Design of the reactive dyes containing large planar multi-conjugated systems and their application in non-aqueous dyeing

The development of pollution-free dyeing technology, including anhydrous dyeing and non-aqueous dyeing technologies, has always been an important way and research hot in energy conservation and emission reduction. Designing new structural dye molecules is the key to water-saving dyeing processes.Herein, three reactive dyes were designed and synthesized, which contained large planar multiconjugated systems and multi-reactive groups. The designed reactive dyes are expected to have high affinity and high fixations in non-aqueous or small bath dyeing processes. The reactive dyes were applied in the decamethylcyclopentasiloxane(DMCS) reverse micelle dyeing for cotton fabric. High exhaustion rate of 99.35%, 98.10% and 98.80%, and fixation rate of 95.15%, 96.34% and 94.40% for three dyes, R1,R2 and R3, could be respectively obtained. The dyes can be fully utilized and had excellent dyeing performance, fastness and levelling properties under the revere micelle dyeing. The cotton fabric is like an oil-water separator in the dyeing process, where the dye micelles rapidly absorb and permeate into the cotton fibers. DMCS circulates around the fabric to transfer mass and energy. After dyeing, the solvent can be separated quickly and reused. The new reactive dyes containing large planar and multi-conjugated systems have potential application in green and sustainable dyeing technology with less wastewater and higher utilization.

Effects of heavy metal ions Cu^(2+)/Pb^(2+)/Zn^(2+)on kinetic rate constants of struvite crystallization

Struvite(MAP)crystallization technology is widely used to treat ammonia nitrogen in waste effluents of its simple operation and good removal efficiency.However,the presence of heavy metal ions in the waste effluents causes problems such as slow crystallization rate and small crystal size,limiting the recovery rate and economic value of the MAP.The present study was conducted to investigate the effects of concentrations of three heavy metal ions(Cu^(2+),Zn^(2+),and Pb^(2+))on the crystal morphology,crystal size,average growth rate,and crystallization kinetics of MAP.A relationship was established between the kinetic rate constant Ktcalculated by the chemical gradient model and the concentrations of heavy metal ions.The results showed that low concentrations of heavy metal ions in the solution created pits on the MAP surface,and high level of heavy metal ions generated flocs on the MAP surface,which were composed of metal hydroxides,thus inhibiting crystal growth.The crystal size,average growth rate,MAP crystallization rate,and kinetic rate constant Ktdecreased with the increase in heavy metal ion concentration.Moreover,the Ktdemonstrated a linear relationship with the heavy metal concentration ln(C/C~*),which provided a reference for the optimization of the MAP crystallization process in the presence of heavy metal ions.

Modeling of the Dyeing Uptake Rate for Direct Dyestuff on Cotton in Batch Dyeing Process Based on Grey System Theory

The grey system theory, with the characteristics of fewer modeling data and higher accuracy, was employed to model the batch dyeing process for the purpose of accurate online control. The GM（1, 1） and GM （0, N） models of the grey system theory were discussed for their feasibilities of modding for batch dyeing process. The combination of direct dyestuff Fast Red F3B on cotton was chosen as a representative of the common dyeing method for describing the modeling process. Firstly, the GM（ 1, 1 ） model and the GM（1, 1） combined with GM（0, N） model were employed to model the equilibrium percentage of dyeing uptake rate. Secondly, an integrated dyeing uptake rate model with three factors （ temperature, salt concentration, and pH） was established based on the adsorption rate equation. Experimental results show that this model has higher accuracy and beetler generalization ability, which can predict the results of batch dyeing process. Due to the application of grey system theory, the model has a lot of advantages, such as being easy to determine the parameter value and small amount of calculation. So it can also be suitable for the same type of combination of dyestuff-fahric by changing the parameters value only.

Application Research on K/S Value in Determination of Reactive Dyes Fixation Rate

Reactive dyes are the main dyes in printing and dyeing of cellulosic fibers.Reactive dyes fixation rate is a vital indicator to measure the degree of the covalent bond between cellulose and reactive dyes.However,the determination of the fixation rate is tedious and time-consumptive.Based on the theory of reactive dyes dyeing and application of modern computer color matching technology,the relationship between K/S value and the fixation rate with the reactive dyes on cotton fabric was studied.The feasibility of K/S value instead of the traditional washing method for the determination of reactive dyes fixation rate was proved.In this study,the K/S value of the fabric has an excellent linear relationship to the reactive dyes fixation rate obtained by the washing method.The reactive dyes fixation rate can be obtained through the K/S correction value.

Chitosan and chemically modified chitosan beads for acid dyes sorption

The capabilities of chitosan and chitosan-EGDE （ethylene glycol diglycidyl ether） beads for removing Acid Red 37 （AR 37） and Acid Blue 25 （AB 25） from aqueous solution were examined. Chitosan beads were cross-linked with EGDE to enhance its chemical resistance and mechanical strength. Experiments were performed as a function ofpH, agitation period and concentration of AR 37 and AB 25. It was shown that the adsorption capacities of chitosan for both acid dyes were comparatively higher than those of chitosan- EGDE. This is mainly because cross-linking using EGDE reduces the major adsorption sites -NH3＋ on chitosan. Langmuir isotherm model showed the best conformity compared to Freundlich and BET. The kinetic experimental data agreed very well to the pseudo second-order kinetic model. The desorption study revealed that after three cycles of adsorption and desorption by NaOH and HCl, both adsorbents retained their promising adsorption abilities. FT-IR analysis proved that the adsorption of acid dyes onto chitosan-based adsorbents was a physical adsorption. Results also showed that chitosan and chitosan-EGDE beads were favourable adsorbers and could be employed as low-cost alternatives for the removal of acid dyes in wastewater treatment.

Temperature dependence of the absolute rate constant for the reaction of ozone with dimethyl sulfide

Absolute rate constants for the reaction of ozone with dimethyl sulfide （DMS） were measured in a 200-L Teflon chamber over the temperature range of 283-353 K. Measurements were carried out using DMS in large excess over ozone of 10 to 1 or greater. Over the indicated temperature range, the data could be fit to the simple Arrhenius expression as kDMS = （9.96 ± 3.61） × 10^-11 exp （-（7309.7 ± 1098.2）/T） cm^3/（molecule.s）. A compared investigation of the reaction between ozone and ethene had a kC2H4 value of （1.35 ± 0.11） × 10^-18 cm^3/（molecule.s） at room temperature.

Predicting Rate Constants for Nucleophilic Reactions of Amines with Diarylcarbenium Ions Using an ONIOM Method

The rate constants of the nucleophilic reactions between amines and benzhydrylium ions were calculated using first-principles theoretical methods. Solvation models including PCM, CPCM, and COSMORS, as well as different types of atomic radii including UA0, UAKS, UAHF, Bondi, and UFF, and several single-point energy calculation methods （B3LYP, B3P86, B3PW91, BHANDH, PBEPBE, BMK, M06, MP2, and ONIOM method） were examined. By comparing the correlation between experimental rate constants and the calculated values, the ONIOM（CCSD（T）/6-311＋＋G（2df,2p）：B3LYP/6-311＋＋G（2df,2p））//B3LYP/6- 31G（d）/PCM/UFF） method was found to perform the best. This method was then employed to calculate the rate constants of the reactions between diverse amines and diarylcarbenium ions. The calculated rate constants for 65 reactions of amines with diarylcarbenium ions are in agreement with the experimental values, indicating that it is feasible to predict the rate constant of a reaction between an amine and a diarylcarbenium ion through ab initio calculation.

Kinetic Rate Constant of Liquid Drainage from Colloidal Gas Aphrons

A kinetic model fitted by the empirical equation has been proposed to describe the liquid drainage behavior. Rate constants （kd） of liquid drainage equation could be obtained from the above empirical equation. In this paper, the stability of the colloidal gas aphrons （CGAs）, the effect of concentrations of sodium dodecyl benzene sulphate （SDBS）, dodecyl trimethylammonium bromide （HTAB） and polyoxyethylene sorbitol anhydride monolaurate（Tween-20）, temperature, stirring speed, stirring time, and various kinds of salts on the kd of liquid drainage are further investigated. The results show that the Arrhenius equation can be successfully used to describe the relation between kd arid absolute temperature （T）, and concentrations of surfactants, stirring speed, stirring time and salinities also have great effect on the kd. At last, the CGAs drainage mechanism is explained from analysis of the rate of liquid drainage as a function of time.

QSBR Study on the Biodegradation Rate Constant of Chloro-phenol Compounds

Structural and thermodynamic parameters of 16 chloro-phenol compounds in water solution were calculated and fully optimized by using Onsager model in self-consistent reaction field（SCRF） based on the B3LYP/6-311G＊＊ level.These quantum chemical parameters were used as theoretical descriptors to correlate with the experimental biodegradation rate constant（Kb） of 16 compounds by stepwise multiple linear regression.As a result,a three-parameter model including molecular average polarizability（α）,entropy（Sθ）,and molar heat capacity at constant volume（CVθ） were established for Kb prediction,which was proposed with correlation coefficient R2 = 0.894.α exhibits the most significant effect on Kb.Variance analysis and standard t-value test were applied to validate the model.As expected,this model exhibits good robustness and prediction ability,which can be used in Kb prediction of analogs.

A model for estimating the rate constant between CO_2-CO gas and molten slag containing iron oxides using optical basicity

A simple model for estimating the rate constant between CO2-CO gas and molten slag containing iron oxides was developed using optical basicity only. In this model, the temperature dependence of the rate constant can be described by the Arrhenius law, and the activation energy can be expressed with a linear function of the slag＇s optical basicity. The model was applied to some molten slag systems, such as FeO, FeO-CaO, FeO-SiO2, FeO-Na2O, FeO-CaO-SiO2, FeO-SiO2-P2O5, FeO-SiOE-Na2O, and FeO-CaO-SiOE-P2O5. A comparison between the predicted results and measured data showed that the model worked well.

Rate Constants for the Reactions of NO_3~.and SO_4^(._) Radicals with Oxalic Acid and Oxalate Anions in Aqueous Solution

Rate constants for the reactions of NO3 and SO4 radicals with oxalic acid and oxalate anions in aqueous solution have been measured using pulse radiolysis and laser flash photolysis.

Constant False Alarm Rate Acquisition Algorithm for Compass B1C Signal

In order to improve the sensitivity of the Compass B1C signal acquisition for the receiver,the principle of constant false alarm rate(CFAR)is applied for the B1C pilot channel acquisition to realize the dynamic adjustment of the threshold of acquisition against the carrier to noise ratio.The non-coherent data/pilot combined acquisition algorithm for B1C signal is analyzed to make full use of the power of the B1C signal under the condition of low carrier to noise ratio.On this basis,to improve the acquisition sensitivity of the receiver,the principle of constant false alarm probability is applied for the non-coherent data/pilot combined acquisition algorithm.Theoretical analysis and simulations show that the non-coherent data/pilot combined acquisition algorithm with CFAR improves the B1C signal acquisition sensitivity of the receiver significantly,and achieves a better Receiver Operating Characteristic compared with the traditional acquisition algorithms.

Theoretical prediction of energy dependence for D+BrO→DBr+O reaction:The rate constant and product rotational polarization

A quasi-classical trajectory（QCT） calculation is used to investigate the vector and scalar properties of the D ＋ Br O → DBr ＋ O reaction based on an ab initio potential energy surface（X1A state） with collision energy ranging from 0.1 kcal/mol to 6 kcal/mol. The reaction probability, the cross section, and the rate constant are studied. The probability and the cross section show decreasing behaviors as the collision energy increases. The distribution of the rate constant indicates that the reaction favorably occurs in a relatively low-temperature region（T 〈 100 K）. Meanwhile, three product angular distributions P（θr）, P（φr）, and P（θr, φr） are presented, which reflect the positive effect on the rotational angular momentum j＇ polarization of the DBr product molecule. In addition, two of the polarization-dependent generalized differential cross sections（PDDCSs）, PDDCS00 and PDDCS20, are computed as well. Our results demonstrate that both vector and scalar properties have strong energy dependence.

Key Role of Some Specific Occupied Molecular Orbitals of Short Chain n-Alkanes in Their Surface Tension and Reaction Rate Constants with Hydroxyl Radicals: DFT Study

Basing on the DFT calculations we propose the new theoretical model which describes both the surface tension σ of the short chain n-alkanes at their normal boiling points and their reaction rate constants with hydroxyl radicals OH• (at 297 ± 2 K) on the basis of their molecular orbital electronic characteristics. It has been shown that intermolecular dispersion attraction within the surface liquid monolayer of these compounds, as well as their reaction rate constants k with OH• radicals are determined by the energies Eorb of the specific occupied molecular orbitals which are the same in the determination of both the above physico-chemical characteristics of the studied n-alkanes. The received regression equations confirm the theoretically found dependences between the quantities of σ and k and the module |Eorb|. For the compounds under study this fact indicates the key role of their electronic structure particularities in determination of both the physical (surface tension) and the chemical (reaction rate constants) properties.

Apparent 1^st order rate constant of photodegradation of formaldehyde by carbon containing TiO2 nanoparticles

The apparent 1^st order rate constant of photodegradation of formaldehyde by carbon containing TiO2 nanoparticles has been investigated by numerical integration of mass transfer equation with measured degradation degree using a tubular photoreactor. The carbon containing TiO2 nanoparticles are synthesized by the oxidation of TiCl4 in propane/air flame CVD process with futile fraction up to 0.3 and carbon mass fractions up to 0.22, respectively. Thin TiO2 film is coated on the wall of the tubular reactor by sedimentation method. Effects of rutile mass fraction and carbon content have been examined on the apparent 1 ^st order rate constant and results show that, at 570ppm of formaldehyde loaded air stream, 80% relative humidity and about 100nm thin TiOa film, the 1^st order rate constant increases with increasing rutile mass fraction up to 0.3, occurs a maximum at the carbon content of about 5% by weight and is about 2.5 times of that at carbon content about zero or above 10%.

Influence of the Specific Surface of Polyester Supermicrofibre on the Dyeing Properties with Disperse Dyes

The influence of the polyester supermicrofiber specific surface on the dyeing properties of these fibres is studied with the purified disperse dye in this study. How the dyeing properties vary with the specific surface is shown. The dyeing properties mainly include dye saturation value, affinity, rate of dye uptake and equilibrium dye uptake etc. The relation between dye sorption behavior and the specific surface of the supermicrofibres is discussed.

Performance of Order-statistics Constant-false-alarm-rate Detector with Noncoherent Integration and Its Application to OTH Radar

Noncoherent integration is often ed for approving performance in detection of radar signal. Order-statistics constant false alarm rate (OS-CFAR) detector has some advantages in clutter and multiple target situations. AnOS-CFAN detector with noncoherent integration after Square law envelope detector is presented and an analysis of detection performance for the chi-Square family of Swerling fluctuating targets is given. Its application to the high frequency(HF) ground wave over-the-horizon (OTH) radar is discussed as well.

Sliding modes of fault activation under constant normal stiffness conditions

Fault activation has been the focus of research community for years.However,the studies of fault activation remain immature,such as the fault activation mode and its major factors under constant normal stiffness(CNS)conditions associated with large thickness of fault surrounding rock mass.In this study,the rock friction experiments were conducted to understand the fault activation modes under the CNS conditions.Two major parameters,i.e.the initial normal stress and loading rate,were considered and calibrated in the tests.To reveal the response mechanism of fault activation,the local strains near the fault plane were recorded,and the macroscopic stresses and displacements were analyzed.The testing results show that the effect of displacement-controlled loading rate is more pronounced under the CNS conditions than that under constant normal load(CNL)conditions.Both the normal and shear stresses drop suddenly when the stick-slip occurs.The decrease and increase of the normal stress are synchronous with the shear stress in the regular stick-slip scenario,but mismatch with the shear stress during the chaotic stick-slip process.The results are helpful for understanding the fault sliding mode and the prediction and prevention of fault slip.

Reaction-path Dynamics and Theoretical Rate Constants for the Reaction of CH_3CH_2OCF_3 with HOOO Radical

A dynamic method is employed to study the reaction mechanisms of CH3CH2OCF3 with the hydrogen trioxy （HOOO） radical. In our paper, the geometries and harmonic vibrational frequencies of all the stationary points and minimum energy paths （MEPs） are calculated at the MPW1K/6-31＋G（d,p） level of theory, and the energetic information along MEPs is further refined by the CCSD/6-31＋G（df, p） level of theory. The rate constants are evaluated with the conventional transition-state theory （TST）, the canonical variational transition-state theory （CVT）, the microcanonical variational transition-state theory （μVT）, the CVT coupled with the small-curvature tunneling （SCT） correction （CVT/SCT）, and the μVT coupled with the Eckart tunneling correction μVT/Eckart） based on the ab initio calculations in the temperature range of 200-3000 K. The theoretical results are important in determining the atmospheric lifetime and the feasible pathways for the loss of HFEs.

A Double-threshold Constant False Alarm Rate Detector And Its Performance Analysis

he cell averaging and the order statistics are two typical algorithms for constant false alarm rate detector in radar system. They have different advantages in stationary noise background and fluctuation clutter environment respectively. This paper presents a doublethreshold constant false alarm rate detector constructed on the basis of synthesizing the advantages of the two algorithms above and avioding their disadvantages. The performance of the detector is analyzed, and the simulation result is given.