Bis [n-(1-oxyl - 2,2,6,6-tetramethylpiperidine -4)-n - ethyldiethanolamine-s, s`] copper (ii) as a reagent for the determination of mercury (ii)

 

(57) Abstract:

The inventive product - bis [N - (1 - oxyl - 2,2,6,6 - tetramethylpiperidine - 4) -N-ethyldiethanolamine - S,S-copper (2), the quantitative output. Polikristallicheskie powder dark brown color, decompose when heated above 205°C. Reagent 1: 2,2,6,6-tetramethyl - 4 - (N-ethylamino)piperidine - 1 - oxyl. Reagent 2: carbon disulfide. Reagent 3: copper sulfate. Reaction conditions: in water, in the presence of sodium hydroxide. 2 Il., table 1.

The invention relates to new chemical compounds that have applications in analytical chemistry, in particular the compound bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidine-4)-N-ethyldiethanolamine - S, S'] copper (II) formula

SC-C, quantitative determination of mercury (II) by electron paramagnetic resonance (EPR).

It is known the use of diethyldithiocarbamate, copper (II) formula

H5C2-CC-C-H5for indirect determination of mercury (II) spectrophotometric method [1]. In this case, the measured change of the light absorption at 438 nm, which decreases with increasing concentration of mercury (II). The main disadvantage with this method of determination of mercury is that the admixture of colored substances, extragenomic in the organic is THIOCARBAMATE copper (II) for determination of mercury (II) by the EPR method, using for this purpose a decline in the intensity of one of the four lines of the EPR spectrum of the complex [2].

The purpose of the invention is the expansion of the range of means for the determination of mercury (II), and the search for a more universal reagents.

This objective is achieved in that, as a reagent for the determination of mercury (II) use bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidine-4)-N-ethyldiethanolamine - S,S'] copper (II), which is obtained by the interaction of the 2,2,6,6-tetramethyl-4(N-ethylamino)piperidine-1-oxyl with carbon disulfide and sodium hydroxide in the presence of salts of copper (II).

P R I m e R 1. In a flat-bottomed flask with a capacity of 150 cm3placed 12.5 g (63 mmol) of 2,2,6,6-tetramethyl-4-(N-ethylamino)piperidine-1-oxyl, 5.0 g (66 mmol) of carbon disulfide, 2.5 g (63 mmol) of sodium hydroxide in 50 ml of distilled water.

The mixture is stirred on a magnetic stirrer at room temperature for 15 minutes Then the reaction mixture was added 8.0 g (32 mmol) of copper sulfate (II) in 25 ml of distilled water. Stirring is continued for another 5 min after loss of spin-labeled dithiocarbamate copper (II). Then the precipitate is transferred to a glass filter, washed with 50 ml of distilled water and dried in air.

Output b is a polycrystalline powder dark brown decomposing when heated above 205aboutC. Elemental analysis for carbon, hydrogen and nitrogen corresponds to theoretical.

Spectrum in the visible region, in chloroform,nm: 435 ( = 13000),

Range of IR ,cm-1: 1490, 1480, 1455 (C...N), 1380, 1085, 985 (C...S),

Range of EPR in chloroform: g1= 2,018, aCu= 27 E,

g2= 2,006, aN= 15,5 E.

The connection structure is proved by analogy with similar compounds.

P R I m m e R 2. We studied the distribution of the reagent, i.e., bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidine-4)-N-ethyldiethanolamine - S, S'] copper (II) in the system chloroform-water depending on the pH of the aqueous phase. LV was created using a buffer solution of tartrate ( 0,025 mol) with the addition of an aqueous sodium hydroxide solution. The concentration of the reagent in the organic phase is nearly constant in the pH range of 6.5-11. When you contact a chloroform solution of the reagent [(Rdtc)2Cu] with an aqueous solution of mercury (II), equal concentrations within 1-2 minutes there is a complete exchange of copper mercury education (Rdtc)2Hg according to the scheme:

Hg2+indays.+ (Rdtc)2Cuorg____ (Rdtc)2Hgorg+ Cu2+indays.< / BR>
The intensity of the EPR spectrum increases, compared to ESU triplet transitions in pure triplet (see Fig.1).

In Fig. 1 shows the effect of the concentration of Hg2+on the EPR spectrum (Rdtc)2Cu, where a) is the original spectrum EPR (Rdtc)2Cu;

b) transient EPR spectrum, when the concentration of Hg2+less concentration (Rdtc)2Cu;

C) the final EPR spectrum when (Rdtc)2Cu is completely transformed into (Rdtc)2Hg.

At lower concentrations of mercury (II) spectrum has a transitional look, but with a pronounced triplet part.

In the range pH 6.5-11 increase in the intensity of the triplet is directly proportional increase in the concentration of Hg2+. Therefore, constructing a calibration graph of the dependence of I on the concentration of Hg2+you can determine the content of Hg2+in aqueous solution with an unknown concentration of mercury (II) (Fig.2).

The influence of foreign ions Tl3+Ag+I-,So3-Bi3+,Pb2+,Co2+, Cu2+,Zn2+, EDTA for the determination of Hg2+spin-labeled dithiocarbamato copper (II). It is established that interfere with the determination ions Ag+I-,SO3-whose presence gives the understatement results from Hg2+. The presence of Tl3+gives an overestimation of the results Hg2+so from these ions should be dismissed on a preliminary basis.

Dry excess Zn2+not interfere with the determination Hg2+.

A method for determining Hg2+tested on the prepared standard solutions of Hg2+that is illustrated in the table.

The measurement results were processed using the methods of mathematical statistics [3], where n is the number of parallel measurements, where C is the concentration of the standard solution Hg2+;

- the average concentration of Hg2+defined by the EPR method;

S - mean square error of a separate definition or sample standard deviation:

S= ;

Sprelative quadratic error or coefficient of variation: Sp= ;

- reproducibility of experience: = tg, k ;

tg ,k - ratio t-test, ( = =0,95), k = n-1;

- confidence interval for the average result;

100% of relative error.

The use of spin-labeled dithiocarbamate copper (II) as a reagent for the determination of mercury (II) by the EPR method has its advantages, in comparison with the prototype. First, the triplet EPR spectrum from the nitroxyl radical is more intense than the Quartet of lines of copper (II). Secondly, with the increase in the number of mercury (II) there is a growth of the triplet component of the EPR spectrum, which allowed the tra EPR decreases, what complicates the exact determination of mercury (II).

The fact that the extinction coefficient of the spin-labeled dithiocarbamate copper (II) at a wavelength of 435 nm is equal to = 13000 and corresponds with the one unlabeled of diethyldithiocarbamate, copper (II), Allows to apply our proposed reagent not only to determine the EPR mercury (II), but for the spectrophotometric its determination on previously described methods [1].

BIS [N-(1-OXYL-2,2,6,6-TETRAMETHYLPIPERIDINE-4)-N-ETHYLDIETHANOLAMINE-S, S'] COPPER (II) AS A REAGENT FOR THE DETERMINATION OF MERCURY (II).

Bis[N-(1-oxyl-2,2,6,6 - tetramethylpiperidine-4)-N-ethyldiethanolamine - S, S'-copper (II) formula

< / BR>
as the reagent for the determination of mercury (II).

 

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