Sensitivity gravimetric

A different type of extremely sensitive gravimetric technique is based on the effe change of mass on the resonance frequency of a vibrating quartz crystal (see Fi 3.12). In this case, the adsorbent must be firmly attached to the crystal. Its area be as small as a few square centimetres and mass changes as low as 10-2 pg ca detected from the frequency shift (Krim and Watts, 1991). 

In an attempt to observe the threshold pressure, Thompson selected a material that one would believe to have a low energy of adsorption. The direct observation of the threshold pressure is possible, if the interaction energy between the surface and the adsorbed molecules is small. This can be easily illustrated with adsorption of N2 or Ar on polytetrafluoroethylene (Teflon ) obtained by Thompson [22], which according to theory should have a very high threshold pressure. The threshold pressure may clearly be seen at a pressure of about 0.01 atm (about 8 Torr), well within (by a factor of at least 10 ) the capability of the most modem instrumentation. Direct observations of threshold pressures, which are lower, require the use of more sensitive gravimetric techniques. This was also found experimentally by Thompson with adsorption data on diamond and alumina that had an ultrahigh vacuum surface cleaning. Since the results of Thompson s polytetrafluoroethylene experiments have not been reported in the open literature, these will be discussed in some detail. 

Sensitivity For any precipitation gravimetric method, we can write the following general equation relating the signal (grams of precipitate) to the absolute amount of analyte in the sample... 

Bromo-2-pyridyla2o)-5-diethylamiQophenol (5-Br-PADAP) is a very sensitive reagent for certain metals and methods for cobalt have been developed (23). Nitroso-naphthol is an effective precipitant for cobalt(III) and is used in its gravimetric determination (24,25). Atomic absorption spectroscopy (26,27), x-ray fluorescence, polarography, and atomic emission spectroscopy are specific and sensitive methods for trace level cobalt analysis (see... 

To measure gas and water vapor permeability, a film sample is mounted between two chambers of a permeability cell. One chamber holds the gas or vapor to be used as the permeant. The permeant then diffuses through the film into a second chamber, where a detection method such as infrared spectroscopy, a manometric, gravimetric, or coulometric method isotopic counting or gas-liquid chromatography provides a quantitative measurement (2). Die measurement depends on the specific permeant and the sensitivity required. 

Coulometric methods are as accurate and precise as conventional gravimetric and volumetric procedures and, in addition, are readily automated. In contrast to gravimetric methods, coulometric procedures are usually rapid, and do not require that the product of the electrochemical reaction be a weighable solid. The methods are moderately sensitive, and offer a reasonably selective means for separating and determining a number of ions. 

The lead content of biological samples is usually very small, rendering gravimetric methods impracticable, and methods have often relied upon the formation of coloured complexes with a variety of dyes. More recently, the development of absorption spectroscopy using vaporized samples has provided a sensitive quantitative method. Oxygen measurements using specific electrodes offer a level of sensitivity which is unobtainable using volumetric gas analysis. 

Cleanup steps are an important component of infrared (IR)-based and gravimetric methods because these methods are very sensitive to nonpetroleum hydrocarbon interferences. Cleanup steps are not always a part of the petroleum analytical process, but when they are necessary, the goals of extract cleanup steps typically include one or more of the following (1) removal of nonpetroleum compounds, (2) isolation of a particular petroleum fraction, and (3) concentration of analytes of interest. 

Methods based on gravimetric analysis (Table 7.2) are also simple and rapid, but they suffer from the same limitations as those of infrared spectrometric methods (Table 7.2). Gravimetric-based methods may be useful for oily sludge and wastewaters, which will present analytical difficulties for other, more sensitive methods. Immunoassay methods for the measurement of total petroleum hydrocarbon are also popular for field testing because they offer a simple, quick technique for in situ quantification of the total petroleum hydrocarbons. 

Our review on the use of oximes and hydroxamic acids in inorganic analytical chemistry showed that these reagents are/were most frequently used for gravimetric determinations, determinations based on complexation, spectrophotometric determinations and separations, while their use for column separations, as electrode sensors, as supporting electrolytes or compounds that enhance sensitivity of determination is less common. Additionally, it was noticed that the analytical chemistry of anions is less advanced than that of cations and for this reason this chapter was limited to analytical chemistry of metallic cations. 

The thermal conductivity detector used in the continuous flow method can sense signals corresponding to less than 0.001 cm of adsorption with 1 % accuracy, causing it to be considerably more sensitive to small amounts of adsorption than the volumetric or gravimetric methods. 

In these, As04 tetrahedra are built into the polyphosphate chains (309). Since the P—0—As bond has much the same sensitivity to hydrolysis as the As—0—As bond, they are rapidly hydrolyzed in aqueous solution to monoarsenate and mixtures of polyphosphates, the mean chain length of which depends on the As P ratio in the starting material (74)- Contrary to an idea based originally on gravimetric analysis (309), the As atoms are not distributed regularly in the chain, but statistically (308). The observation that, after careful hydrolysis, the phosphate content is exclusively in the form of polyphosphates provides chemical proof of catenation in the poly-arsenatophosphate anions. When arsenatophosphates with more than five P atoms per atom of As are hydrolyzed by hot water trimetaphosphates are formed, just as they are formed for all other high-molecular polyphosphates in solution (316). 

The various gravimetric methods for vapour permeability discussed above are all essentially simple but require great care to achieve good reproducibility, are time consuming, and are not generally sensitive enough to measure very low transmission rates. 

The sensitivity of the sample or the sensor to vapor transfer must also be considered. Here, the quantity of material represented by the sample or by the sensor is important. Vapor pressure is established by the presence of a particular number of molecules in a defined volume of space. The transfer of water molecules into the vapor phase may cause a measurable change in the gravimetric water contents of the sample and sensor. It is necessary that the sample water content (or the initial sample weight) be known. It may also be necessary to... 

Several experimental methods are applied to measure adsorption isotherms. The main problem is to determine the amount adsorbed. One method is a gravimetric measurement. In a gravimetric measurement the weight increase as a function of the pressure is determined. The adsorbent, usually in the form of a powder, is placed into a bulb and kept at the desired temperature. The bulb is mounted on a sensitive balance. Before the experiment, the bulb is... 

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