphur

In this paper, a closed form analytical approach for a recently presented kinetic model proposed in Milani and Milani (Polym Test, 2013, under review) to interpret NR sulphur vulcanization in presence of either experimental or surrogate rheometer curves is proposed. The model has kinetic base and is aimed at predicting, by means of a very refined approach, the vulcanization degree of NR vulcanized with sulphur. It needs as input only rheometer curves to fit and provides as output kinetic constants of the single reactions occurring during the crosslink process. In Milani and Milani (Polym Test, 2013, under review) a cure chemical scheme constituted by five reactions occurring in series and parallel was adopted. The chemical scheme, translated mathematically into a differential equations system, was suitably re-arranged and a single analytical equation was derived, representing rubber crosslink degree evolution upon time. The main drawback of such procedure is that the five kinetic constants corresponding to each reaction were determined through a standard non-linear least squares procedure, trying to minimize the deviation of the analytical cure curve from experimental data. Such a limitation is here superseded and a major improvement is proposed utilizing (1) a closed form solution which does not require any optimization algorithm and (2) finding analytically a starting point for the unknown kinetic constants, very near to the actual solution and thus very convenient for a successive least squares minimization. In the model, it is shown how the analytical condition deduced from the scorch point (second derivative of the rheometer curve equal to zero) and two further conditions, e.g. the time at 90 % of vulcanization and the reversion percentage, allow the simple direct evaluation of kinetic constants, providing a closed form analytical formula to predict well the state of cure of the rubber under consideration. To assess the results obtained with the model proposed, several examples on two different NRs are discussed. The approach proved to be extremely robust and much faster when compared with the model proposed by Milani and Milani (Polym Test, 2013, under review).     

Study of some UV filters stability in chlorinated water and identification of halogenated by-products by gas chromatography-mass spectrometry

This work studies the stability of three UV filters: 2-ethylhexyl salicylate (ES), 2-ethylhexyl 4-(dimethylamino) benzoate (EHPABA) and 2-hydroxy-4-methoxybenzophenone (BP-3), in water samples containing low concentrations of free chlorine. Moreover, 2,4-dihydroxybenzophenone (2,4-DHBP), a metabolite of BP-3, was also included in some of the performed assays. Experiments were carried out considering free chlorine and analytes concentrations at the microg mL(-1) and ng mL(-1) level, respectively. Gas chromatography with mass spectrometry was used to follow the time course of target compounds and to identify their halogenated by-products. Concentration of water samples with solid-phase extraction cartridges and derivatization (silylation) of some species were also employed to improve their detectability. Under the experimental conditions explored in this work, ES showed an acceptable stability whereas the rest of species reacted with free chlorine at significant rates following pseudo-first-order kinetics. Their half-lives ranged from 0.4 to 25 min depending on the UV filter, chlorine concentration, water pH and presence of bromide traces. For EHPABA a relatively simple degradation pathway was established. It consisted of aromatic substitution of one atom of hydrogen per chlorine or bromide. The same reaction pattern was observed for BP-3 leading, in this case, to mono- and di-halogenated by-products. In addition, several halogenated forms of 3-methoxyphenol were identified as BP-3 cleavage by-products.     

Poly α-ester degradation studies. IV. Rheological studies of polymer degradation

The Farol-Weissenberg rheogoniometer has been used to follow molecular weight changes during the degradation of certain poly-α-esters in the melt state. By observing the change in melt viscosity at low shear rates it had been shown that the decomposition of the poly(isopropylidene carboxylate) is substantially first-order with respect to the molecular weight of the residual polymer. The derived kinetic parameters are in good agreement with those previously obtained by other techniques. This provides a substantial piece of supporting evidence for the view that degradation takes place predominantly by intramolecular ester interchange involving the formation of 1,1,4,4,-tetramethylglycollide. The introduction of β-chlorine atoms into the polymer structure leads to a more complex degradation pattern. Thus the presence of a single β chlorine atom per repeat unit, as in poly(3-chloro-2-methyl-2-hydroxypropionic acid) leads to a substantially similar dependence on molecular weight with the added complication of progressive crosslinking which becomes more apparent in later stages of the reaction. This crosslinking reaction plays an increasingly important part as the extent of chlorination of the polymer is increased. In addition, the presence of chlorine leads to an increased sensitivity of the degradation reaction to the presence of oxygen.     

Intensification of the performance of kinetic inhibitors in the presence of polyethylene oxide and polypropylene oxide for simple gas hydrate formation in a flow mini-loop apparatus

The main objective of the present work is enhancement of the performance of gas hydrate kinetic inhibitors in the presence of polyethylene oxide (PEO) and polypropylene oxide (PPO) for simple gas hydrate formation in a flow mini-loop apparatus. PEO and PPO are high molecular weight polymers that are not kinetic inhibitors by their self. For this investigation, a laboratory flow mini-loop apparatus was set up to measure the induction time and rate of gas hydrate formation when a hydrate-forming substance (such as C1, C3, CO₂ and i-C4) is contacted with water containing dissolved inhibitor in presence or absence of PEO or PPO under suitable temperature and pressure conditions. In each experiment, water containing inhibitors blend saturated with pure gas is circulated up to a required pressure. Pressure is maintained at a constant value during experimental runs by means of required gas make-up. The effect of PEO and PPO on induction time and gas consumption during hydrate formation is investigated in the presence or absence of PVP (polyvinylpyrrolidone) and l-tyrosine as kinetic inhibitors. Results were shown that the induction time is prolonged in the presence of PEO or PPO compared to the inhibitor only. Inclusion of PPO into a kinetic hydrate inhibitor solution shows a higher enhancement in its inhibiting performance compare to PEO. Thus, the induction time for simple gas hydrate formation in presence of kinetic hydrate inhibitor with PPO is higher, compare to kinetic hydrate inhibitor with PEO.     

Assessing the long-term performance of polyethylene stabilised with phenolic antioxidants exposed to water containing chlorine dioxide

The addition of chlorine dioxide disinfectant to tap water prevents the spread of infection but has a serious drawback in that it degrades materials used in piping, including pipes made of polyethylene. Efficient methods are required to assess the long-term performance of different combinations of antioxidants and polyethylene grades. We have previously presented a screening method which exposes solutions of phenolic antioxidants in squalane (a liquid, low molar mass analogue of polyethylene) to 70 °C water containing either chlorine dioxide or chlorine. This method assesses the stability of the antioxidants towards these aqueous chlorinated media by determining the oxidation induction time through differential scanning calorimetry. The same experimental set-up with two modifications was used in developing a new method. A 0.3 mm thick polyethylene tape replaced the squalane phase and the supply of fresh water containing chlorine dioxide (10 ppm at pH = 6.8) was continuous; this required minimum attention from the operator over the longer exposure time periods used. Tapes of medium-density polyethylene containing 0.1 wt.% of six different phenolic antioxidants were studied. A linear relationship was established between the times to reach antioxidant depletion in the polyethylene tape samples and the times in the squalane samples (with the same antioxidants at the same concentration). A linear relationship was also found between the initial antioxidant consumption rates in polyethylene and squalane. Infrared spectroscopy and scanning electron microscopy of drawn samples revealed the onset of surface oxidation and surface embrittlement in tape samples exposed beyond the time for antioxidant depletion.     

Chlorinated polyethylene. II. Chlorine distribution on the polymer chains

The nature of substitution in a slurry-phase chlorination of high-density polyethylene was studied using NMR and IR spectroscopy. The ratios of γ (or greater) methylenes were obtained from the NMR at different chlorine levels and compared with the theoretically predicted values based on a statistical treatment for substitution polymers. The results indicted that, unlike chlorosulfonated polyethylene, chlorinated polyethylene shows a hindered-type substitution. Molecular weight of the parent polyethylene, the degree of chlorination and the degree of residual crystallinity of the samples have no bearing on the type of substitution.