Gravimetric control

The analysis of isotherms of gas at the temperature interval 233 - 293 K and pressure interval 0.1-6 MPa was realized by the gravimetric control of the sample (200-400 g) during adsorption/desorption cycle. The experimental set-up is shown in Fig. 5. 

An automated drop-on-demand system with real-time gravimetric control for precise dosage formulation has been developed (48). The modular drug dispensing system includes a microdispensing valve unit and is fully automated. Volumes ranging from nl to yl can be dosed with high accuracy. 

Solubility losses are minimized by carefully controlling the composition of the solution in which the precipitate forms. This, in turn, requires an understanding of the relevant equilibrium reactions affecting the precipitate s solubility. Eor example, Ag+ can be determined gravimetrically by adding Ch as a precipitant, forming a precipitate of AgCl. 

In a gravimetric analysis a measurement of mass or change in mass provides quantitative information about the amount of analyte in a sample. The most common form of gravimetry uses a precipitation reaction to generate a product whose mass is proportional to the analyte. In many cases the precipitate includes the analyte however, an indirect analysis in which the analyte causes the precipitation of another compound also is possible. Precipitation gravimetric procedures must be carefully controlled to produce precipitates that are easily filterable, free from impurities, and of known stoichiometry. 

Potassium is analyzed in chemicals that are used in the fertilizer industry and in finished fertilizers by flame photometric methods (44) or volumetric sodium tertraphenylboron methods (45) as approved by the AO AC. Gravimetric deterrnination of potassium as K2PtClg, known as the Lindo-Gladding method (46), and the wet-digestion deterrnination of potassium (47) have been declared surplus methods by the AO AC. Other methods used for control purposes and special analyses include atomic absorption spectrophotometry, inductively coupled plasma (icp) emission spectrophotometry, and a radiometric method based on measuring the radioactivity of the minute amount of the isotope present in all potassium compounds (48). 

Polymerization-grade chloroprene is typically at least 99.5% pure, excluding inert solvents that may be present. It must be substantially free of peroxides, polymer [9010-98-4], and inhibitors. A low, controlled concentration of inhibitor is sometimes specified. It must also be free of impurities that are acidic or that will generate additional acidity during emulsion polymerization. Typical impurities are 1-chlorobutadiene [627-22-5] and traces of chlorobutenes (from dehydrochlorination of dichlorobutanes produced from butenes in butadiene [106-99-0]), 3,4-dichlorobutene [760-23-6], and dimers of both chloroprene and butadiene. Gas chromatography is used for analysis of volatile impurities. Dissolved polymer can be detected by turbidity after precipitation with alcohol or determined gravimetrically. Inhibitors and dimers can interfere with quantitative determination of polymer either by precipitation or evaporation if significant amounts are present. 

Specifications, Analysis, and Toxicity. Dicyandiamide is identified quaHtatively by paper chromatography and quantitatively by ultraviolet spectrometry of the chromatogram. More commonly, total nitrogen analysis is used as a purity control or the dicyandiamide is converted by hydrolysis to guanylurea, which is determined gravimetrically as the nickel salt (50). Methods based on the precipitation of silver dicyandiamide picrate are sometimes used (51). Dicyandiamide can also be titrated with tetrabutylammonium hydroxide ia pyridine solution. Table 4 gives a typical analysis of a commercial sample. Dicyandiamide is essentially nontoxic. It may, however, cause dermatitis. 

Imperforate Bowl Tests The amount of supernant hquid from spin tubes is usually too small to warrant accurate gravimetric analysis. A fixed amount of shiny is introduced at a controlled rate into a rotating imperforate bowl to simulate a continuous sedimentation centrifuge. The liquid is collected as it overflows the ring weir. The test is stopped when the solids in the bowl build up to a thickness which affects centrate quality. The solid concentration of the centrate is determined similarly to that of the spin tube. 

The main principles of instrument design are summarized in Table 10.23. In filtration, e.g. for gravimetric analysis, selection of filter material (Table 10.22) requires careful consideration in terms of application, strength, collection efficiency, compatibility with pump, water uptake, etc. Humidity-controlled balance rooms, iTiicrobalances and careful handling techniques may be required. 

Standard instrument control and pacing signals are generally acceptable for common feeder system operation. Volumetric and gravimetric feeders are usually adaptable to operation from any standard instrument signals. 

When solution must be pumped, consideration should be given to use of holding tanks between the dry feed system and feed pumps, and the solution water supply should be controlled to prevent excessive dilution. The dry feeders may be started and stopped by tank level probes. Variable-control metering pumps can then transfer the alum stock solution to the point of application without further dilution. Means should be provided for calibration of the chemical feeders. Volumetric feeders may be mounted on platform scales. Belt feeders should include a sample chute and box to catch samples for checking actual delivery with set delivery. Gravimetric feeders are usually furnished with totalizers only. Remote instrumentation is frequently used with gravimetric equipment, but seldom used with volumetric equipment. 

Volumetric or gravimetric feeders may be used, but volumetric feeders are usually selected only for installations where comparatively low feed rates are required. Dilution does not appear to be important, therefore, control of the amount of water used in the feeding operation is not considered necessary. Inexpensive hydraulic jet agitation may be furnished in the wetting chamber of the feeder as an alternative to mechanical agitation. The jets should be sized for the available water supply pressure to obtain proper mixing. 

As the flow rate and quantity of liquor are the most important controllable variables in developing design data, a feed pump suitable for accurate and continuous flow is required. Depending on the size of the pilot column system, the use of peristaltic, diaphragm, piston-type or centrifugal pumps are recommended. The feed pump should be used in combination with a volumetric or gravimetric flow control... 

The main advantage of the gravimetric technique is that it requires a much smaller sample than the stoichiometric technique. In many cases, samples as small as 70 mg are sufficient. Accurate temperature and pressure control and measurement are still required, but gas adsorption on the metal walls of the equipment is no longer a concern because it is only the weight gain of the sample that is measured. 

In electro-gravimetric analysis the element to be determined is deposited electroly tically upon a suitable electrode. Filtration is not required, and provided the experimental conditions are carefully controlled, the co-deposition of two metals can often be avoided. Although this procedure has to a large extent been superseded by potentiometric methods based upon the use of ion-selective electrodes (see Chapter 15), the method, when applicable has many advantages. The theory of the process is briefly discussed below in order to understand how and when it may be applied for a more detailed treatment see Refs 1-9. 

In the common method of electro-gravimetric analysis, a potential slightly in excess of the decomposition potential of the electrolyte under investigation is applied, and the electrolysis allowed to proceed without further attention, except perhaps occasionally to increase the applied potential to keep the current at approximately the same value. This procedure, termed constant-current electrolysis, is (as explained in Section 12.4) of limited value for the separation of mixtures of metallic ions. The separation of the components of a mixture where the decomposition potentials are not widely separated may be effected by the application of controlled cathode potential electrolysis. An auxiliary standard electrode (which may be a saturated calomel electrode with the tip of the salt bridge very close to the cathode or working electrode) is inserted in the... 

Before discussing the problems of control laboratories, it is important to have a clear picture of the revolutionary changes which have been, and still are, taking place in the field of analytical chemistry. One has only to observe the recent issues of Analytical Chemistry, noting especially the editorials of Murphy (14) and the articles of Muller (13), to recognize the trend away from the classical gravimetric and volumetric methods of 20 years ago. 

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