Abstract: Chitosans, CSs, in solution are increasingly used in a range of geometric properties in various academic and industrial sectors, especially in the domain of pharmaceutical and biomedical engineering. In order to provide a tailoring guide of CSs to the applicants, gamma (γ)-irradiation technology and simple viscosity measurements have been used in this study. Accordingly, CS solid discs (0.5 cm thickness and 2.5 cm diameter) were exposed in air to Cobalt-60 (γ)-radiation, at room temperature and constant 50 kGy dose for different periods of exposer time (tγ). Diluted solutions of native and different irradiated CS were then prepared by dissolving 1.25 mg cm-3 of each polymer in 0.1 M NaCl/0.2 M CH3COOH. The single-concentration relative viscosity (ƞr) measurements were employed to obtain their intrinsic viscosity ([ƞ]) values and interrelated parameters, like: the molar mass (Mƞ), hydrodynamic radiuses (RH,ƞ), radius of gyration (RG,ƞ), and second virial coefficient (A2,ƞ) of CSs in the solution. The results show an exponential decrease of ƞr, [ƞ], Mƞ, RH,ƞ and RG,ƞ with increasing tγ. This suggests the influence of random chain-scission of CSs glycosidic bonds, with rate constant kr and kr-1 (lifetime τr ~ 0.017 min-1 and 57.14 min, respectively). The results also show an exponential decrease of A2ƞ with increasing tγ, which can be attributed to the growth of excluded volume effect in CS segments by tγ and, hence, better solution quality. The results are represented in following scaling laws as a tailoring guide to the applicants: RH,ƞ = 6.98 x 10-3 Mr0.65; RG,ƞ = 7.09 x 10-4 Mr0.83; A2,ƞ = 121.03 Mƞ,r-0.19.
Abstract: Due to the need for a rigorous mathematical model that can help to estimate kinetic properties for soluble-insoluble systems, through voltammetric experiments, a Nicholson Semi Analytical Approach was used in this work for modeling and prediction of theoretical linear sweep voltammetry responses for reversible, quasi reversible or irreversible electron transfer reactions. The redox system of interest is a one-step metal electrodeposition process. A rigorous analysis of simulated linear scan voltammetric responses following variation of dimensionless factors, the rate constant and charge transfer coefficients in a broad range was studied and presented in the form of the so called kinetic zones diagrams. These kinetic diagrams were divided into three kinetics zones. Interpreting these zones leads to empirical mathematical models which can allow the experimenter to determine electrodeposition reactions kinetics whatever the degree of reversibility. The validity of the obtained results was tested and an excellent experiment–theory agreement has been showed.
Abstract: One-dimensional (1D) nanostructures like nanowires, nanotubes, and nanorods find variety of practical application owing to their unique physico-chemical properties. In this work, TiO2 nanowires were synthesized by direct oxidation of titanium particles in a unique microwave plasma jet reactor. The prepared TiO2 nanowires manifested the flexible features, and were characterized by using X-ray diffraction, Brunauer-Emmett-Teller (BET) surface area analyzer, UV-Visible and FTIR spectrophotometers, Scanning electron microscope, and Transmission electron microscope. Further, the photodegradation efficiency of these nanowires were tested against toxic organic dye like methylene blue (MB) and the results were compared with the commercial TiO2. It was found that TiO2 nanowires exhibited superior photocatalytic performance (89%) as compared to commercial TiO2 (75%) after 60 min of reaction. This is attributed to the lower recombination rate and increased interfacial charge transfer in TiO2 nanowire. Pseudo-first order kinetic modelling performed with the experimental results revealed that the rate constant of photodegradation in case of TiO2 nanowire was 1.3 times higher than that of commercial TiO2. Superoxide radical (O2˙−) was found to be the major contributor in the photodegradation mechanism. Based on the trapping experiments, a plausible mechanism of the photocatalytic reaction is discussed.
Abstract: The main hypothesis of the dynamics of solid phase microextraction (SPME) is that steady-state mass transfer is respected throughout the SPME extraction process. It considers steady-state diffusion is established in the two phases and fast exchange of the analyte at the solid phase film/water interface. An improved model is proposed in this paper to handle with the situation when the analyte (atrazine) is in contact with colloid suspensions (carboxylate latex in aqueous solution). A mathematical solution is obtained by substituting the diffusion coefficient by the mean of diffusion coefficient between analyte and carboxylate latex, and also thickness layer by the mean thickness in aqueous solution. This solution provides an equation relating the extracted amount of the analyte to the extraction a little more complicated than previous models. It also gives a better description of experimental observations. Moreover, the rate constant of analyte obtained is in satisfactory agreement with that obtained from the initial curve fitting.
Abstract: An organoclay (HDTMA-B) was prepared from sodium bentonite (Na-B). The starting material was modified using the hexadecyltrimethylammonium ion (HDTMA+) in the amounts corresponding to 100 % of the CEC value. Batch experiments were carried out in order to model and optimize the sorption of Congo red dye from aqueous solution. The pseudo-first order and pseudo-second order kinetic models have been developed to predict the rate constant and the sorption capacity at equilibrium with the effect of temperature, the solid/solution ratio and the initial dye concentration. The equilibrium time was reached within 60 min. At room temperature (20 °C), optimum dye sorption of 49.4 mg/g (98.9%) was achieved at pH 6.6, sorbent dosage of 1g/L and initial dye concentration of 50 mg/L, using surfactant modified bentonite. The optimization of adsorption parameters mentioned above on dye removal was carried out using Box-Behnken design. The sorption parameters were analyzed statistically by means of variance analysis by using the Statgraphics Centurion XVI software.
Abstract: The main objective of this research was to study the differences of aluminum hydrolytic products between two PACl preparation methods. These two methods were the acidification process of freshly formed amorphous Al(OH)3 and the conventional alkalization process of aluminum chloride solution. According to Ferron test and 27Al NMR analysis of those two PACl preparation procedures, the reaction rate constant (k) values and Al13 percentage of acid addition process at high basicity value were both lower than those values of the alkaline addition process. The results showed that the molecular structure and size distribution of the aluminum species in both preparing methods were suspected to be significantly different at high basicity value.
Abstract: Three emerging contaminants (amitriptyline hydrochloride, methyl salicylate and 2-phenoxyethanol) frequently found in waste-waters were selected to be individually degraded in ultra-pure water by the combined advanced oxidation process constituted by UV radiation and chlorine. The influence of pH, initial chlorine concentration and nature of the contaminants was firstly explored. The trend for the reactivity of the selected compounds was deduced: amitriptyline hydrochloride > methyl salicylate > 2-phenoxyethanol. A later kinetic study was carried out and focused on the specific evaluation of the first-order rate constants and the determination of the partial contribution to the global reaction of the direct photochemical pathway and the radical pathway. A comparison between the rate constant values among photochemical experiments without and with the presence of Cl2 reveals a clear increase in the oxidation efficiency of the combined process with respect to the photochemical reaction alone. In a second stage, the simultaneous oxidation of mixtures of the selected contaminants in several types of water (ultrapure water, surface water from a reservoir, and two secondary effluents) was also performed by the same combination UV/Cl2 under more realistic operating conditions. The efficiency of this combined system UV/Cl2 was compared to other oxidants such as the UV/S2O82- and UV/H2O2 AOPs. Results confirmed that the UV/Cl2 system provides higher elimination efficiencies among the AOPs tested.
Abstract: Power law approximation was used in this study to evaluate the reaction orders of calcium oxide, CaO catalyzed transesterification of refined cottonseed oil and methanol. The kinetics study was carried out at temperatures of 45, 55 and 65 oC. The kinetic parameters such as reaction order 2.02 and rate constant 2.8 hr-1g-1cat, obtained at the temperature of 65 oC best fitted the kinetic model. The activation energy, Ea obtained was 127.744 KJ/mol. The results indicate that the transesterification reaction of the refined cottonseed oil using calcium oxide catalyst is approximately second order reaction.
Abstract: Fixed bed adsorption has become a frequently used
industrial application in wastewater treatment processes. Various low
cost adsorbents have been studied for their applicability in treatment
of different types of effluents. In this work, the intention of the study
was to explore the efficacy and feasibility for azo dye, Acid Orange 7
(AO7) adsorption onto fixed bed column of NaOH Treated eggshell
(TES). The effect of various parameters like flow rate, initial dye
concentration, and bed height were exploited in this study. The
studies confirmed that the breakthrough curves were dependent on
flow rate, initial dye concentration solution of AO7 and bed depth.
The Thomas, Yoon–Nelson, and Adams and Bohart models were
analysed to evaluate the column adsorption performance. The
adsorption capacity, rate constant and correlation coefficient
associated to each model for column adsorption was calculated and
mentioned. The column experimental data were fitted well with
Thomas model with coefficients of correlation R2 ≥0.93 at different
conditions but the Yoon–Nelson, BDST and Bohart–Adams model
(R2=0.911), predicted poor performance of fixed-bed column. The
(TES) was shown to be suitable adsorbent for adsorption of AO7
using fixed-bed adsorption column.
Abstract: In this study, we investigated the thixotropic behavior
of two clays used in fabrication of ceramic. The structural kinetic
model (SKM) was used to characterize the thixotropic behavior of
two different kinds of clays used in fabrication of ceramic. The SKM
postulates that the change in the rheological behavior is associated
with shear-induced breakdown of the internal structure of the clays.
This model for the structure decay with time at constant shear rate
assumes nth order kinetics for the decay of the material structure with
a rate constant.
Abstract: Anammox is a novel and promising technology that has changed the traditional concept of biological nitrogen removal. The process facilitates direct oxidation of ammonical nitrogen under anaerobic conditions with nitrite as an electron acceptor without addition of external carbon sources. The present study investigated the feasibility of Anammox Hybrid Reactor (AHR) combining the dual advantages of suspended and attached growth media for biodegradation of ammonical nitrogen in wastewater. Experimental unit consisted of 4 nos. of 5L capacity AHR inoculated with mixed seed culture containing anoxic and activated sludge (1:1). The process was established by feeding the reactors with synthetic wastewater containing NH4-H and NO2-N in the ratio 1:1 at HRT (hydraulic retention time) of 1 day. The reactors were gradually acclimated to higher ammonium concentration till it attained pseudo steady state removal at a total nitrogen concentration of 1200 mg/l. During this period, the performance of the AHR was monitored at twelve different HRTs varying from 0.25-3.0 d with increasing NLR from 0.4 to 4.8 kg N/m3d. AHR demonstrated significantly higher nitrogen removal (95.1%) at optimal HRT of 1 day. Filter media in AHR contributed an additional 27.2% ammonium removal in addition to 72% reduction in the sludge washout rate. This may be attributed to the functional mechanism of filter media which acts as a mechanical sieve and reduces the sludge washout rate many folds. This enhances the biomass retention capacity of the reactor by 25%, which is the key parameter for successful operation of high rate bioreactors. The effluent nitrate concentration, which is one of the bottlenecks of anammox process was also minimised significantly (42.3-52.3 mg/L). Process kinetics was evaluated using first order and Grau-second order models. The first-order substrate removal rate constant was found as 13.0 d-1. Model validation revealed that Grau second order model was more precise and predicted effluent nitrogen concentration with least error (1.84±10%). A new mathematical model based on mass balance was developed to predict N2 gas in AHR. The mass balance model derived from total nitrogen dictated significantly higher correlation (R2=0.986) and predicted N2 gas with least error of precision (0.12±8.49%). SEM study of biomass indicated the presence of heterogeneous population of cocci and rod shaped bacteria of average diameter varying from 1.2-1.5 mm. Owing to enhanced NRE coupled with meagre production of effluent nitrate and its ability to retain high biomass, AHR proved to be the most competitive reactor configuration for dealing with nitrogen laden wastewater.
Abstract: Amoxicillin is an antibiotic which is widely used to
treat various infections in both human beings and animals. However,
when amoxicillin is released into the environment, it is a major
problem. Amoxicillin causes bacterial resistance to these drugs and
failure of treatment with antibiotics. Liquid membrane is of great
interest as a promising method for the separation and recovery of the
target ions from aqueous solutions due to the use of carriers for the
transport mechanism, resulting in highly selectivity and rapid
transportation of the desired metal ions. The simultaneous processes
of extraction and stripping in a single unit operation of liquid
membrane system are very interesting. Therefore, it is practical to
apply liquid membrane, particularly the HFSLM for industrial
applications as HFSLM is proved to be a separation process with
lower capital and operating costs, low energy and extractant with
long life time, high selectivity and high fluxes compared with solid
membranes. It is a simple design amenable to scaling up for industrial
applications. The extraction and recovery for (Amoxicillin) through
the hollow fiber supported liquid membrane (HFSLM) using
aliquat336 as a carrier were explored with the experimental data. The
important variables affecting on transport of amoxicillin viz.
extractant concentration and operating time were investigated. The
highest AMOX- extraction percentages of 85.35 and Amoxicillin
stripping of 80.04 were achieved with the best condition at 6 mmol/L
[aliquat336] and operating time 100 min. The extraction reaction
order (n) and the extraction reaction rate constant (kf) were found to
be 1.00 and 0.0344 min-1, respectively.
Abstract: This paper is about method to produce a stable and
accurate constant output pulse width regardless of the amplitude,
period and pulse width variation of the input signal source. The pulse
generated is usually being used in numerous applications as the
reference input source to other circuits in the system. Therefore, it is
crucial to produce a clean and constant pulse width to make sure the
system is working accurately as expected.
Abstract: Anaerobic modeling is a useful tool to describe and
simulate the condition and behaviour of anaerobic treatment units for
better effluent quality and biogas generation. The present
investigation deals with the anaerobic treatment of brewery
wastewater with varying organic loads. The chemical oxygen demand
(COD) and total suspended solids (TSS) of the influent and effluent
of the bioreactor were determined at various retention times to
generate data for kinetic coefficients. The bio-kinetic coefficients in
the modified Stover–Kincannon kinetic and methane generation
models were determined to study the performance of anaerobic
digestion process. At steady-state, the determination of the kinetic
coefficient (K), the endogenous decay coefficient (Kd), the maximum
growth rate of microorganisms (μmax), the growth yield coefficient
(Y), ultimate methane yield (Bo), maximum utilization rate constant
Umax and the saturation constant (KB) in the model were calculated to
be 0.046 g/g COD, 0.083 (d¯¹), 0.117 (d-¹), 0.357 g/g, 0.516 (L
CH4/gCODadded), 18.51 (g/L/day) and 13.64 (g/L/day) respectively.
The outcome of this study will help in simulation of anaerobic model
to predict usable methane and good effluent quality during the
treatment of industrial wastewater. Thus, this will protect the
environment, conserve natural resources, saves time and reduce cost
incur by the industries for the discharge of untreated or partially
treated wastewater. It will also contribute to a sustainable long-term
clean development mechanism for the optimization of the methane
produced from anaerobic degradation of waste in a close system.
Abstract: The kinetics of Cu(II) transport through a bulk liquid membrane with different membrane materials was investigated in this work. Three types of membrane materials were used: fresh cooking oil, waste cooking oil and kerosene, each of which was mixed with di-2-ethylhexylphosphoric acid (carrier) and tributylphosphate (modifier). Kinetic models derived from the kinetic laws of two consecutive irreversible first-order reactions were used to study the facilitated transport of Cu(II) across the source, membrane and receiving phases of bulk liquid membrane. It was found that the transport kinetics of Cu(II) across the source phase was not affected by different types of membrane materials but decreased considerably when the membrane materials changed from kerosene, waste cooking oil to fresh cooking oil. The rate constants of Cu(II) removal and recovery processes through the bulk liquid membrane were also determined.
Abstract: Iron in groundwater is one of the problems that render the water unsuitable for drinking. The concentration above 0.3 mg/L is common in groundwater. The conventional method of removal is by precipitation under oxic condition. In this study, iron removal under anaerobic conditions was examined by batch experiment as a main purpose. The process involved by purging of groundwater samples with H2S to form iron sulfide. Removal up to 83% for 1 mg/L iron solution was achieved. The removal efficiency dropped to 82% and 75% for the higher initial iron concentrations 3.55 and 5.01 mg/L, respectively. The average residual sulfide concentration in water after the process was 25*g/L. The Eh level during the process was -272 mV. The removal process was found to follow the first order reaction with average rate constant of 4.52 x 10-3. The half-life for the concentrations to reduce from initial values was 157 minutes.
Abstract: Four phenylurea herbicides (isoproturon, chlortoluron, diuron and linuron) were dissolved in different water matrices in order to study their chemical degradation by using UV radiation, ozone and some advanced oxidation processes (UV/H2O2, O3/H2O2, Fenton reagent and the photo- Fenton system). The waters used were: ultra-pure water, a commercial mineral water, a groundwater and a surface water taken from a reservoir. Elimination levels were established for each herbicide and for several global quality parameters, and a kinetic study was performed in order to determine basic kinetic parameters of each reaction between the target phenylureas and these oxidizing systems.
Abstract: Curing of paints by exposure to UV radiations is
emerging as one of the best film forming technique as an alternative
to traditional solvent borne oxidative and thermal curing coatings.
The composition and chemistry of UV curable coatings and role of
multifunctional and monofunctional monomers, oligomers, and
photoinitiators have been discussed. The limitations imposed by
thermodynamic equilibrium and tendency for acrylic double bond
polymerizations during synthesis of multifunctional acrylates have
been presented. Aim of present investigation was thus to explore the
reaction variables associated with synthesis of multifunctional
acrylates. Zirconium oxychloride was evaluated as catalyst against
regular acid functional catalyst. The catalyzed synthesis of glyceryl
acrylate and neopentyl glycol acrylate was conducted by variation of
following reaction parameters: two different reactant molar ratios-
1:4 and 1:6; catalyst usage in % by moles on polyol- 2.5, 5.0 and 7.5
and two different reaction temperatures- 45 and 75 0C. The reaction
was monitored by determination of acid value and hydroxy value at
regular intervals, besides TLC, HPLC, and FTIR analysis of
intermediates and products. On the basis of determination of reaction
progress over 1-60 hrs, the esterification reaction was observed to
follow 2nd order kinetics with rate constant varying from 1*10-4 to
7*10-4. The thermal and catalytic components of second order rate
constant and energy of activation were also determined. Uses of
these kinetic and thermodynamic parameters in design of reactor for
manufacture of multifunctional acrylate ester have been presented.
The synthesized multifunctional acrylates were used to formulate and
apply UV curable clear coat followed by determination of curing
characteristics and mechanical properties of cured film. The overall
curing rates less than 05 min. were easily attained indicating
economical viability of radiation curable system due to faster
production schedules
Abstract: In this study, the kinetic of biogas production was studied by performing a series laboratory experiment using rumen fluid of animal ruminant as inoculums. Cattle manure as substrate was inoculated by rumen fluid to the anaerobic biodigester. Laboratory experiments using 400 ml biodigester were performed in batch operation mode. Given 100 grams of fresh cattle manure was fed to each biodigester and mixed with rumen fluid by manure : rumen weight ratio of 1:1 (MR11). The operating temperatures were varied at room temperature and 38.5 oC. The cumulative volume of biogas produced was used to measure the biodigester performance. The research showed that the rumen fluid inoculated to biodigester gave significant effect to biogas production (P
Abstract: ZnO nanocrystals with mean diameter size 14 nm
have been prepared by precipitation method, and examined as
photocatalyst for the UV-induced degradation of insecticide diazinon
as deputy of organic pollutant in aqueous solution. The effects of
various parameters, such as illumination time, the amount of
photocatalyst, initial pH values and initial concentration of
insecticide on the photocatalytic degradation diazinon were
investigated to find desired conditions. In this case, the desired
parameters were also tested for the treatment of real water containing
the insecticide. Photodegradation efficiency of diazinon was
compared between commercial and prepared ZnO nanocrystals. The
results indicated that UV/ZnO process applying prepared
nanocrystalline ZnO offered electrical energy efficiency and
quantum yield better than commercial ZnO. The present study, on the
base of Langmuir-Hinshelwood mechanism, illustrated a pseudo
first-order kinetic model with rate constant of surface reaction equal
to 0.209 mg l-1 min-1 and adsorption equilibrium constant of 0.124 l
mg-1.