Formaldehyde colorimetric determination

Type 1 sample in the air above the water, type 2 sample in the water, EN ISO 14 184 part 1 = Japan Law 112, part 2 = AATCC 112. BS 6806 part 3 is a slight modification of AATCC 112. BS 6806 part 2 is called a free formaldehyde test method, but it also covers released formaldehyde, caused by elevated reaction temperature and the use of concentrated sulfuric acid for the colour development before colorimetrical determination. 

Equilibrium Jar Method, Colorimetric Determination of Formaldehyde Using Chromotropic Acid Reagent for Product Testing - GPAM 203.6" Georgia Pacific Corporation, 1979. 

The concentration of carbon dioxide reduction products (formic acid, formaldehyde, and methanol) in the reactor at the end of each run is listed in Table 1. The methanol concentration was determined by gas chromatography using a Porpac T column. Formic acid was determined with an Dionex ion chromatography column, and the formaldehyde was determined with a colorimetric chromatropic acid analysis (J ). We did not examine the solution or gas phase for methane. 

Fig. 9.7 Robot station for colorimetric determination of formaldehyde in water. (Courtesy of Zymark).

The European Pharmacopoeia has two different colorimetric methods for limit testing of free formaldehydes based on a condensation of the formaldehyde being determined with acetylacetone and MBTH respectively. 

In addition, the total organic carbon content of the liquid phase was detmnined (TOC Analyser "DC 190" by Schmidlin), and the concentrations of acids were analyzed by ion chromatography (HPLC pump and colunrn thermostat by Bischoff column "Aminex HPX-87H", 300 mm x 7.8 eluent 0.4 mmol/1 H2SO4 UV detector "L-4250" and refractive index detector "RI71", both by Merck). Formaldehyde was determined colorimetrically by a UV-Vis spectrometer (Dr. Lange) immediately after the reaction. 

This reaction, which is reported (111) to involve the steps shown in Eqs. 93 and 94, seldom gives the stoichiometric yield of chlorine dioxide, possibly because chlorate is formed. Nevertheless, it finds employment in the colorimetric determination of sugars (114, 130, 131, 132, 211) and has been suggested as a means of in situ production of chlorine dioxide in bleaching (226) by using formaldehyde. 

Part 23 Determination of formaldehyde and hexamethylenetetramine (HMTA) in food simulants In the case of HMTA, it is treated with acid and heated to release formaldehyde. Formaldehyde in simulant is determined colorimetrically by reaction with chromotropic add in the presence of sulfuric acid... 

Figure 15.8 (a) Time course of the activity restoration of formalin-treated RNase A during incubation at 50°C (0-2h) and 65°C (2-4h) in TAE buffer, pH 7.0. (b) Time course of the activity restoration of formalin-treated RNase A during incubation at 65°C in TAE buffers of various pH values. All RNase A preparations were freed of excess formaldehyde by dialysis prior to the assay. The RNase A activity was determined with a colorimetric assay using cytidine 2,3,-cyclophosphate as the substrate as described by Crook et al.54 Note that the slopes of the curves decrease with incubation time at 65°C, which is near the denaturation temperature of native RNase A. This loss of activity is likely due to the competing effect of protein denaturation of the recovered RNaseA at this temperature. See Rait et al.10 for details. 

Ammonium chloride is analyzed by treatment with formaldehyde (neutralized with NaOH) and the product HCl formed is analyzed by titration using an acid-base color indicator such as phenolphthalein. Alternatively, it may be mixed with caustic soda solution and distdled. The distillate may be analyzed for NH3 by titration with H2SO4 or by colorimetric Nesslerization or with an ammonia-selective electrode (APHA, AWWA, WEF. 1995. Standard Methods for the Examination of Water and Wastewater. 19th ed. Washington, DC, American Pubhc Health Association). The presence of ammonia or any other ammonium compound would interfere in the test. The moisture content in NH4CI may be determined by Karl—Fischer method. 

Methanol can be determined colorimetrically but must usually be distilled from the reaction mixture before being analyzed. Wood and Siddiqui (27) described a simple and precise spectrophotometric method for measuring methanol in an assay for PE. The method involved permanganate oxidation of methanol to formaldehyde and reaction of the formaldehyde with pentane-2,4-dione. The color reaction was developed directly in the PE reaction mixture without interference from the pectin. However, Termote et al. (28)... 

To a 20-mL aliquot of sample adjusted for pH between 11.5 and 12, add 2 to 3 drops of 10% formaldehyde solution. Stir and then allow the solution to stand for 10 min. After this, add the reagents and follow the procedure given above to determine the cyanide amenable to chlorination by colorimetric method. 

Free formaldehyde is reacted with acetylacetone in the presence of an excess of an ammonium salt to form the yellow fluorescent compound, 3,5-diacetyl-1,4-dihydrolutidine and subsequently determined spectrophotometrically in methods A-E (14). In these methods, the test sample must be colorless and free from other carbonyl compounds. Some other derivatives have been used to analyze formaldehyde. For example, formaldehyde was reacted with sodium 4,5-dihydroxy-2,7-naphthalene disulfonate in sulfuric acid solution to yield a purple color (580 nm) and then subjected to colorimetric analysis. A purple-colored pararosaniline derivative was used to analyze formaldehyde in air (15). Air sample was passed through an aqueous solution which contained 0.4% of 3-methyl-2-benzothiazolone hydrazone hydrochloride and then a dye produced was determined at 635 or 670 nm (16). Molecular sieve (1.6 mm pettet) was used to trap formaldehyde in air samples. The formaldehyde... 

Barzana E, Klibanov AM, Karel M. 1989. A colorimetric method for the enzymatic analysis of gases The determination of ethanol and formaldehyde vapors using solid alcohol oxidase. Anal Biochem 182 109-115. 

Hoogenboom BE, Hynes RW, Mann CM, et al. 1987. Validation of a colorimetric method for determination of atmospheric formaldehyde. Am Ind Hyg Assoc J 48 420-424. 

The need for an automated and reliable system for formaldehyde determination is now clearly recognized. In response to this need, an automated and microprocessor-controlled flow injection analysis (FIA) system was developed in our laboratory. This system is based on the use of the modified pararosaniline colorimetric method (j6). The simplicity, versatility, good precision, high sampling rate, complete automation and relatively low cost of the system make it attractive for the analysis of large numbers of formaldehyde samples. In this chapter, sufficient background in the principle of FIA will be presented to allow the readers to evaluate the technique and its potential application to the routine analysis of formaldehyde will be explored. 

Ambient formaldehyde determinations taken during large scale test chamber studies and field investigations are based on two colorimetric analyses. The two methods are a modification of NIOSH P CAM 125 and the CEA 555 continuous formaldehyde monitor. 

Methyl Esters In Pectin. A titration method has been reported twT in which methyl ester levels are calculated from the number of equivalents of standard sodium hydroxide required to neuturalize the pectin sample before and after saponification. The copper titration procedure described earlier for determination of galac-turonic acid residues in pectin (15), is also used to determine methyl ester levels from the increase in copper-binding after hydrolysis of the esters. An accurate and sensitive colorimetric method (M) is rather time-consuming, but several samples can be run in parallel. Samples are saponified, the released methanol oxidized to formaldehyde, and the formaldehyde determined by spectrophometric assay (4l2nm) of its condensation product with pentane-2,4-dione. 

The reactivity of nucleophilic sites of phloroglucinol nucleis with aldehydes has been known for a long time. Using formaldehyde a condensation product is formed which precipitates and can be determined gravimetrically [111]. Colorimetric procedures using substituted benzaldehydes are more popular. The most often used substituted benzaldehyde is vanillin (4-hydroxy-3-methoxybenzaldehyde). Protocols based on dimethylaminocinnamaldehyde have gained interest in the last few years, whereas 2,4-dimethoxybenzaldehyde [132]- although more sensitive than vanillin [133] - is not anymore used. 

A purple dye is formed from formaldehyde and pararosaniline in the presence of sodium sulfite (see Eq. 1). Miksch et al. (1981) postulated the formation of a colorless Schiff base from acidified pararosaniline and formaldehyde in the first step. Under acidic conditions this intermediate reacts with SO2 to form the chromophore. The strong absorbance at 570 nm is used for colorimetric detection. Other aldehydes such as acetaldehyde, acrolein and propanal interfere, but at pH < 1.0 the reaction is specific for formaldehyde. In the presence of atmospheric SOj a toxic Hg(II)-reagent is necessary for the elimination of sulfite formed fi-om SO2. Although the sensitivity of the modified pararosaniline method is limited and it is susceptible to interference, is has been one of the most widely used techniques for the determination of formaldehyde (VDI3484, Part 1 Roffael, 1993). 

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