Extraction kinetics of cerium(IV) from sulfuric acid medium by the primary amine N1923 using a constant interfacial area cell with laminar flow

BACKGROUND: Thermodynamic studies on Ce(IV) extraction with primary amine N1923 demonstrate that primary amine N1923 is an excellent extractant for separation of Ce(IV) from Re(III). In order to clarify the mechanism of extraction and to optimize the parameters in practical extraction systems used in the rare earth industry, the extraction kinetics was investigated using a constant interfacial area cell with laminar flow in the present work.RESULTS: The data indicate that the rate constant (k(ao).) becomes constant when stirring speed exceeds 250 rpm. The apparent forward extraction rate is calculated to be 10(-1.70). The activation energy (E.) was calculated to be 20.5 kJ/mol from the slope of log kao against 1000/T. The minimum bulk concentration of the extractant necessary to saturate the interface (C-min) is lower than 10(-5) mol L-1.CONCLUSION: Studies of interfacial tension and the effects of stirring rate and specific interfacial area on the extraction rate show that the extraction rate is kinetically controlled, and a mass transfer model has been proposed. The rate equation has been obtained as: -d[Ce(IV)]/dt = 10(-1.70)[Ce(IV)] [(RNH3)(2)SO4](1.376). The rate-controlling step has been evaluated from analysis of the experimental results.

Kinetics of Y(III) stripping for the system Y/HCl/Cyanex 272-P507/heptane with constant interfacial area cell with laminar flow

Kinetics and mechanism of stripping of yttrium(III) previously extracted by mixtures of bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272, HA), and 2-ethylhexyl phosphonic acid mono-2-ethylhexl ester (P507, HB) dissolved in heptane have been investigated by constant interfacial-area cell by laminar flow. The corresponding equilibrium stripping equation and equilibrium constant were obtained. The studies of effects of the stirring rate and temperature on the stripping rate show that the stripping regime is dependent on the stripping conditions. The plot of interfacial area on the rate has shown a linear relationship. This fact together with the strong surface activity of mixtures of Cyanex 272 and P507 at heptane-water interfaces makes the interface the most probable locale for the chemical reactions. The stripping rate constant is obtained, and the value is compared with that of the system with Cyanex 272 and P507 alone. It is concluded that the stripping ability with the mixtures is easier than that of P507 due to lower the activation energy of the mixtures. The stripping rate equation has also been obtained, and the rate-determining steps are the two-step interfacial chemical reactions as predicted from interfacial reaction models.

Kinetics of cerium(IV) extraction with DEHEHP from HNO3-HF medium using a constant interfacial cell with laminar flow

Studies of the extraction kinetics of cerium(IV) into n-heptane solutions of di(2-ethylhexyl)-2-ethylhexyl phosphonate DEHEHP from HNO3-HF solutions have been carried out using a constant interfacial cell with laminar flow. The experimental hydrodynamic conditions were chosen so that the contribution of diffusion to the measured rate of reaction was minimized. The data were analyzed in terms of pseudo-first order constants. The effects of the stirring rate, specific interfacial area, and temperature on the extraction rate showed that the most probable reaction zone is in the aqueous homogeneous phase. The results were compared with those of the system without HF. It was concluded that the presence of HF decreases the extraction rate of cerium. The addition of HF increases the activation energy for the forward reaction from 21.2 to 55.3 kJ/mol and for the reverse process from 57.9 to 79.0 kJ/mol. According to the experimental data correlated as a function of the concentration of the relevant species involved in the extraction reaction, the corresponding rate equation was deduced as follows:-d[Ce]/dt = k[Ce] center dot B-0.62 center dot HF-0.58 center dot [NO3-](0.57)

EASTMAN-AQ/NIII MODIFIED ELECTRODE CHARACTERIZATION AND APPLICATION IN FLOW-INJECTION DETERMINATION OF CARBOHYDRATES AND AMINO-ACIDS

A novel Eastman-AQ/Ni(II) chemically modified electrode (CME) produced by "double coating step" deposition of a poly(ester sulphonic acid) polymer film and Ni2+-containing crystalline species onto glassy carbon instead of a metallic nickel electrode exhibited stable electrocatalytic oxidation of numerous alpha-hydrogen compounds including carbohydrates, amines and amino acids. In cyclic voltammetry, the electrocatalysis appeared with an irreversible anodic wave at +0.55 V (vs. Ag/AgCl). The CME was adapted for constant-potential amperometric detection of these compounds in flow injection analysis. Using the CME, the linear response concentration range was between 1.0 x 10(-5) and 5.0 x 10(-2) mol/l and the detection limit was 5.0 x 10(-6) mol/l for glucose. The stability of the CME was adequate for routine quantitative application.

Geophysical signatures associated with fluid flow and gas hydrate occurrence in a tectonically quiescent sequence, Qiongdongnan Basin, South China Sea

Interpretation of high-resolution two-dimensional (2D) and three-dimensional (3D) seismic data collected in the Qiongdongnan Basin, South China Sea reveals the presence of polygonal faults, pockmarks, gas chimneys and slope failure in strata of Pliocene and younger age. The gas chimneys are characterized by low-amplitude reflections, acoustic turbidity and low P-wave velocity indicating fluid expulsion pathways. Coherence time slices show that the polygonal faults are restricted to sediments with moderate-amplitude, continuous reflections. Gas hydrates are identified in seismic data by the presence of bottom simulating reflectors (BSRs), which have high amplitude, reverse polarity and are subparallel to seafloor. Mud diapirism and mounded structures have variable geometry and a great diversity regarding the origin of the fluid and the parent beds. The gas chimneys, mud diapirism, polygonal faults and a seismic facies-change facilitate the upward migration of thermogenic fluids from underlying sediments. Fluids can be temporarily trapped below the gas hydrate stability zone, but fluid advection may cause gas hydrate dissociation and affect the thickness of gas hydrate zone. The fluid accumulation leads to the generation of excess pore fluids that release along faults, forming pockmarks and mud volcanoes on the seafloor. These features are indicators of fluid flow in a tectonically-quiescent sequence, Qiongdongnan Basin. Geofluids (2010) 10, 351-368.

A moored underwater energy conservation system for profiling measurement

There is a need to obtain the hydrologic data including ocean current, wave, temperature and so on in the South China Sea. A new profiling instrument which does not suffer from the damage due to nature forces or incidents caused by passing ships, is under development to acquire data from this area. This device is based on a taut single point mid-water mooring system. It incorporates a small, instrumented vertically profiling float attached via an electromechanical cable to a winch integral with the main subsurface flotation. On a pre-set schedule, the instrument float with sensors is winched up to the surface if there is no strip passing by, which is defined by an on-board miniature sonar. And it can be immediately winched down to a certain depth if the sonar sensor finds something is coming. Since, because Of logistics, the area can only be visited once for a long time and a minimum of 10 times per day profiles are desired, energy demands are severe. To respond to these concerns, the system has been designed to conserve a substantial portion of the potential energy lost during the ascent phase of each profile and subsequently use this energy to pull the instrument down. Compared with the previous single-point layered measuring mode, it is advanced and economical. At last the paper introduces the test in the South China Sea.

A unified criterion for initiation of sediment motion and inception of sheet flow under water waves

A unified criterion is developed for initiation of non-cohesive sediment motion and inception of sheet flow under water waves over a horizontal bed of sediment based on presently available experimental data. The unified threshold criterion is of the single form, U-o = 2 pi C[1 + 5(T-R/T)(2)](-1/4), where U-o is the onset velocity of sediment motion or sheet flow, T is wave period, and C and T-R are the coefficients. It is found that for a given sediment, U-o initially increases sharply with wave period, then gradually approaches the maximum onset velocity U-o = 2 pi C and becomes independent of T when T is larger. The unified criterion can also be extended to define sediment initial motion and sheet flow under irregular waves provided the significant wave orbital velocity and period of irregular waves are introduced in this unified criterion.

The variability of eddy kinetic energy in the South China Sea deduced from satellite altimeter data

We used fifteen years (1993-2007) of altimetric data, combined from different missions (ERS-1/2, TOPEX/Poseidon, Jason-1, and Envisat), to analyze the variability of the eddy kinetic energy (EKE) in the South China Sea (SCS). We found that the EKE ranged from 64 cm(2)/s(2) to 1 390 cm(2)/s(2) with a mean value of 314 cm(2)/s(2). The highest EKE center was observed to the east of Vietnam (with a mean value of 509 cm(2)/s(2)) and the second highest EKE region was located to the southwest of Taiwan Island (with a mean value of 319 cm(2)/s(2)). We also found that the EKE structure is the consequence of the superposition of different variability components. First, interannual variability is important in the SCS. Spectral analysis of the EKE interannual signal (IA-EKE) shows that the main periodicities of the IA-EKE to the east of Vietnam, to the southwest of Taiwan Island, and in the SCS are 3.75, 1.87, and 3.75 years, respectively. It is to the south of Taiwan Island that the IA-EKE signal has the most obvious impact on EKE variability. In addition, the IA-EKE exhibit different trends in different regions. An obvious positive trend is observed along the east coast of Vietnam, while a negative trend is found to the southwest of Taiwan Island and in the east basin of Vietnam. Correlation analysis shows that the IA-EKE has an obvious negative correlation with the SSTA in Nio3 (5A degrees S-5A degrees N, 90A degrees W-150A degrees W). El Nio-Southern Oscillation (ENSO) affects the IA-EKE variability in the SCS through an atmospheric bridge-wind stress curl over the SCS. Second, the seasonal cycle is the most obvious timescale affecting EKE variability. The locations of the most remarkable EKE seasonal variabilities in the SCS are to the east of Vietnam, to the southwest of Taiwan, and to the west of Philippines. To the east of Vietnam, the seasonal cycle is the dominant mechanism controlling EKE variability, which is attributed primarily to the annual cycle there of wind stress curl. In this area, the maximum EKE is observed in autumn. To the southwest of Taiwan Island, the EKE is enlarged by the stronger SCS circulation, which is caused by the intrusion branch from the Kuroshio in winter. Finally, intra-annual and mesoscale variability, although less important than the former, cannot be neglected. The most obvious intra-annual and mesoscale variability, which may be the result of baroclinic instability of the background flow, are observed to the southwest of Taiwan Island. Sporadic events can have an important effect on EKE variability.

Determination of fractional energy loss of waves in nearshore waters using an improved high-order Boussinesq-type model

Fractional energy losses of waves due to wave breaking when passing over a submerged bar are studied systematically using a modified numerical code that is based on the high-order Boussinesq-type equations. The model is first tested by the additional experimental data, and the model's capability of simulating the wave transformation over both gentle slope and steep slope is demonstrated. Then, the model's breaking index is replaced and tested. The new breaking index, which is optimized from the several breaking indices, is not sensitive to the spatial grid length and includes the bottom slopes. Numerical tests show that the modified model with the new breaking index is more stable and efficient for the shallow-water wave breaking. Finally, the modified model is used to study the fractional energy losses for the regular waves propagating and breaking over a submerged bar. Our results have revealed that how the nonlinearity and the dispersion of the incident waves as well as the dimensionless bar height (normalized by water depth) dominate the fractional energy losses. It is also found that the bar slope (limited to gentle slopes that less than 1:10) and the dimensionless bar length (normalized by incident wave length) have negligible effects on the fractional energy losses.

Wave generation by the falling rock in the two-dimensional wave tank

Wave generation by the falling rock in the two-dimensional wave tank is experimentally and numerically studied, where the numerical model utilizes the boundary element method to solve the fully nonlinear potential flow theory. The wave profiles at different times are measured in the laboratory, which are also used to test the numerical model. Comparisons show that the experimental and numerical results are in good agreement, and the numerical model can be used to simulate the wave generation due to the submarine rock falling. Further numerical tests on the influences of the rock size, density, initial position and the falling angle on the wave elevation of the generated waves are performed, respectively. The results show that the size and density of the rock have strong effects on the maximum elevation of the generated wave, while the effects of the initial position and the falling angle of the rock are also significant. When the size or the density of the rock increases, the maximum elevation of the generated wave increases. The same effect on the generated wave would be produced if the initial position of the rock becomes closer to the surface, or the falling angle between the falling route and the vertical direction turns larger. In addition, the present numerical tests reveal that the submarine rock falling provides a new generation method for the breaking wave in the wave tank.

Distribution of the nonlinear random ocean wave period

Because of the intrinsic difficulty in determining distributions for wave periods, previous studies on wave period distribution models have not taken nonlinearity into account and have not performed well in terms of describing and statistically analyzing the probability density distribution of ocean waves. In this study, a statistical model of random waves is developed using Stokes wave theory of water wave dynamics. In addition, a new nonlinear probability distribution function for the wave period is presented with the parameters of spectral density width and nonlinear wave steepness, which is more reasonable as a physical mechanism. The magnitude of wave steepness determines the intensity of the nonlinear effect, while the spectral width only changes the energy distribution. The wave steepness is found to be an important parameter in terms of not only dynamics but also statistics. The value of wave steepness reflects the degree that the wave period distribution skews from the Cauchy distribution, and it also describes the variation in the distribution function, which resembles that of the wave surface elevation distribution and wave height distribution. We found that the distribution curves skew leftward and upward as the wave steepness increases. The wave period observations for the SZFII-1 buoy, made off the coast of Weihai (37A degrees 27.6' N, 122A degrees 15.1' E), China, are used to verify the new distribution. The coefficient of the correlation between the new distribution and the buoy data at different spectral widths (nu=0.3-0.5) is within the range of 0.968 6 to 0.991 7. In addition, the Longuet-Higgins (1975) and Sun (1988) distributions and the new distribution presented in this work are compared. The validations and comparisons indicate that the new nonlinear probability density distribution fits the buoy measurements better than the Longuet-Higgins and Sun distributions do. We believe that adoption of the new wave period distribution would improve traditional statistical wave theory.

Simulation of the ocean surface mixed layer under the wave breaking

A one-dimensional mixed-layer model, including a Mellor-Yamada level 2.5 turbulence closure scheme, was implemented to investigate the dynamical and thermal structures of the ocean surface mixed layer in the northern South China Sea. The turbulent kinetic energy released through wave breaking was incorporated into the model as a source of energy at the ocean surface, and the influence of the breaking waves on the mixed layer was studied. The numerical simulations show that the simulated SST is overestimated in summer without the breaking waves. However, the cooler SST is simulated when the effect of the breaking waves is considered, the corresponding discrepancy with the observed data decreases up to 20% and the MLD calculated averagely deepens 3.8 m. Owing to the wave-enhanced turbulence mixing in the summertime, the stratification at the bottom of the mixed layer was modified and the temperature gradient spread throughout the whole thermocline compared with the concentrated distribution without wave breaking.

Numerical modeling of water wave interaction with a soft mud bed

A vertical 2-D numerical model is presented for simulating the interaction between water waves and a soft mud bed. Taking into account nonlinear rheology, a semi-empirical rheological model is applied to this water-mud model, reflecting the combined visco-elasto-plastic properties of soft mud under such oscillatory external forces as water waves. In order to increase the resolution of the flow in the neighborhood of both sides of the inter-surface, a logarithmic grid in the vertical direction is employed for numerical treatment. Model verifications are given through comparisons between the calculated and the measured mud mass transport velocities as well as wave height changes.

Numerical wave flume study on wave motion around submerged plates

Nonlinear interaction between surface waves and a submerged horizontal plate is investigated in the absorbed numerical wave flume developed based on the volume of fluid (VOF) method. The governing equations of the numerical model are the continuity equation and the Reynolds-Averaged Navier-Stokes (RANS) equations with the k-epsilon turbulence equations. Incident waves are generated by an absorbing wave-maker that eliminates the waves reflected from structures. Results are obtained for a range of parameters, with consideration of the condition under which the reflection coefficient becomes maximal and the transmission coefficient minimal. Wave breaking over the plate, vortex shedding downwave, and pulsating flow below the plate are observed. Time-averaged hydrodynamic force reveals a negative drift force. All these characteristics provide a reference for construction of submerged plate breakwaters.