Carbon dioxide sampling

Nevertheless, SFC also has its drawbacks for example, only a limited number of samples are soluble in supercritical fluids. In supercritical carbon dioxide, for instance, only relatively nonpolar solutes are soluble. As a rule of thumb, solutes that are soluble in organic solvents having a polarity less than or equal to that of n-heptane are usually also soluble in supercritical carbon dioxide. Samples that are soluble in water are insoluble in CO2. 

Its purpose is twofold first of all to prevent any particles of the analysis sample, which is to be added next, from percolating through the coarse porous w ire-form " copper oxide and so into that portion of the tube heated by the furnace and secondly as a heat insulator, to present the sample being heated too rapidly by the nearby furnace. Both these safeguards are required, as otherwise some portion of the sample would be decomposed as soon as the furnace was sw-itched on the nitrogen so produced would be carried away during the initial sweeping of the air out of the tube with the carbon dioxide stream, and would not be collected. Low results w ould thus be obtained. 

Heat reagent-grade material for 1 hr at 255-265°C. Cool in an efficient desiccator. Titrate sample with acid to pH 4-5 (first green tint of bromocresol green), boil the solution to eliminate the carbon dioxide, cool, and again titrate to pH 4-5. Equivalent weight is one-half the formula weight. 

Values of the uptake at saturation, of butane, carbon dioxide and nitrogen, by a sample of carbon, expressed as a volume of liquid v,. The carbon had been "burnt off" to different extents by heating in oxygen at 500°C on a sorption... 

One method for measuring the temperature of the sea is to measure this ratio. Of course, if you were to do it now, you would take a thermometer and not a mass spectrometer. But how do you determine the temperature of the sea as it was 10,000 years ago The answer lies with tiny sea creatures called diatoms. These have shells made from calcium carbonate, itself derived from carbon dioxide in sea water. As the diatoms die, they fall to the sea floor and build a sediment of calcium carbonate. If a sample is taken from a layer of sediment 10,000 years old, the carbon dioxide can be released by addition of acid. If this carbon dioxide is put into a suitable mass spectrometer, the ratio of carbon isotopes can be measured accurately. From this value and the graph of solubilities of isotopic forms of carbon dioxide with temperature (Figure 46.5), a temperature can be extrapolated. This is the temperature of the sea during the time the diatoms were alive. To conduct such experiments in a significant manner, it is essential that the isotope abundance ratios be measured very accurately. 

The concentration of is determined by measurement of the specific P-activity. Usually, the carbon from the sample is converted into a gas, eg, carbon dioxide, methane, or acetylene, and introduced into a gas-proportional counter. Alternatively, Hquid-scintiHation counting is used after a benzene synthesis. The limit of the technique, ca 50,000 yr, is determined largely by the signal to background ratio and counting statistics. 

Carbonate is measured by evolution of carbon dioxide on treating the sample with sulfuric acid. The gas train should iaclude a silver acetate absorber to remove hydrogen sulfide, a magnesium perchlorate drying unit, and a CO2-absorption bulb. Sulfide is determined by distilling hydrogen sulfide from an acidified slurry of the sample iato an ammoniacal cadmium chloride solution, and titrating the precipitated cadmium sulfide iodimetrically. 

Fig. 8. The evolution of stoichiometric quantities of carbon dioxide formed from the total photorninerali2ation of 100 ppm of creosote in water under a saturated oxygen atmosphere. A 25-mL sample having 75.5 wt % C was used. The dashed line corresponds to the expected stoichiometric quantity of CO2.

Organic Carbon. The total organic carbon (TOC) in a water sample is determined by injecting a microliter sample into a heated, packed tube in a stream of oxygen. The water is vapori2ed and carbon is converted to carbon dioxide, which is detected with a nondispersive infrared analy2er. 

The temperature and extract content must be controUed regularly. Two weeks before bottling the beer should have a carbon dioxide content of 0.50 wt %, and samples are often taken for organoleptic tests. 

Total carbon in beryUium is determined by combustion of the sample, along with an accelerator mixture of tin, iron, and copper, in a stream of oxygen (15,16). The evolved carbon dioxide is usuaUy measured by infrared absorption spectrometry. BeryUium carbide can be determined without interference from graphitic carbon by dissolution of the sample in a strong base. BeryUium carbide is converted to methane, which can be determined directly by gas chromatography. Alternatively, the evolved methane can be oxidized to carbon dioxide, which is determined gravimetricaUy (16). 

Ion-selective electrodes can also become sensors (qv) for gases such as carbon dioxide (qv), ammonia (qv), and hydrogen sulfide by isolating the gas in buffered solutions protected from the sample atmosphere by gas-permeable membranes. Typically, pH glass electrodes are used, but electrodes selective to carbonate or sulfide may be more selective. 

Molecular Weight EPA Method 3 is used to determine carbon dioxide and oxygen concentrations and dry molecular weight of the stack-gas stream. Depending on the intended use of the data, these values can be obtained with an integrated sample (see Fig. 25-28) or a grab sample (see Fig. 25-29). In addition, the instrumental analyzer... 

With the grab sampling technique, a samphng probe is placed at the center of the stack, and a sample is drawn direcfly into an Orsat analyzer or a Fyrite-type combustion-gas analyzer. The sample is then analyzed for carbon dioxide and oxygen content. With these data, the diy molecular weight of the gas stream can then be calculated. 

The instrumental analyzer procedure, EPA Method 3A, is commonly used for the determination of oxygen and carbon dioxide concentrations in emissions from stationary sources. An integrated continuous gas sample is extracted from the test location and a portion of the sample is conveyed to one or more instrumental analyzers for determination of O9 and CO9 gas concentrations (see Fig. 25-30). The sample gas is conditioned prior to introduction to the gas analyzer by removing particulate matter and moisture. Sampling is conducted at a constant rate for the entire test run. Performance specifications and test procedures are provided in the method to ensure reliable data. 

When the operating conditions are uniform and steady (there are no fluctuations in flow rate or in concentration of CO in the gas stream), the continuous sampling method can be used. A sampling probe is placed in the stack at any location, preferably near the center. The sample is extracted at a constant sampling rate. As the gas stream passes through the sampling apparatus, any moisture or carbon dioxide in the sample gas stream is removed. The CO concentration is then measured by a nondispersive infrared analyzer, which gives direct readouts of CO concentrations. 

The time necessary for completion of the reaction may vary from 0.5 to 4 hours, depending on the actual activity of the alumina. The progress of conversion should be monitored by infrared analysis of a concentrated sample of the solution. Stirring should be continued for 15 minutes after the nitroso band at 1540 cm. has disappeared. A strong diazo band at about 2100 cm. will then be present. The carbonyl band at 1750 cm. initially due to nitrosocarbamate, will usually not disappear completely during the reaction, because some diethyl carbonate is formed in addition to carbon dioxide and ethanol. Diethyl carbonate is removed during the work-up procedure. 

The cooled mixture is transferred to a 3-1. separatory funnel, and the ethylene dichloride layer is removed. The aqueous phase is extracted three times with a total of about 500 ml. of ether. The ether and ethylene chloride solutions are combined and washed with three 100-ml. portions of saturated aqueous sodium carbonate solution, which is added cautiously at first to avoid too rapid evolution of carbon dioxide. The non-aqueous solution is then dried over anhydrous sodium carbonate, the solvents are distilled, and the remaining liquid is transferred to a Claisen flask and distilled from an oil bath under reduced pressure (Note 5). The aldehyde boils at 78° at 2 mm. there is very little fore-run and very little residue. The yield of crude 2-pyrrolealdehyde is 85-90 g. (89-95%), as an almost water-white liquid which soon crystallizes. A sample dried on a clay plate melts at 35 0°. The crude product is purified by dissolving in boiling petroleum ether (b.p. 40-60°), in the ratio of 1 g. of crude 2-pyrrolealdehyde to 25 ml. of solvent, and cooling the solution slowly to room temperature, followed by refrigeration for a few hours. The pure aldehyde is obtained from the crude in approximately 85% recovery. The over-all yield from pyrrole is 78-79% of pure 2-pyrrolealdehyde, m.p. 44 5°. 

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