Carbon monoxide measurements, infrared

The EPA Method 10 discusses measuring carbon monoxide emissions from stationary sources from continuous samples extracted from an exhaust stack where the sample is measured with nondispersive infrared (NDIR) analyzer. Possible interferences include water, carbon dioxide, and carbon monoxide. Method lOA tells how to make certified carbon monoxide measurements from continuous emission monitoring systems (CEMS) at petroleum refineries. 

There are a few common methods of measuring oxygen concentration in the gas phase. Electrochemical sensors and paramagnetic sensors are typically used to measure oxygen concentration on a wet and dry basis, respectively. Carbon monoxide (CO) is most commonly measured using a nondispersive infrared technique. A gas sample flows between an infrared radiation source and an infrared detector. Carbon monoxide absorbs infrared radiation, hence the difference in intensity proportional to the concentration of CO in the gas sample. 

Reference methods for criteria (19) and hazardous (20) poUutants estabHshed by the US EPA include sulfur dioxide [7446-09-5] by the West-Gaeke method carbon monoxide [630-08-0] by nondispersive infrared analysis ozone [10028-15-6] and nitrogen dioxide [10102-44-0] by chemiluminescence (qv) and hydrocarbons by gas chromatography coupled with flame-ionization detection. Gas chromatography coupled with a suitable detector can also be used to measure ambient concentrations of vinyl chloride monomer [75-01-4], halogenated hydrocarbons and aromatics, and polyacrylonitrile [25014-41-9] (21-22) (see Chromatography Trace and residue analysis). 

The methods of choice for beryUium oxide in beryUium metal are inert gas fusion and fast neutron activation. In the inert gas fusion technique, the sample is fused with nickel metal in a graphite cmcible under a stream of helium or argon. BeryUium oxide is reduced, and the evolved carbon monoxide is measured by infrared absorption spectrometry. BeryUium nitride decomposes under the same fusion conditions and may be determined by measurement of the evolved nitrogen. Oxygen may also be determined by activation with 14 MeV neutrons (20). The only significant interferents in the neutron activation technique are fluorine and boron, which are seldom encountered in beryUium metal samples. 

A variety of instmments are available to analyze carbon monoxide in gas streams from 1 ppm to 90%. One group of analyzers determines the concentration of carbon monoxide by measuring the intensity of its infrared stretching frequency at 2143 cm . Another group measures the oxidation of carbon monoxide to carbon dioxide electrochemically. Such instmments are generally lightweight and weU suited to appHcations requiring portable analyzers. Many analyzers are equipped with alarms and serve as work area monitors. 

The primary reference method used for measuring carbon monoxide in the United States is based on nondispersive infrared (NDIR) photometry (1, 2). The principle involved is the preferential absorption of infrared radiation by carbon monoxide. Figure 14-1 is a schematic representation of an NDIR analyzer. The analyzer has a hot filament source of infrared radiation, a chopper, a sample cell, reference cell, and a detector. The reference cell is filled with a non-infrared-absorbing gas, and the sample cell is continuously flushed with ambient air containing an unknown amount of CO. The detector cell is divided into two compartments by a flexible membrane, with each compartment filled with CO. Movement of the membrane causes a change in electrical capacitance in a control circuit whose signal is processed and fed to a recorder. 

Carbon monoxide and carbon dioxide can be measured using the FTIR techniques (Fourier transform infrared techniques see the later section on the Fourier transform infrared analyzer). Electrochemical cells have also been used to measure CO, and miniaturized optical sensors are available for CO 2 monitoring. 

Solutions of Ru3(CO)i2 in carboxylic acids are active catalysts for hydrogenation of carbon monoxide at low pressures (below 340 atm). Methanol is the major product (obtained as its ester), and smaller amounts of ethylene glycol diester are also formed. At 340 atm and 260°C a combined rate to these products of 8.3 x 10 3 turnovers s-1 was observed in acetic acid solvent. Similar rates to methanol are obtainable in other polar solvents, but ethylene glycol is not observed under these conditions except in the presence of carboxylic acids. Studies of this reaction, including infrared measurements under reaction conditions, were carried out to determine the nature of the catalyst and the mechanism of glycol formation. A reaction scheme is proposed in which the function of the carboxylic acid is to assist in converting a coordinated formaldehyde intermediate into a glycol precursor. 

Sell, J. A. Herz, R. K. Monroe, D. R. "Dynamic Measurement of Carbon Monoxide Concentrations in Automotive Exhaust Using Infrared Diode Laser Spectroscopy" SAE Paper No. 800463, 1980. 

Carbon monoxide on metals forms the best-studied adsorption system in vibrational spectroscopy. The strong dipole associated with the C-O bond makes this molecule a particularly easy one to study. Moreover, the C-0 stretch frequency is very informative about the direct environment of the molecule. The metal-carbon bond, however, falling at frequencies between 300 and 500 cm1, is more difficult to measure with infrared spectroscopy. First, its detection requires special optical parts made of Csl, but even with suitable equipment the peak may be invisible because of absorption by the catalyst support. In reflection experiments on single crystal surfaces the metal-carbon peak is difficult to obtain because of the low sensitivity of RAIRS at low frequencies [12,13], EELS, on the other hand, has no difficulty in detecting the metal-carbon bond, as we shall see later on. 

Rh-Rh vector may donate electron density to the empty Rh-Rh (T -orbital and/or overlap through back-bonding with either of the fiUed n MOs [103]. Infrared measurements of Rh2f4-CO adducts demonstrate clearly a red shift in the C=0 stretching frequency relative to imhgated carbon monoxide [104]. These results are consistent with electron delocalization from the Rh-Rh n into the low-lying Similarly, back-... 

Measurements of the infrared spectra of carbon monoxide on supported palladium and Pd-Ag atoms (75a) shed light on the relative importance of the ensemble and ligand effects. Three CO absorption bands were observed on palladium and its alloys at 2060,1960, and 1920 cm-1. 

Equilibration with carbon monoxide at room temperature and low pressure (a few torr ) yielded the rhodium(I)-dicarbonyl compound (13) in addition to the Rh(I)(C0) paramagnetic complexe (11). The structure of this complex was elucidated by ESCA and UV measurements (13) which showed that the trivalent rhodium was indeed reduced to the monovalent state and by infrared spectroscopy which provided evidence for a gem dicarbonyl (14). Use of 1 1 C0 ... 

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