Reagent indicator tube based on chromogenic dispersed silica

FIELD: chemistry.

SUBSTANCE: filler used is chromogenic ion-exchange dispersed silica with covalently grafted hydrazones or formazans.

EFFECT: high sensitivity and selectivity of detecting metals.

3 tbl, 4 dwg, 14 ex

 

The invention relates to analytical chemistry, specifically to chemical indicators on solid media, and can be used for rapid determination of the maximum allowable and dangerous concentrations of metals in drinking water, surface waters, land, sewage; air mixtures, soil; food products; processing objects (for example, for the analysis of gasoline) using reagent indicator tubes (it).

Specific changes the color of the filler in it during the reaction allows visual analysis of linearly-color method: the length of the colored zone of the filler.

Known indicator tube filled with dispersed silica gel (SG) with adsorbed analytical reagents or reagent introduced into the xerogel to form a defined substances in aqueous media painted compounds: dodecylamino-6-tridecylamine chloride with titianium for determination of bismuth (III) [1. Willow CENTURIES, Zaporozhets O.A., Sukhan V.V., etc. // Naukovi notes NaUKMA. Ser. Chem. science. 2000. Vol.18. S.80.], brombenzene for determination of cadmium [2. Zolotov Y.A., tsysin GI, Dmitrienko YEAR, Morosanova H. Sorption preconcentration of trace components from solutions. Application in inorganic analysis. M.: Nauka, 2007. S-251], 1-nitroso-2-naphthol - for the determination of cobalt (II [2, 3. Maksimova IM, kuhto A.A., Morosanova H. and others // Ukr. Anal. Chemistry. 1994. V.49. No. 7. S], 1-(2-pyridylazo)-2-naphthol - for the determination of copper (II) [4. Maksimova IM, Morosanova H., kuhto A.A., etc. // Ukr. Anal. Chemistry. 1994. V.49. No. 12. S] or to determine the amount of heavy metals [2], diethyldithiocarbamate lead - for the determination of copper (II) [5. Morosanova H., I.V. Pletnev, Semenova N.V., etc. // Ukr. Anal. Chemistry. 1994. V.49. No. 7. S], chromazurol, pyridinium - to determine iron (III) [6. Morosanova H., Azarov ZH.M., Zolotov Y.A // Zavodskaya laboratoriya. Diagnostics of materials. 2003. T. No. 7. S], phenanthrolin and ascorbic acid for the determination of iron (II, III) [7. Zaporozhets O.A., Gaver L.M., Sukhan V.V. // Talanta. 1998. V.46. P.1387], dithizonate zinc for mercury determination [8. Zaporozhets O., Petruniock N., Sukhan V. // Talanta. 1999. V.50. P.865], 1-(2-thiazolylazo)-2-naphthol - to determine zinc [9. Zaporozhets O., Petruniock N., Bessarabova O. and Sukhan V. // Talanta. 1999. V.49. P.899], 1-(2-thiazolylazo)-resorcinol - for the determination of palladium (II) [10. Ivanov V.M., Kuznetsov, O.V. // Ukr. Anal. Chemistry. 1995. T. No. 5. S].

Known indicator tube with filler, incorporating particulate Almagell and ecovalence immobilized thereon a light - sulfosalicylic acid or o-phenanthrolin for iron determination in gasoline [11. Grandfathers A.G. and others Pat. EN 2339942, C1. 2008. Bull. No. 33. (G01N 33/22; 31/22, 21/78)].

To achieve low concentrations (Cmi is ) test the complexation is adsorbed on the carrier ligands with defined metal ions in solutions spend the concentration of the analyte mode "pumping" of the sample through it with the help of a plunger, a medical syringe or peristaltic pump, thus it is possible to achieve Withmin10-20 times less in comparison with the technique of "dropping" it into the solution.

Basic common disadvantage of the above it held on the media reagents is that the adsorption fixation does not provide complete retention of reagents on the matrix at different time and number of samples modes of contact test tool to the analyzed solution when pumping the sample through it that is not completely prevent erosion and leaching of products from media, while achievable Withminfor the above tubes varies in the range of 0.06 to 0.6 mg/l of water or 1 mg/l of gasoline and limits the sensitivity at this level.

In addition, the selectivity is also limited because all of the above reagents are in one degree or another group. For example, 1-(2-pyridylazo)-2-naphthol used to determine the amount of heavy metals [2] and separate metals from this amount, masking accompanying interfering metals [4].

Closest to the technical essence and achievement n ilusha sensitivity to the stated object is it for the determination of copper and iron on the basis of silica, modified polyhexamethylene guanidine (phmg) and sulfadiazine reagents: bathocuproine for copper and bathophenanthroline, Tyrone and chromotrope acid - iron [12. V.N. Losev, S.L., Didukh. // Journal of Siberian Federal University. Chemistry 1 (2010 3) 64-72]. While on the surface of the silica, there is an intermediate organic layer from pgmg due to the formation of hydrogen bonds between the amino groups and hydroxyl groups of the surface of the silica, and the layer of pgmg are themselves reagents, all the parts are supramolecular ensemble of three substances, linked by intermolecular hydrogen bonds. It (inner diameter 2 mm, height 5 cm) filled with dry sorbent height 3 cm, and when the analysis was pumped through it 20 ml of test solution, which was allowed, due to a larger volume of solution, to provide greater sensitivity and accuracy. When this happened staining of the sorbent in the indicator tube. The length of the colored zone increases proportionally to the increase in the concentration of the analyte in the analyzed solution. The content of copper and iron in the analyzed solutions were determined by the length of the colored zone, built in similar conditions by passing solutions with known concentrations of metals. The limits of detection of copper (I) and iron (II) was appropriate to estwenno 0.0025 and 0.0005 mg/l

The lack of fillers for it in the prototype is the presence of an additional layer of sorbent between the silica and the reagent, which complicates the manufacturing method and the structure of it. Another drawback of it is the limited selectivity and poor reproducibility. In addition, with the help of these it is impossible to determine copper (I) and iron (II) in the presence of oxidants.

Thus, each of the known reagent it has its advantages and its scope. However, none of them can provide simultaneous combination of relevant analytical metrological characteristics such as high sensitivity and selectivity for the determination of trace metals in a wide range of maximum permissible and dangerous concentrations in various liquid media, while simplifying the structure and the method of obtaining it.

The basis of the invention is the creation of the reagent indicator tube, the composition and the form of which provide an absolute hold on the media covalently grafted reagent, which in turn ensures the implementation of highly sensitive rapid test method selective semi-quantitative and quantitative determination of toxic substances in liquid media at the level of from 0.0005 mg/l and above.

The technical result of izobreteny is - increase the sensitivity and selectivity of the determination of metals using it while simplifying the design and method of manufacture, increase resistance to erosion during use.

This technical result is achieved by the fact that the indicator reagent tube-based chromogenic silica according to the invention as filler contains chromogenic ion-dispersed silica with covalently grafted hydrazones I-III or formazane IV-XIV General formula

where

The invention is illustrated by figures 1-4, in which:

figure 1 - photo of powder diasorb-100-OCHAG (I), with grain size 63-200 μm and pore size 100 Å (10 nm) after treatment with a solution of iron (III).

figure 2 - absorption spectra of 1-oxo-4-chloro-1,2-dihydroisoquinoline-3-argersinger (I) with grain size 63-200 μm (curves 1, 2) and their complexes with iron (III) (curves 3, 4), dry (curves 1, 3) and wet (curves 2, 4). The powder was placed in a round cell with a depth of 1 mm and a diameter of 8 mm on the white Teflon plate.

figure 3 spectra of PRP is the position in the function of Kubelka-Munch F=(1-R) 2/2R, where R is the reflection coefficient of the powder of 1-(2-carboxyphenyl)-5-(4-methyl-6-methoxypyridine-2-yl)-formatovacia-100 (V) and its complexes with metals.

figure 4 - the reflectance spectra of the functions of Kubelka-Munch F=(1-R)2/2R, where R is the reflection coefficient of the powder of 1-(2-carboxymethoxy)-5-(benzoxazol-2-yl)-formatindicator-100 (XI) and its complexes with metals.

All spectra were taken with a mini-spectrophotometer "Gretag Magbeth iLPro" (USA), with an input window of diameter 4 mm

A method of obtaining a chromogenic silica is that kremnezemnyi treated with hydrazines with getting hydroconcrete progressing with diazo compounds to obtain formosacitation.

As initial reagents used 1-oxo-4-chloro-1,2-dihydroisoquinoline-3-oil-, 8-hydroxy-3,5-dichlorphenol-2-yl-, 4-carboxy-6-phenylpyrimidine-2-yl, thiazol-2-yl-, benzoxazol-2-yl-, 4-methyl-6-methoxypyridine-2-yl-, 6-methyl-3,4-dihydro-4-oxopyrimidine-2-yl-, 6-methyl-5-ethyl-2-(4-ethyl-3,5-di-n-propyl-1H-pyrazole-1-yl)-pyrimidine-4-elhedrine; and phenyl-, 2-chloro-, 2-carboxy-; 2-methoxy-, 2-carboxymethoxy-, 5-methylpyrazole-3-yl-, 2-thiazolyl-diazocompounds [13. Ostrovskaya V.M. Pat. Of the Russian Federation. 2126963 1999. Bull. No. 6].

Advantages of the invention are illustrated by the examples it with fillers of chromogenic ion exchange silica with covalently bound to revitali the hydrazones or formazane, the methods of their fabrication and optical properties of these silica in their interaction with metal ions: visual contrast color transitions or spectra absorption or reflection, as well as the mapping of the metrological characteristics of it, known it, with non-covalent (adsorption) the application of the indicators in the determination of metals using it along the length of the formed colored zone, calibrated according to standard concentrations of metals.

Offer it on certain metals have a high selectivity. The selectivity factor in 10-200 times higher than that of Monomeric analogues of the reactant having functional chromogenic polydentate grouping as silica, but fixed adsorption. Chromogenic ion-dispersed silica with covalently grafted reagents differ in that the internal cavity is open only for ions with a defined chemical structure; ion-exchange surface of silica is implemented only complexes 1:1 coordination. The metal ions (M), which when interacting with loose ligands (L) to form compounds of structure M:L, where L>1, may not participate in the formation of compounds with covalently attached by ohanami for steric reasons, which increases the selectivity of it. Introduction strong metalloplastikovye the th, such as carboxypropyl (V, VI, IX), results in the group of reagents for the determination of the generalized indicator of the amount of metals with high sensitivity.

Fillers it has an active exchange functional groups, they limit diffuse leaching of ions from the internal cavities and provide the concentration of ions with simultaneous development of color. Therefore, in the presented examples, the detection limits of ions of metals: bismuth, iron, indium, cadmium, cobalt, copper, manganese, Nickel, palladium, mercury, lead, silver, zinc, achieve value in a particular case from 0.0005 to 0.01 mg/l depending on the type of it and the method of testing samples.

Below are examples of the preparation of the indicator test tools and their use for the determination of trace metals in water or in automotive gasoline.

Example 1. It is Iron (III)-Test on the basis of 1-oxo-4-chloro-1,2-dihydroisoquinoline-3-argersinger (I).

Kremnezemnogo group disobliged different brands [14. Ostrovskaya V.M., Vazirov GG, Marchenko DU Pat. EN 2400468, 2010, bull. No. 27] treated with 0.3%solution of 1-oxo-4-chloro-1,2-dihydroisoquinoline-3-Algeria (OHAG) in dimethylformamide (DMF) for 3 h, then separated from the reaction solution, washed on the Frit with propanol-2, aqueous solution with pH 1-3 and deionized the ode and ether.

Received chromogenic polydentate hydrotalcites I (diasorb-KIHG different brands, table 1) white with ions of iron (III) forms a connection, painted in purple color with different shades depending on the particle size and the size of the nanopores on them. Other metals color reaction does not give. Dry gidrosistema I fill it with a height of 70 mm, an inner diameter of 1 or 2 mm at a predetermined height. Determination of iron (III) it does not interfere with iron ions (II), copper, cadmium, cobalt, Nickel, lead, zinc and other heavy metals, and also alkali and alkaline earth metals. Table 1 presents data on the properties of it depending on the brand of silica and contact conditions with a solution of iron (III). It is established that the optimal mark on statistical exchange capacity (SOY), brightness and clarity of the coloring of the indicator zone (OF), rate of pumping, the action of capillary forces is diasorb-100, 63-200 (particle size 63-200 μm and pores of 10 nm=100 Å), (Figure 1). Absorption spectra of diasorb-100-OCHAG (I), with grain size 63-200 μm and pore size of 10 nm and its complex with iron (III) is represented in figure 2, which applied to obtain desorbitation and decorporation - fillers for it.

The results are presented in table 1.

Sorption-dynamic properties of the it-Iron (III)-Test with an inner diameter of 1 mm, height 70 mm standard Pumping solutions through it's Iron (III)-Test with fillers of various brands
No.Brand silicaSizeSOY, m-EQ./gV* ml/5 min through it, the height of the filler h it
Particles, micronsThen, nm (Å)h=60 mmh=60 mmh=12 mm
WaterGasolineGasoline
1Diasorb-60-KIHG40-636 (60)0,180,20,53
2Diasorb-60-KIHG63-2006 (60)0,051,5319
3Diasorb-60-KIHG200-5006 (60)0,19512>30
4Diasorb-250-KIHG100-20025 (250)0,0722,515
5Diasorb-250-KIHG200-35525 (250)0,04414>30
6Diasorb-250-KIHG315-50025 (250)0,031027>30
7Diasorb-350-KIHG40-7035 (350)0,230,515
8Diasorb-500-KIHG100-200 50 (500)0,024526
9Diasorb-100-KIHG63-20010 (100)0,212826
10Diasorb-100-KIHG63-20010 (100)0,22210>30
Notes: * V is the volume of solution pumped through the tube for 5 min with a syringe

Example 2. It is Iron (II, III)Test on the basis of 8-hydroxy-5,7-dichlorphenol-6-illigratsdara-100 (II)

Disobliged-100, grain 63-200 μm treated with 0.3%solution of 2-hydrazino-5,7-dichloro-8-Honolulu in DMF for 3 h, then purified as in example 1. Received hydrazones II painted in yellow, has a SOY iron (III) 0.20 m-EQ./g and forms iron (II) and (III) at pH 3-4 connection, painted in dark green color. Color reaction do not interfere with ions of copper, cadmium, cobalt, Nickel, lead, zinc and other heavy metals, and alkali and alkali-earth. It serves as a description of the but in the example 1.

Example 3. It is Iron (II, III)-Test 2 on the basis of 4-carboxy-6-phenylpyrimidine-2-illigratsdara-100 (III)

Get hydrazones III as in example 1 with the difference that, as a derivative of hydrazine using 4-carboxy-6-phenyl-pyrimidine-2-ilkerin. The resulting hydrotalcites III is white and forms at pH 2-4 with iron ions connection, painted in red color. It is prepared as described in example 1.

Example 4. It is Copper (II)Test on the basis of 1-phenyl-5-(4-methyl-6-methoxypyridine-2-yl)-formatovacia-100 (IV)

Disobliged-100, grain 63-200 µm process of 0.2%aqueous acetic acid solution of 2-hydrazino-4-methyl-6-methoxypyridazine at pH 3, the reaction solution is removed, the powder was washed with ethanol, 5%acetic acid, water, then dried. Get 4-methyl-6-methoxypyridine-2-argersinger-100, which is then treated with diazobenzene in a mixture of 15 parts by weight of DMF and 12 parts by weight of acetate buffer with pH 6 for 15 min, separated from the reaction solution, washed with water, propanol-2, acetone, and dried. The resulting formazan diasorb-100 (IV) is light yellow in color and forms at pH 5-7 with ions of copper (II) compound a dark purple color, and other non-ferrous metals reactions does not. It was prepared as described in example 1.

Example 5. It is Metal-Test on the basis of 1-(2-carboxyphenyl)-5-(4-methyl-6-methoxypyridine-2-yl)-formazane the Orb-100 (V)

Get formatindicator V, as in example 4 with the difference that in the second stage of the synthesis hydrazones process instead of diazobenzene diazotized Anthranilic acid in borate solution with a pH of 9.5. Get the product of V in the form of a yellow powder, which forms at pH 5-7 colored compound with iron ions, cadmium brown; cobalt, Nickel - black-blue; copper blue; mercury - brown, zinc - purple-brown color. It is prepared as described in example 1. The reflectance spectra of formatovacia V and its complexes with heavy metals is shown in figure 3. The lower bound defined concentration of total metals 0.005 mg/l, with the volume pumped through it samples 20 ml Sensitivity 5.10-8M. While at lower pH 2-3 it forms a very sensitive selective reaction only with copper (II).

Example 6. It indium-Test on the basis of 1-(2-carboxymethoxy)-5-(4-methyl-6-methoxypyridine-2-yl)-formatovacia-100 (VI)

Get formatindicator-100, as in example 4 with the difference that in the second stage of synthesis instead of diazobenzene use diazotized 2-aminophenoxyethanol acid carbonate solution with a pH of 9.5. Get formatindicator-100 (VI) yellow. It is prepared as described in example 1. It manifests at pH 1-2 high selectivity to India, with which it forms the connection SYN is the first color, Withmin0.03 mg/l

Example 7. It Zinc Test on the basis of 1(5)-phenyl-5(1)-(3,4-dihydro-6-methyl-4-oxo-[3H]-pyrimidine-2-yl) formatovacia-100 (VII)

Get formatindicator VII, as in example 4 with the difference that in the first stage instead of 2-hydrazino-4-methyl-6-methoxypyridazine use 2-hydrazino-6-methyl-[3H]-pyrimidine-4-one. The product VII, grain 63-200 µm, yellow-orange, and zinc ions form at pH 7-9 connection, painted in dark red color, it is prepared as described in example 1.

Example 8. It-Cadmium-Test on the basis of 1(5)-(2-methoxyphenyl)-5(1)-(3,4-dihydro-6-methyl-4-oxo-[3H]-pyrimidine-2-yl) formatovacia-100 (VIII)

Get decorporate VIII as in example 7, with the difference that in the second stage instead of diazobenzene use 2-methoxybutanol (diazotized ortho-anisidine). Diasorb has a dark orange color and forms at a pH of 6-8 with a cadmium compound red-brown color. It is prepared as described in example 1.

Example 9. It Bismuth-Test on the basis of 1-(2-carboxymethoxy-5-[6-methyl-5-ethyl-2-(4-ethyl-3,5-di-n-propyl-1H-pyrazole-1-yl)-pyrimidine-4-yl]-formatovacia-100 (IX)

Get formatindicator IX, as in example 5 with the difference that instead of 2-hydrazino-4-methyl-6-methoxypyridazine use 4 hydrazino-6-methyl-5-ethyl-2-(4-ethyl-3,5-di-n-propyl-1H-pyrazole-1-yl)-pyrimidine. The product is painted in yellow and at pH 1-2 forms with virutalbox blue. It is prepared as in example 1.

Example 10. It Metal Test 2 on the basis of 1-phenyl-5-(benzoxazol-2-yl)-formatovacia-100 (X)

Get formatindicator X, as in example 4 with the difference that instead of 2-hydrazino-4-methyl-6-methoxypyridazine use 2-hydrazinobenzothiazole. Formatindicator X has a brownish-yellow color; at pH 5 forms complexes with iron ions (II), cadmium, Nickel, mercury, zinc, purple, copper, blue, cobalt blue, black color, heavy metals detected visually when the total concentration of 0.005 mg/l In acidic medium at pH 1-3 observed selective reaction with palladium ions with the formation of compound dark green color. It is prepared as described in example 1.

Example 11. It is Metal-Test 3 based on 1-(2-carboxymethoxy)-5-(benzoxazol-2-yl)-formatovacia-100 (XI)

Get formatindicator XI as in example 10, with the difference that instead of diazobenzene use 2-diazofunction acid and the process is conducted at a pH of 8-10. Formatindicator X has a dark yellow colour; at pH 5-6 forms complexes with metal ions: copper, iron (II), cadmium, cobalt, manganese (II), zinc - purple-black color; iron (III), Nickel, mercury, silver - brown; lead black and green. The reflectance spectra of formatovacia-100 (XI) and its complexes with heavy metals are given in figure 4. It is prepared as described in the example 1. The lower bound defined concentration of total metals 0.005 mg/l when the volume pumped through it samples 20 ml of a Sensitivity of 5·10-8M. the reflectance Spectra of powder XI and its complexes with heavy metals show that these complexes have significant similarity: the minimum reflection and maximum absorption in the region of 580-620 nm. It can be used to quantify the amount of heavy metals in natural, technological and wastewater containing lead.

Example 12. It Cobalt-Test based on [3(5)-methylpyrazole-5(3)-yl]-5(1)-(benzothiazol-2-yl)-1(5)-formatovacia-100 (XII)

Formatindicator XII, get as in example 10, with the difference that, as the use of hydrazine 2-hydrazinobenzothiazole; as disasstable - 3(5)-diazo-5(3)-methylpyrazole. Powder XII has orange color, and with cobalt (II) forms a complex green-black color. It is prepared as described in example 1.

Example 13. It is Mercury-Test based on the 1,5-bis(2-thiazolyl)-formatovacia-100 (XIII)

Formatindicator XIII receive, as in example 12 with the difference that for processing aldehydes using 2-hydrazinolysis, and then it is treated with 2-diazotization. Product XIII - powder light brown color, forms at pH 0.2-2 with Hg (II) selective reaction with the formation of compound blue-black color. Color reactions with other the metal ions are formed only when > 2. It is prepared as described in example 1.

Example 14. It Palladium (II)Test on the basis of 1-phenyl-5-(4,6-demateriali-2-yl)-formatovacia-100 (XIV)

Get formatindicator XIV, as in example 4 with the difference that in the first stage instead of 2-hydrazino-4-methyl-6-methoxypyridazine use 2-hydrazino-4,6-demateriali, and the product is a powder, grain 63-200 µm, yellow and palladium ions forms at pH 1-2 connection, painted in dark green color. It is prepared as described in example 1.

Advantages of the invention are illustrated by the mapping of the metrological characteristics of it from examples 1, 2, 4, 5, 7-9, 11-14 known of it in the definition of the same metals in water (table 2) and from examples 1, 2, 5 - in gasoline (table 3). From these tables it is seen that all of it with fillers of chromogenic ion exchange silica with covalently grafted hydrazones or formazane have advantages in sensitivity in the determination of metals in water or gasoline before known it.

Thus the use of the invention allows to achieve increased sensitivity and selectivity for the determination of metals using it while simplifying the design and method of manufacture, increase resistance to erosion during use.

Table 2
The lower boundary of the designated content (Cmin) metals (M) in water by using it in the "pumping" and their comparison with known it based on silica with ecovalence immobilized reagents in the "pumping"
MIt is based on diasorb-100 Å with a grain size 63-200 μm# exampleWithminmg/lIt ecovalence (adsorption) immobilizovannymi reagents according to the literature dataWithminmg/lLit. link
Bi (III)It Bismuth-Test IX90,03H**, thiocyanic0.11
Cd (II)It Cadmium Test VIII80.05Brombenzene0.12
Co (II)It Cobalt-Test XII120.0051-Nitroso-2-naphthol 0.032, 3
Cu (II)It is Copper (II)-Test IV40.011-(2-Pyridylazo)-2-naphthol0.052, 4
Cu (II)It is Metal-Test-1 V copper*50.001Diethyldithiocarbamate Pb0.0015
Fe (III)It is Iron (III)-Test 1 (I)10.0005Chromazurol, pyridinium0.26
Fe (II, III)It is Iron (II, III)Test 2 (II)20.002Phenanthrolin, ascorbic the0.0057
Hg (II)It Mercury Test XIII130.005Dithizonate zinc0.0058
Zn (II) It Zinc Test VII70.0051-(2-Thiazolylazo)-2-naphthol0.0159
Pd (II)It Palladium (II)-Test XIV140.0011-(2-Thiazolylazo)-resorcinol0.00510
ΣMIt is Metal-Test-3 XI115·10-8M1-(2-Pyridylazo)-2-naphthol5·10-4M2
Notes: * In a more acidic environment. ** Dodecylamino-6-tridecylamine chloride.

Table 3
The lower boundary of the designated content (Cmin) metals (M) in gasoline by using it and their comparison with known it ecovalence immobilized reagents (mode pumping 2-5 ml of gasoline through it)
MIt based on diasorb-100 Å with a grain size 63-200 MK is mg/l (h mm)*A prototype of itmg/l (h mm)Lit. link
Reagents immobilized
Fe (II, III)It is Iron (II, III)-Test1 (10)Sulfosalicylic acid or ortho-phenantroline10 (3)11
Fe (III)It is Iron (III)-Test1 (11)---
Cu (II)It is Metal-Test for copper*1 (8)---
Note: * the length of the colored zone h

Thus, the present invention allows to create a flat tube with the covalent grafting of reagents in the filler, which improves the sensitivity and selectivity of the determination of trace metal ions by using indicator tubes.

Reagent indicator tube based chromogenic silica distinguishing the I, that as filler contains chromogenic ion-dispersed silica with covalently grafted hydrazones I-III or formazane IV-XIV General formula

where








 

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1 dwg

FIELD: ecology.

SUBSTANCE: method comprises phytoindication on age of woody vegetation. Determination of the upper limit of affection of a mountain valley with avalanche stream, at which avalanching no vegetation is left on the slopes of the valley, is carried out by measuring the difference in height between the bottom of the valley and the lower limit of the phytometer - autochthonous birch forests, which grow over the affected slope; assessment of date of affection is determined by measuring the amount of annual rings on wood cores drilled by the age-related borer, or on transverse saw cuts at the base of trunks at the level of root collar of the largest trees in the newly formed growing stocks, renewable in the affected area lower the autochthonous birch forests.

EFFECT: method enables to improve efficiency of detection of signs of hazardous natural phenomena.

1 dwg, 1 ex

FIELD: agriculture.

SUBSTANCE: soil sample is passed through a stream of water. On the surface of the soil sample a load is placed. Beginning of dipping of the load is fixed. The parameters of the sample and the water flow are measured. The coefficient of soil filtration is calculated from the measured parameters. The value of the concentration of fulvic acid in the water stream, passed through the soil sample, is recorded. In reducing the concentration value by 10% of the initial value the fulvic acid solution is added into the stream of water directed into the soil sample, restoring the value of the fulvic acid concentration in the stream of water passed through the soil sample, to the initial value.

EFFECT: use of the claimed method extends functional capabilities of determining the filtration coefficient of soil, enables to determine quickly and accurately the filtration coefficient of soil exposed to fulvic acids, in the zone of prevalence of podzolic soils.

1 tbl, 1 ex

FIELD: agriculture.

SUBSTANCE: method comprises the device of cuts, power measurement of layer of membranes of soil biological organisms in the beginning and end of the observation period and the calculation. At that the power of the packed layer of membranes of testate amoebas is measured. The amount of change in the power of peat layer is calculated by the formula Hsrab=a·h, where Hsrab is reduction value of the peat layer power, cm; h is the power of packed layer of membranes of testate amoebas, cm; a is a coefficient. The coefficient a is determined by the formula a=(H1-H2)/(h1-h2), where H2, H1 is the power of the peat layer and h2, h1 is power of the packed layer of membranes of testate amoebas, respectively at the end and the beginning of the observation period.

EFFECT: method enables to determine quickly and accurately the amount of change of power of the peat layer on reclaimed land.

1 ex

FIELD: agriculture.

SUBSTANCE: controlled area in the planting is chosen and prepared, the procedure for controlling of soil respiration is carried out in the chosen controlled area in the planting by measuring the amount of accumulation (loss) of gaseous respiratory substrate CO2 (O2) in a sealed chamber, with which the controlled area is covered. Preparation of controlled area additionally includes such sowing seeds when a part of the area is left unsown. For measurement two different sealed chambers are used separately and alternately, with one of which the part of controlled area of the planting just sown with plants is covered entirely, and with another one additionally to the above area the unsown part of the controlled area of the planting is covered partially or completely. At that the amount of soil respiration attributable to the square of the controlled area of planting is calculated by determining the difference between the measurement results obtained with the above sealed chambers, multiplied by the ratio of the square of the controlled area of planting to the difference of squares of bases of above two sealed chambers.

EFFECT: ability to study in the field, and at the same time the interaction integrity of the root and ground parts of plants is not violated.

1 dwg

FIELD: oil and gas industry.

SUBSTANCE: at first sample of tested oil product with fixed volume is passed through water-coagulating agent placed between turns of a flat spiral mounted in a cavity of the element having shape of a truncated cone. When the sample is passed along the spiral the time for coagulation of free water microdrops in the sample is extended. Then the sample of the tested oil product is passed through a filter membrane with a deposited layer of water-sensitive chemical agent. At that by means of the hollow element having shape of a truncated cone this sample is localised at the surface of this water-sensitive chemical agent and water availability or concentration is evaluated by its colour changing. Additionally water concentration in the sample of the tested oil product is evaluated against decrease of the sample fixed volume before the water-sensitive chemical agent changes its colour.

EFFECT: improved accuracy of the analysis.

1 dwg

FIELD: engines and pumps.

SUBSTANCE: proposed method consists in application of the dependence of kerosene compatibility with rubber upon content of antioxidant therein for determination of antioxidant amount in tested kerosene. Rubber seal ring is used as the rubber specimen in proposed method. Said ring is compressed to 20% of its thickness, placed in tested kerosene to fix compression force continuously during the entire test for determination of compatibility of kerosene with rubber. Compatibility index is calculated by the formula including maximum rubber ring compression force and ring compression force after 3 hours of holding said ring in kerosene at 150°C.

EFFECT: perfected method.

3 dwg, 3 tbl, 1 ex

FIELD: blasting operations.

SUBSTANCE: method consists in calculation of a value of a criterion showing increase of volume of explosive gases in comparison to initial charge volume based on fixation of quantity of destructed material in a metal marker plate at end influence on it of a tightly adjacent cylindrical charge of a test liquid explosive with initiation of explosion from the charge end that is opposite in relation to that adjacent to the plate in order to assess k coefficient of polytrope of explosion products as per an equation solved relative to k with further assessment of destructive properties of exploded charge as per the value of the above criterion that is calculated from the specified ratio.

EFFECT: improving assessment informativity and reliability.

2 cl, 1 dwg

FIELD: mining.

SUBSTANCE: to predict disposition of mineral coals to self-ignition, a model is created, which imitates natural processes of hydrothermall and fluidogenic conversion of coals in foci of self-ignition of pit beds. Continuous flow filtration of air and water mix is carried out via a ground coal sample, placed into a quartz reactor with the specified heating mode to temperature not exceeding temperature of coal self-ignition. Then the quartz reactor is cooled down to room temperature, and continuous flow filtration is repeated. The start of sample thermal destruction is fixed by reaction of indicator gas with water-alkaline solution. By the angle of opening of curves corresponding to the first and repeated heating in the chart they determine speed of exothermic reaction behaviour. The time for incubation period of self-ignition is calculated, which is a predictive factor of disposition of mineral coals to self-ignition.

EFFECT: development of a model that imitates natural processes of low temperature hydrothermal and fluidogenic conversion of coals in foci of self-ignition of pit beds.

10 cl, 5 dwg

FIELD: chemistry.

SUBSTANCE: fuel or air stream is passed at a constant rate through a water separator consisting of multiple cells arranged in series one after the other, formed by a coagulator and a separating grid, and water obtained from separation on a porous partition wall is removed into a settling tank. Pressure in front and behind the partition wall is constantly or periodically measured; information on the pressure measurements is transmitted to an analytical recording unit; hydraulic resistance of the porous partition wall is calculated based on the pressure difference; the obtained data are then used to determine the amount of water retained by the porous polyvinyl formal of the coagulator; based on the obtained calibration data on change in hydraulic resistance of the porous partition wall depending on water content in the coagulator and in the fuel stream, and based on said data, the amount of water contained in the fuel is determined. An apparatus for realising the method is also described.

EFFECT: high accuracy and reliability, easy determination.

8 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: amount of resins before and after washing with n-heptane (washed resins) is determined according to GOST 1567, and presence of a detergent additive in the motor petrol is determined from the difference in the amount of resins before and after washing with n-heptane. There are no detergent additives in the motor petrol if there is no difference between the amount of resins before and after washing with n-heptane. Conversely, if a detergent additive was added to the petrol, there is a considerable difference in the amount of resins before and after washing with n-heptane.

EFFECT: high reliability of determination.

1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to methods of inspecting explosive substances and forensic identification preparations. The method of labelling an explosive substance involves adding a labelling composition to the explosive substance, said composition containing identifiers, the number of which is equal to the number of properties to the labelled. The identifiers used are a mixture of polyorganosiloxanes with different molecular chain lengths, wherein each property matches an identifier in form of a polyorganosiloxane with a corresponding molecular chain length and corresponding "exit time" (retention) on a chromatogram. Thus a "chemical barcode" is formed in the explosive substance, which is read from the chromatrogram based on the principle of the presence or absence of a component at a certain time of its "exit" (retention). The method is suitable for labelling mixed and separate explosive substances, as well as components thereof, for example inorganic oxidants, particularly ammonia nitrate.

EFFECT: method provides high reliability of identifying an explosive substance with a simple process of determining its code.

4 dwg

FIELD: chemistry.

SUBSTANCE: method involves determining resins washed with n-heptane in gasoline before and after adding the analysed additive according to GOST 1567, wherein the gasoline used contains washed resins in amount of at least 5 mg per 100 ml gasoline (e.g. secondary gasoline - catalytic and thermal cracking, viscosity breaking, coking, polymerisation etc, usually with high content of olefin hydrocarbons). The analysed additive is added in amount of 0.03-0.1 wt %. Presence of detergent properties in the analysed additive is determined from the difference in the amount of washed resins in the gasoline before and after adding the analysed additive.

EFFECT: high reliability of determination.

1 tbl

FIELD: chemistry.

SUBSTANCE: method involves measuring the reaction force of gasification products when burning a sample of solid fuel, armoured on the side surface, wherein the reaction force and time for complete combustion of the sample of solid fuel placed in a constant volume explosion apparatus are measured, at pressure in the range of (0.5-1.5)MPa, generated by an inert gas, e.g. nitrogen or argon, wherein the volume of the explosion apparatus and the mass of the sample are in a given ratio, and the value of the unit pulse of is determined using a calculation formula.

EFFECT: enabling determination of a unit pulse using small fuel samples in laboratory conditions without using large stand equipment and explosion-proof boxes.

2 dwg

FIELD: chemistry.

SUBSTANCE: method, which is meant for establishing safe application and combat applicability of artillery munitions, involves sample collection by applying filter paper to liquid droplets on the surface of ballistit powder, followed by dissolving the collected sample in acetone or water heated to 80°C, with addition of 10% potassium hydroxide solution after dissolving in acetone or copper hydroxide after dissolving in water and with evaluation of the result from the colour of the solutions in red-violet colour in the first case or light-blue colour in the second case.

EFFECT: rapid confirmation of detection.

1 dwg

FIELD: metallurgy.

SUBSTANCE: submersible end of bearing pipe is equipped with metering head with submersible end and circumferential side surface. Said metering head with submersible end is furnished with at least one transducer or inlet for samples chamber arranged inside this device. Note here that said circumferential side surface of bearing pipe or metering head with accommodates inlet extending through intake channel into forechamber arranged inside said pipe or metering head. Forechamber end opposite metering head submersible end has inlet extending into slag sampling chamber arranged inside the device on forechamber side opposite said submersible end.

EFFECT: high-quality samples, precise analysis.

13 cl, 3 dwg

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