Abstract The sorption behavior of 3.18×10?6 mol l?1 solution of Tm(III) metal ions onto 7.25 mg l?1 of 1‐(2‐pyridylazo)‐2‐naphthol (PAN) loaded polyurethane foam (PUF) has been investigated at different temperatures i.e. 303 K, 313 K, and 323 K. The maximum equilibration time of sorption was 30 minutes from pH 7.5 buffer solution at all temperatures. The various rate parameters of adsorption process have been investigated. The diffusional activation energy (ΔEads) and activation entropy (ΔSads) of the system were found to be 22.1±2.6 kJ mol?1 and 52.7±6.2 J mol?1 K?1, respectively. The thermodynamic parameters such as enthalpy (ΔH), entropy (ΔS), and Gibbs free energy (ΔG) were calculated and interpreted. The positive value of ΔH and negative value of ΔG indicate that sorption is endothermic and spontaneous in nature, respectively. The adsorption isotherms such as Freundlich, Langmuir, and Dubinin–Radushkevich isotherm were tested experimentally at different temperatures. The changes in adsorption isotherm constants were discussed. The binding energy constant (b) of Langmuir isotherm increases with temperature. The differential heat of adsorption (ΔHdiff), entropy of adsorption (ΔSdiff) and adsorption free energy (ΔGads) at 313 K were determined and found to be 38±2 kJ mol?1, 249±3 J mol?1 K?1 and –40.1±1.1 kJ mol?1, respectively. The stability of sorbed complex and mechanism involved in adsorption process has been discussed using different thermodynamic parameters and sorption free energy. 相似文献
This article provides evidences that hydride transfer is an important primary step in ozone reactions of formate and tertiary butanol in aqueous media. In both systems, one argument is the fact that the free hydroxyl radical yields are relative low ((40 ± 4)% and (7 ± 0.8)% for formate and tertiary butanol, respectively). Another hint is the high exergonicity of these reactions: ΔG = –249 kJ mol?1 for formate/ozone system and ΔG = –114 kJ mol?1 for hydride transfer followed by a methyl shift in the reaction between tertiary butanol and ozone. In addition, the main product of tertiary butanol ozonolysis is butan-2-one [(89 ± 3)%], a compound that is formed only via hydride transfer. For the reaction of ozone with formate an activation energy of (54.6 ± 1.2) kJ mol?1 and a pre-exponential term of (2.5 ± 1.2) × 1011 were determined (in the presence of tertiary butanol as ?OH scavenger) whereas for tertiary butanol the two activation parameters were (68.7 ± 1.9) kJ mol?1 and (2.0 ± 1.5) × 109, respectively. 相似文献
The parameters affecting the initial adsorption rates of Astrazone Blue dye (Basic Blue 69) on to wood have been studied. A simple model has been proposed to determine the external mass transfer coefficients and these have been compared with values obtained using a more complex procedure. The external mass transfer coefficient, β, has been shown to vary linearly with agitation and initial dye concentration using log-log coordinates; furthermore β is independent of particle size. The effect of temperature has been studied and the activation energy for the process is 44 ± 2 kJ mol?1. Similar correlations were obtained for the adsorption of Telon Blue dye (Acid Blue 25) on wood. Using log-log correlations, the external mass transfer coefficient was found to vary with (rev min?1)0.14, C0?0.27; and a small dependence on particle size was also observed. The activation energy for the external mass transfer process was 25 ± 2 kJ mol?1. 相似文献
The influence of the apatite on the efficiency of neutralization and on heavy metal removal of acid mine waste water has been studied. The analysis of the treated waste water samples with apatite has shown an advanced purification, the concentration of the heavy metals after the treatment of the waste water with apatite being 25 to 1000 times less than the Maximum Concentration Limits admitted by European Norms (NTPA 001/2005). In order to establish the macro‐kinetic mechanism in the neutralization process, the activation energy, Ea, and the kinetic parameters, rate coefficient of reaction, kr, and kt were determined from the experimental results obtained in “ceramic ball‐mill” reactor. The obtained values of the activation energy Ea >> 42 kJ mol?1 (e.g. Ea = 115.50 ± 7.50 kJ mol?1 for a conversion of sulphuric acid ηH2SO4 = 0.05, Ea = 60.90 ± 9.50 kJ mol?1 for η H2SO4 = 0.10 and Ea = 55.75 ± 10.45 kJ mol‐1 for η H2SO4 = 0.15) suggest that up to a conversion of H2SO4 equal 0.15 the global process is controlled by the transformation process, adsorption followed by reaction, which means surface‐controlled reactions. At a conversion of sulphuric acid η H2SO4 > 0.15, the obtained values of activation energy Ea < 42 kJ mol‐1 (e.g. Ea = 37.55 ± 4.05 kJ mol‐1 for η H2SO4 = 0.2, Ea = 37.54 ± 2.54 kJ mol‐1 for η H2SO4 = 0.3 and Ea = 37.44 ± 2.90 kJ mol‐1 for η H2SO4 = 0.4) indicate diffusion‐controlled processes. This means a combined process model, which involves the transfer in the liquid phase followed by the chemical reaction at the surface of the solid. Kinetic parameters as rate coefficient of reaction, kr with values ranging from (5.02 ± 1.62) 10‐4 to (8.00 ± 1.55) 10‐4 (s‐1) and transfer coefficient, kt, ranging from (8.40 ± 0.50) 10‐5 to (10.42 ± 0.65) 10‐5 (m s‐1) were determined. 相似文献
The objective of this work was to evaluate the kinetics and thermodynamics parameters and the effects of anionic, cationic and nonionic surfactants and polyethylene glycol on the activity and stability of a crude esterase extracted from soybeans (Glycine max L.). The activation energy for thermal inactivation was calculated from the Arrhenius plot was found to be 59.4 kJ mol?1 and the ΔH* 56.82 kJ mol?1 at 40 °C, which was the optimum temperature for enzyme activity. The ΔS* and ΔG* of the enzyme were found to be 61.67 kJ mol?1 and 15.50 J mol?1 K?1, respectively, at the optimum temperature. The activity was only enhanced by the cationic surfactants cetyltrimethylammonium bromide and tetradecylmethylammonium bromide at a concentration of 3.0 mM. The anionic surfactant showed a positive effect on enzyme activity at the concentrations of 1.5 and 3.0 mM. Aqueous PEG (polyethylene glycols) solutions activated the esterase, and maximum activation (170 %) occurred with the addition of 6 kDa PEG. PEG with molecular weights of 0.4 and 10 kDa enhanced enzyme stability at 40 °C. 相似文献
The article describes transport of Pb(II) through bulk liquid membrane (BLM) containing calix[6]arene hexaester derivative (1) as a carrier. The effect of various parameters such as temperature, carrier concentration, stirring speed and type of solvent on the Pb(II) transport efficiency of the carrier through BLM was evaluated. The activation energy values for the extraction and re-extraction were found as 56.33 kJ mol?1 and 14.79 kJ mol?1, respectively. These values demonstrate that the process is diffusionally controlled by Pb(II). Observations indicate that the membrane entrance and exit rate constants (k1, k2) increase with increasing stirring speed as well as carrier concentration and decrease with increasing temperature. The effect of solvent on k1 and k2 was found to be in the order of CH2Cl2 > CHCl3 > CCl4. 相似文献
The kinetic and thermodynamic features of free‐radical batch emulsion polymerization of a sugar monomer (3‐MDG) and butyl acrylate (BA) were investigated in a power compensation calorimeter. The homopolymerizations as well as the copolymerization have been studied. The overall activation energy of 3‐MDG homopolymerization was 140 ± 3.8 kJ · mol?1, the polymerization enthalpy was ΔHMDG = ?51.6 ± 1.9 kJ · mol?1 and the calculated adiabatic temperature rise was ΔTad = 78.5 K. The effects of the initiator and the emulsifier concentrations on the 3‐MDG/BA batch copolymerization kinetics and on the colloidal properties of the final sugar latexes were studied at 60 °C. At higher emulsifier and initiator concentration, respectively, the polymerization rate increases and the particle size decreases, but the trends do not conform to the Smith‐Ewart theory. Polydisperse sugar latex particles with a mean diameter in the range of 50–67 nm were obtained.
Relationship between the activation energy and the conversion for BA (open symbols) and 3‐MDG (solid symbols). 相似文献
The kinetics of the oxirane cleavage of epoxidized soybean oil (ESO) by methanol (Me) without a catalyst was studied at 50,
60, 65, 70 °C. The rate of oxirane ring opening is given by k[Ep][Me]2, where [Ep] and [Me] are the concentrations of oxiranes in ESO and methanol, respectively and k is a rate constant. From the temperature dependence of the kinetics thermodynamic parameters such as enthalpy (ΔH), entropy (ΔS), free energy of activation (ΔF) and activation energy (ΔEa) were found to be 76.08 (±1.06) kJ mol−1, −118.42 (±3.12) J mol−1 k−1, 111.39 (±2.86) kJ mol−1, and 78.56 (±1.63) kJ mol−1, respectively. The methoxylated polyols formed from the oxirane cleavage reaction , were liquid at room temperature and had
three low temperature melting peaks. The results of chemical analysis via titration for residual oxiranes in the reaction
system showed good agreement with IR spectroscopy especially the disappearance of epoxy groups at 825, 843 cm−1 and the emergence of hydroxy groups at the OH characteristic absorption peak from 3,100 to 3,800 cm−1. 相似文献
This work reports the experimental results of kinetics study of n-butylparaben (BP) degradation in H2O2/UV systems. A pseudo–steady-state and competition kinetic approaches were used to determine the reaction rate constants between the BP and ?OH. In competition kinetics atrazine (2.30?×?109 M?1?s?1) was used as a reference compound. The measured rate constants for ?OH reaction with BP ranged from (3.84 ± 0.12)?×?109 M?1?s?1 to (8.56 ± 0.90)?×?109 M?1?s?1 depending on solution pH and temperature. Values of the rate constant obtained using different methods were in good agreement. The calculated activation energy was equal to 19.01 ± 1.02 kJ mol?1. 相似文献