Cyanides measurement

There is a discrepancy between the cyanide criteria for both aquatic and drinking water standards and the current analytical technology. The criteria are stated for free cyanide (which Includes hydrocyanic acid and the cyanide ion), but the EPA approved analytical methodology for total cyanide measures the free and combined forms (11). This test probably overestimates the potential toxicity. An alternative method (cyanides amenable to chlorination) measures those cyanide complexes which are readily dissociated, but does not measure the iron cyanide complexes which dissociate in sunlight. This method probably tends to underestimate the potential toxicity. Other methods have been proposed, but similar problems exist (12). The Department of Ecology used the EPA-approved APHA procedure which includes a distillation step for the quantification of total cyanide (13,14). A modification of the procedure which omits the distillation step was used for estimation of free cyanide. Later in the study, the Company used a microdiffusion method for free cyanide (15). 

Schneider, J., V. Burger, and F. Arnold, Methyl Cyanide and Hydrogen Cyanide Measurements in the Lower Stratosphere Implications for Methyl Cyanide Sources and Sinks, . /. Geophys. Res., 102, 25501-25506 (1997). 

Table 11. Stability constants for complexation of Np(V) with azide and cyanide measured using...

As an illustrative example, consider the vibrational energy relaxation of the cyanide ion in water [45], The mechanisms for relaxation are particularly difficult to assess when the solute is strongly coupled to the solvent, and the solvent itself is an associating liquid. Therefore, precise experimental measurements are extremely usefiil. By using a diatomic solute molecule, this system is free from complications due to coupling... 

Cyanide compounds are classified as either simple or complex. It is usually necessary to decompose complex cyanides by an acid reflux. The cyanide is then distilled into sodium hydroxide to remove compounds that would interfere in analysis. Extreme care should be taken during the distillation as toxic hydrogen cyanide is generated. The cyanide in the alkaline distillate can then be measured potentiometricaHy with an ion-selective electrode. Alternatively, the cyanide can be determined colorimetricaHy. It is converted to cyanogen chloride by reaction with chloramine-T at pH <8. The CNCl then reacts with a pyridine barbituric acid reagent to form a red-blue dye. 

Assay of hydrogen cyanide can be done by specific gravity or silver nitrate titration. Sulfur dioxide in hydrogen cyanide can be deterrnined by infrared analysis or by reaction of excess standard iodine solution and titration, using standard sodium thiosulfate or by measurement of total acidity by... 

The heat capacity of sodium cyanide has been measured between 100 and 345 K (48). To convert to cal, divide by 4.184. 

Other ions, eg, ferrate, chloride, and formate, are determined by first removing the cyanide ion at ca pH 3.5 (methyl orange end point). Iron is titrated, using thioglycolic acid, and the optical density of the resulting pink solution is measured at 538 nm. Formate is oxidized by titration with mercuric chloride. The mercurous chloride produced is determined gravimetricaHy. Chloride ion is determined by a titration with 0.1 Ai silver nitrate. The end point is determined electrometricaHy. 

AH ahphatic aldehydes and most ketones react to form cyanohydrins. The lower reactivity of ketones, relative to aldehydes, is attributed to a combination of electron-donating effects and increased steric hindrance of the second alkyl group in the ketones. The magnitude of the equiUbrium constants for the addition of hydrogen cyanide to a carbonyl group is a measure of the stabiUty of the cyanohydrin relative to the carbonyl compound plus hydrogen cyanide ... 

Procedure. Place 10.0 mL of the working lead solution in a 250 mL separatory funnel, add 75 mL of the ammonia-cyanide-sulphite solution and then by the cautious addition of dilute hydrochloric acid adjust the pH of the solution to 9.5 (pH-meter). This operation must be carried out slowly if the pH of the solution falls even temporarily below 9.5, HCN may be liberated and so use of a fume cupboard is necessary. Now add 7.5 mL of the dithizone reagent to the separatory funnel, followed by a further 17.5 mL of chloroform. Shake for 1 minute, allow the layers to separate, then remove the chloroform layer. Measure the absorbance of this against a blank solution, using a 1 cm cell and a wavelength of 510 nm (green filter). 

In order to concentrate the lead extract, remove the lead from the organic solvent by shaking this with three successive 10 mL portions of the dilute hydrochloric acid solution, collecting the aqueous extracts in a 250 mL beaker. To the combined extracts add 5 mL of 20 per cent ascorbic acid solution and adjust to pH 4 by the addition of concentrated ammonia solution. Place the beaker in a fume cupboard, add 3 mL of the 50 per cent potassium cyanide solution and immediately adjust the pH to 9-10 with concentrated ammonia solution. Transfer the solution to a 250 mL separatory funnel with the aid of a little de-ionised water, add 5 mL of the 2 per cent NaDDC reagent, allow to stand for one minute and then add 10 mL of methyl iso butyl ketone. Shake for one minute and then separate and collect the organic phase, filtering it through a fluted filter paper. This solution now contains the lead and is ready for the absorption measurement. 

These results, considered in relation to the direct addition tests of monomer and hydrogen cyanide in the previous table, demonstrate that there is no reason to expect styrene monomer extraction into soft drinks, even at levels well below those we can measure analytically. They also reinforce our hydrogen cyanide data. Further, they indicate that these beverages are not more extractive of Lopac containers than the normal simulating solvents. The tests confirm the chemical safety of the containers as beverage packages. 

Ignasiak et al. (1975) also measured the infrared spectra of (Z)- and ( >diazo-cyanides and demonstrated clearly that neither of the isomers was identical with the corresponding diazoisocyanide (Ar-N2-NC, see Sec. 6.4), as proposed at the beginning of this century. 

Rate constants for the substitution reactions of square-planar dithio-phosphates and dithiocarbonate complexes of Ni(II), Pd(II), and Pt(II), with ethylenediamine and cyanide ion as nucleophiles, have been measured in methanol. The results were compared with those obtained in previous investigations, and interpreted in terms of the stabilities of 5-coordinate species that are formed prior to substitution (377). 

Experimental A photometric method was found in the literature which seemed to suit the particular circumstances. Two cyanide stock solutions were prepared, and an electromechanical dispenser was used to precisely prepare solutions of 20, 40,. .., 240 respectively 10, 30, 50,. .., 250 fig CN /100 ml. 10 ml of each calibration solution were added to 90 ml of the color-forming reagent solution and the absorbance was measured using 1-cm cuvettes. (See Table 4.17 (left and middle panels) and data file CYANIDE.dat.)... 

Table 4.17. Absorption Measurements on Cyanide Calibration Solutions...

When phenyl phosphate is the substrate, the released phenol is conveniently measured using the reaction described by Powell and Rind and Ring based on 4-amino antipyrine (4-AAP) and ferri-cyanide. It is possible to incorporate the 4-AAP directly into the buffered substrate mixture, so that color can be developed... 

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