DeVarda method

There are two important hydrogenation (or reduction) — titration procedures for the detn of N as ammonia. The Devarda method involves the quant reduction of nitrates to ammonia in alkaline soln using an Ai-Cu-Zn alloy. The ammonia evolved is distd into standard sulfuric acid... 

Carter et al, Modified Devarda Method for the Determination of Nitrogen in Nitrocellulose ,... 

Refs on Analysis of NG 1) Marshall 2(1917), pp 739—40 (Estimation of small quantities by reaction with phenol disulfonic acid to form. PA and colorimetric measurement against K nitrate standards) 2) Koehler et al, AnnChimAnal-ChimAppl 2, 271-2(1920) CA H 3794(1920) (Devarda method) 3) W.W. Becker, lECAnalEd 5, 152-4(1933) CA 27, 2909U933)(Redox method for NG and NGc in the presence of DNT)... 

Devarda Method of Analysis. The nitrogen in inorganic nitrates or nitrites can easily be determined by using Devarda metal. In this procedure a weighed sample of nitrate (or nitrite) is dissolved in w contained in a special Devarda flask, and, after making the soln strongly alkaline with.NaOH, a few grams of Devarda alloy are added. 

Frey has pointed out that a disadvantage of the Devarda method is the fine spray which is produced and which must be prevented from being carried over into the standard acid. He has designed a distillation apparatus which obviates this difficulty. 

Analytical Procedures. Standard methods for analysis of food-grade adipic acid are described ia the Food Chemicals Codex (see Refs, ia Table 8). Classical methods are used for assay (titration), trace metals (As, heavy metals as Pb), and total ash. Water is determined by Kad-Fisher titration of a methanol solution of the acid. Determination of color ia methanol solution (APHA, Hazen equivalent, max. 10), as well as iron and other metals, are also described elsewhere (175). Other analyses frequendy are required for resia-grade acid. For example, hydrolyzable nitrogen (NH, amides, nitriles, etc) is determined by distillation of ammonia from an alkaline solution. Reducible nitrogen (nitrates and nitroorganics) may then be determined by adding DeVarda s alloy and continuing the distillation. Hydrocarbon oil contaminants may be determined by ir analysis of halocarbon extracts of alkaline solutions of the acid. 

Ferrous Sulfdte Titration. For deterrnination of nitric acid in mixed acid or for nitrates that are free from interferences, ferrous sulfate titration, the nitrometer method, and Devarda s method give excellent results. The deterrnination of nitric acid and nitrates in mixed acid is based on the oxidation of ferrous sulfate [7720-78-7] by nitric acid and may be subject to interference by other materials that reduce nitric acid or oxidize ferrous sulfate. Small amounts of sodium chloride, potassium bromide, or potassium iodide may be tolerated without serious interference, as can nitrous acid up to 50% of the total amount of nitric acid present. Strong oxidizing agents, eg, chlorates, iodates, and bromates, interfere by oxidizing the standardized ferrous sulfate. 

Devarda s Method. Nitrogen in nitrates or nitric acid also may be deterrnined by the Kjeldahl method or by Devarda s method. The latter is both convenient and accurate when no organic nitrogen is present. The nitrate is reduced by Devarda s alloy to ammonia in an alkaline solution. The ammonia is distilled and titrated with standard acid. 

The reagent is employed for the determination of ammonia in very dilute ammonia solutions and in water. In the presence of interfering substances, it is best to separate the ammonia first by distillation under suitable conditions. The method is also applicable to the determination of nitrates and nitrites these are reduced in alkaline solution by Devarda s alloy to ammonia, which is removed by distillation. The procedure is applicable to concentrations of ammonia as low as 0.1 mgL-1. 

A method of analysis based on converting nitrate groups to ammonia with Devarda s alloy is described by Smeenk (Ref 103). PETN is dissolved in ethanol and the ammonia formed is titrated with standard acid soln... 

Various other reducing methods are employed for the conversion of (3-nitro alcohols to amino alcohols, namely, electrochemical reduction.107 The selective electrohydrogenation of ni-troaliphatic and nitroaromatic groups in molecules containing other groups that are easy to hydrogenate (triple bond, nitrile, C-I) are carried out in methanol-water solutions at Devarda copper and Raney cobalt electrodes (Eq. 6.55).107... 

The Department of the Environment UK [155] has described a number of alternative methods for the determination of total oxidised nitrogen (nitrate and nitrite) in aqueous solution, while specific methods for nitrate and nitrite are also included. Among the methods for total oxidised nitrogen, one is based on the use of Devarda s alloy for reduction of nitrate to ammonia, and another uses copperised cadmium wire for reducing nitrate to nitrite, which is determined spectrophotometrically. Nitrate may also be determined spectrophotometrically after complex formation with sulfosalicylic acid or following reduction to ammonia, the ammonia is eliminated by distillation and determined titrimetrically. Other methods include direct nitrate determination by ultraviolet spectrophotometry, measurements being made at 210 nm, and the use of a nitrate-selective electrode. Details of the scope, limits of detection, and preferred applications of the methods are given in each case. 

Kjeldahl Method. A method of detg the N in an organic compd by digesting the substance with coned sulfuric acid in the presence of catalysts such as selenium, Devarda s alloy, etc. This treatment transforms the N into Amm sulfate. By adding an excess of caustic and distg the liberated ammonia into a measured quantity of standard sulfuric acid (which is later titrated), it is possible to determine the amount of N in the substance... 

F.D. Snell L.S. Ettre, Eds, "Encyclopedia of Industrial Chemical Analysis , Vol 14J. Wiley-In ter science, NY (1972), pp 498—500(F.A. Lowenheim, "Nitrogen Compounds-Analysis of Mixed Acid 17) Ibid, p 467 (Devarda s Method)... 

Devarda s method -m tritium preparation [DEUTERIUM AND TRITIUM - TRITIUM] (Vol 8)... 

A method [17] has been described for the determination of nitrate and nitrite nitrogen and ammonium ions in the 2 M potassium chloride extracts of moist soils. Firstly, an aliquot of the extract is made alkaline and the released ammonia determined via an ammonia-selective probe or titrimetrically. The nitrate in the ammonia-free extract is then reduced to ammonia with Devarda s alloy and the ammonia removed by distillation and determined titrimetrically. The concentration of nitrite in the extract is then determined spectrophoto-metrically as the red dye formed by coupling diazotised sulfanilic acid with N naphthylethylenediamine hydro chloride. 

Nitrogen is determined by the Kjeldahl method using Devarda s alloy. The complex and the alloy are placed in a standard Kjeldahl apparatus and the ammonia distilled off from a 7.5 M sodium hydroxide solution into 2% boric acid. The ammonia is titrated with standard hydrochloric acid using bromocresol green-methyl red as indicator. 

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