Oscillation condition for a series piezoelectric sensor. Application to the determination of urease activity in plant seeds

The oscillating conditions for a series piezoelectric quartz crystal (SPQC) are proposed and verified experimentally. The influence of the cell constant and oscillator phase on the oscillational ability of the SPQC was investigated. It is shown that the SPQC possesses excellent oscillational ability in low or high conductivity solutions, but in solution of intermediate conductivity, the oscillational ability decreases with increasing oscillator phase or decreasing cell constant, sometimes resulting in a cease-to-oscillate zone. The SPQC was applied to determine the urease activity in plant seeds with a detection limit of 0.004 U ml⁻¹, based on the change in conductivity.     

Influence of oscillator phase on oscillation frequency and sensitivity of an electrode-separated piezoelectric sensor

Theoretical consideration was proposed for the influences of the oscillator phase on the response nature of an electrode-separated piezoelectric sensor (ESPS) to liquid properties and verified experimentally. For the oscillators with different phases, the oscillation frequency of the ESPS may increase, maintain nearly constant or decrease with increasing conductivity in low conductivity solutions. The sensitivity of response to density and viscosity increases slightly with increasing oscillator phase. The response to permittivity depends hardly on the oscillator phase. In addition, the dependence of the oscillation frequency of the ESPS on the supply voltage of the oscillator was explained. The ESPS was used to determine atropine sulfate with a detection limit of 1.6×10~7 mol/L.     

Sub-microlitre permittivity detectors for high-performance liquid chromatography

A theoretical model is developed for the response of permittivity detectors working at radiofrequency for h.p.l.c. applications. Three types of cell were tested: a coil cell, a parallel-ring cell and a two-wire intrusive cell. All offer small cell volumes (ca. 700 nl for the coil cell, 9 nl for the parallel-ring cell and 40 nl for the intrusive two-wire cell). The last cell, with a 20-MHz Franklin oscillator, is shown to be most useful for conventional and microbore h.p.l.c., offering low instrument noise and reasonable sensitivity. The model is shown qualitatively to describe the observed response well. The coil cell also offers the possibility of monitoring conductivity changes in electrolyte solutions through frequency-change measurements. The theoretical response function indicates that the oscillator frequency is proportional to the square root of the eluate conductivity.     

A new piezoelectric response model for population growth of bacteria

A piezoelectric response model on the population growth of microorganism is proposed. This model is based on a novel population growth model, which has a more obvious ecological meaning and the fact that the series piezoelectric quartz crystal (SPQC) sensor responses to conductivity changes of the medium during the growth of the microorganism. From the response model four parameters can be obtained including the maximum specific growth rate mu(m), saturated population size N(m), and two constants C and K(1). The influence of the parameters on the response curve is discussed in which the influences of mu(m) and N(m) are more obvious. With the proposed model the quantitative determination of bacteria may be more accurate than the frequency detection time (FDT) method. Then the growth of Escherichia coliform (E. coli) monitored with a SPQC sensor is compared with the simulated growth curve obtained by the proposed model and a good agreement is obtained.     

Oscillation Conditions for An Electrode-separated Piezoelectric Sensor in Electrolyte Solution

IntroductionRecently,anelectrode-separatedpiezoelectricsensor(ESPS),asanewtypeofchemicalsensors,hasbeenreportedandemployedinchemistryofsolu-tionL1-4J.Inthiskindofpiezoelectricsensors,thehighfrequencyexcitationelec-tricfieldisappliedtothequartzdiskbymeansofaso1utionlayer.Hence,thefrequencyofanESPSismoresensitivetothepermittivityandconductivityofthesolutionthanthatofaclassicalliquidpiezoelectricquartzcrysta1(PQC).TousetheESPSmorereasonably,thetheoryforthiskindofsensorsissti1lrequired'Ino…     

A Rapid Method for Determination of Growth of Thiobacillus Ferrooxidans by Series Piezoelectric Quartz Crystal

ABSTRACT

A rapid and simple method for monitoring the growth of Thiobacillus ferrooxidans is put forward by using a series piezoelectric quartz crystal (SPQC). The SPQC was applied to continuously determine the variation of frequency shift during the culture of Thiobacillus ferrooxidans, with a conductive electrode as the probe. The frequency shift as a function of time agrees with a typical 'S - shape' model, a piezoelectric sensor responding well to the growth of Thiobacillus ferrooxidans. The fundamentals for determination of the bacterial growth activity using the SPQC is also described; the frequency shift is only dependent on the electrical conductivity of the solution and the dielectric constant.     

THEORY AND APPLICATIONS OF FREQUENCYMETRIC TITRATION

Theory on frequencymetric titration has been proposed based on equivalent circuit of piezoelectric quartz crystal (PQC) in liquid and oscillation equation of TTL-PQC oscillator, and the theoretical equation derived representing the frequency shift with respect to the solution conductivity. Practical examples of various types of titration are given in this paper.     

盐水振荡研究的新发现

在对化学振荡的研究中,无论是溶液均相氧化还原形成的振荡反应,还是界面扩散受阻形成的界面振荡,都普遍采取各种电极法来监测。前文[1,2]研究了各种不同电极监测液膜振荡的变化,本文将讨论不同的电极方法在监测盐水振荡现象过程中的新发现。1970年,地球物理学家Martin[3]发现把     

乳液引发的电化学振荡

丹尼尔电池;可逆;蓄电池;乳液引发的电化学振荡     

Development of a new equation of state for mixed salt and mixed solvent systems,and application to vapour–liquid and solid (hydrate)–vapour–liquid equilibrium calculations

An equation of state that can be used for phase equilibrium and other thermodynamic property calculations at high pressures is developed for systems that contain aqueous solutions of strong electrolytes and molecular species. The proposed equation of state is based upon contributions to the Helmholtz free energy from a non-electrolyte term and three electrolyte terms. The non-electrolyte term comes from the Trebble–Bishnoi equation of state and the electrolyte terms consist of a Born energy term, a mean spherical approximation term and a newly developed hydration term. The application of the proposed equation of state to aqueous systems containing mixed salts and mixed solvents is illustrated by calculating the vapour–liquid equilibrium (VLE) and solid (Clathrate hydrate)–vapour–liquid equilibrium (SVLE) conditions for several systems. The solubility of CO₂ in salt water systems is examined at elevated pressures. As well, the new equation of state is used in conjunction with the model of van der Waals and Platteeuw to predict the SVLE conditions for gas hydrate forming systems in the presence of single salts, mixed salts and a mixture of aqueous salts and methanol. It is found that the new equation of state is able to accurately represent the experimental data over a wide range of pressure, temperature and salt concentration.     

Electrodeless piezoelectric quartz crystal and its behaviour in solutions

An electrodeless piezoelectric quartz crystal system was constructed with a quartz crystal plate, electrolyte solutions and platinum plates or rods immersed in the solutions for connecting to an oscillator, instead of the electrodes. The crystal without electrodes oscillates in the solutions. The frequency varies with temperature, specific conductance of the solutions and the mass change of the plate caused by the adsorption of material from the solution in, the same way as a normal piezoelectric quartz crystal with electrodes.     

Oscillating frequency of piezoelectric quartz crystal in solutions

Oscillating frequencies of a piezoelectric crystal were measured in various solutions. One side of the crystal surface was coated with a silicon sealant. This coating was useful for measuring the oscillation of crystals in solutions for a wide range of products of density (?) and viscosity (η) and in electrolyte solutions. For measurement in solutions, the frequency change depended on the circuit used, whereas for measurements in air the circuit did not influence the frequency change. All experimental data showed that the frequency change from pure water, ΔF_w, followed ΔF_w = ? K(√?η ? √?_wη_w) except for electrolyte and polymer solutions, where K is a proportionality constant, η_w the density of pure water and η_w the viscosity of water.     

Modeling hydrate formation conditions in the presence of electrolytes and polar inhibitor solutions

In this paper, a new predictive model is proposed for prediction of gas hydrate formation conditions in the presence of single and mixed electrolytes and solutions containing both electrolyte and a polar inhibitor such as monoethylene glycol (MEG), diethylene glycol (DEG) and triethylene glycol (TEG). The proposed model is based on the γ–φ approach, which uses modified Patel–Teja equation of state (VPT EOS) for characterizing the vapor phase, the solid solution theory by van der Waals and Platteeuw for modeling the hydrate phase, the non-electrolyte NRTL-NRF local composition model and Pitzer–Debye–Huckel equation as short-range and long-range contributions to calculate water activity in single electrolyte solutions. Also, the Margules equation was used to determine the activity of water in solutions containing polar inhibitor (glycols). The model predictions are in acceptable agreement with experimental data. For single electrolyte solutions, the model predictions are similar to available models, while for mixtures of electrolytes and mixtures of electrolytes and inhibitors, the proposed model gives significantly better predictions. In addition, the absolute average deviation of hydrate formation pressures (AADP) for 144 experimental data in solutions containing single electrolyte is 5.86% and for 190 experimental data in mixed electrolytes solutions is 5.23%. Furthermore, the proposed model has an AADP of 14.13%, 5.82% and 5.28% in solutions containing (Electrolyte + MEG), (Electrolyte + DEG) and (Electrolyte + TEG), respectively.     

Electrical conductivity of graphite suspensions in potassium chloride solutions in direct- and alternating-current electric fields

Electrical conductivity of graphite dispersions in aqueous KCl solutions has been measured. The measurements have been performed in alternating- (1000 Hz) and direct-current electric fields. In an alternating-current electric field, at electrolyte concentrations of 0.0005–0.01 М, the conductivity increases as depending on the mass fraction of the dispersed phase. In 0.1 М solutions, a decrease in the conductivity of the suspension is followed by an increase at dispersed phase contents of higher than 15 wt %. In a direct-current electric field, the conductivity of graphite suspensions (0.001–0.01 М KCl) varies slightly and increases at dispersed phase contents of higher than 15 wt %. In 0.1 М solutions, the specific conductivity of the suspension initially decreases and, then, increases at dispersed phase concentrations above 15 wt %. The unusual electrical properties of the suspensions have been explained as being results of variations in the capacitive and active components of the conductivity of graphite dispersions in electrolytes within the framework of a topological model. Particle polarization and a relatively high capacitive component of the conductivity mainly contribute to an increase in the conductivity of the suspensions in 0.0005–0.01 М electrolytes in the alternating-current electric field. A decrease in the conductivity of suspensions in 0.1 М electrolytes is due to a negative difference between the capacitive and active components of the specific conductivity. It has been assumed that the aggregation of graphite particles yields conducting structures at dispersed phase concentrations above 15 wt %.     

Asymmetry of diffusion permeability of bi-layer membranes

To reveal the reason of asymmetry of the diffusion permeability of bi-layer electrodialysis membranes the following problems have been solved using the model of "homogeneous porous membrane": - diffusion of non-electrolyte solutions across a bi-layer membrane; - diffusion of electrolyte solutions across a non-charged bi-layer membrane; - diffusion of electrolyte solutions across a charged single layer membrane; - diffusion of electrolyte solutions across a charged bi-layer membrane. It is shown that the main factor responsible for the asymmetry is the difference between absolute values of densities of fixed charges (or so called "exchange capacities") of different layers of a membrane under investigation. Only in this case the ratio of the thickness of the membrane layers as well as the ratio of ion diffusivities contributes also to the asymmetry of the diffusion permeability. In the present review we survey and generalize our previous investigations and propose a new theory of asymmetry of diffusion permeability of bi-layer membranes. We have deduced explicit algebraic formulas for the degree of asymmetry of diffusion permeability of bi-layer membranes under consideration.     

Dielectric analysis of nanofiltration membrane in electrolyte solutions: influences of electrolyte concentration and species on membrane permeation

Dielectric properties of a nanofiltration membrane immersed in dilute aqueous electrolyte solutions were measured, and frequency dependence of capacitance and conductance of the systems was analyzed, based on the interfacial polarization theory, giving values of permittivity and conductivity of the membrane and the solutions. Permittivity, epsilon m, of the membrane slightly decreased whereas conductivity, km, of the membrane increased with increasing electrolyte concentration, as a result of entrance of ions into the membrane. The ratio of membrane/solution conductivity, km/kw, also depended on the electrolyte concentration, showing that distribution of ions in the membrane and in solutions follow Donnan equilibrium, due to the presence of negative fixed charges in the membrane. New expressions were derived from Donnan equilibrium principle to explain this phenomenon, and negative fixed charge concentration ce of the membrane was obtained; thus the Donnan potential, DeltaPhi Don, of the membrane in solutions at various concentrations could be calculated. The new expressions could be expected to be usable to analyze ion permeation property through membrane.     

Electrode modification and the response of the acoustic shear wave device operating in liquids

The effect of electrode polarity, geometry, and stray capacitance on the performance of the thickness-shear mode acoustic wave sensor operating in electrolytes and solutions of biomolecules has been studied. In contrast to the well-known mass-based response of the device operating in the gas phase, the response in a liquid is governed by several factors including acoustoelectric and fringing field effects, which are known to be active at the edges of the electrodes. In order to investigate and utilize these effects, we modified the electrode geometry to increase the edge length, which, in turn, raises the sensitivity of the device. These changes which constituted either complete coverage of the back of the device with electrode material, or the removal of disks and lines from the electrode surface, resulted in a two to three times enhancement of sensor response. Such modifications that extend device sensitivity beyond the electrode area to the quartz region of the sensing structure also provide a better surface for the immobilization of various probes. We verified the enhancing ability of the modified electrodes for the case of adsorption of the protein avidin and neutravidin, followed by their affinity reactions with biotinylated biomolecules. It was found that the active electrode in contact with electrolyte exhibits a sensitivity of about twice that of the grounded electrode. The existence of stray capacitance around the cell was confirmed by shielding the cell assembly with a bath of concentrated KCl solution. This shielding effect was measured to be about 25-60 Hz in series resonant frequency and -1000 Hz in parallel resonant frequency.     

Hydrodynamic flows in electrowetting

Hydrodynamic flows are generated inside a droplet in electrowetting when an ac voltage is applied. To discover the characteristics and origin of the flows, we investigated the flow pattern for a sessile droplet for various needle-electrode positions, electrolyte concentrations, and applied electrical frequencies. Two distinct types of flows were observed under current experimental conditions. In the typical experimental condition, a quite fast flow appears in the low-frequency range of about 10 Hz to 15 kHz. A different type of flow is observed in the high-frequency range of about 35 to 256 kHz, but this frequency range depends significantly on the electrolyte concentration. Most typically, the flow directions are different for the two flows. A shape oscillation of a droplet was observed in the low-frequency range by a high-speed camera. The flow in the low-frequency range is insensitive to the conductivity of the solution and may be caused by the interfacial oscillation of the droplet. The flow at high frequency is very sensitive to the conductivity of the solution and electrode position, so the high-frequency flow is believed to be caused by some electrohydrodynamic effect.