CS200399B1 - Process for treatment of natural medicinal iodinated mineral water for balneoterapeutic purposes - Google Patents

Description

The present invention provides a method for treating natural medicinal, iodine mineral waters for balneotherapeutic purposes by releasing elemental iodine from iodides by anodic oxidation.

The natural iodine and iodine healing mineral waters used contain at least 5 J ”. 1 ^_1 (in some countries 1 and J “. ^{* 1 *} ). The resorption of iodine by human skin and mucous membranes increases substantially when the poison is present in water not in ionized form but in the form of dissolved elemental iodine.

Therefore, iodides in mineral waters are oxidized to elemental iodine for therapeutic purposes. In the world spa there are basically two methods of oxidation - spontaneous oxidation of iodides and oxidation by chemical agents.

Spontaneous oxidation is probably caused by microorganisms (SKRUSE H., SPITZV H.Wiener wedge. Wochenschr. 67, 1955, 601 - 605). It takes place in large storage tanks, which are expensive to build. The degree of oxidation (element, iodine concentration) is not completely controllable, so the value of the balneotherapeutic agent is not constant.

Oxidation with chemical agents - the most commonly used method with chloraain B, has the disadvantage of the risk of overdose or incomplete mixing, which may result in adverse effects of the QSidating agent and its residues on the skin of the patient. Oxidation of iodides in iodine mineral water using ozone has been described by DEUTINGER-SKRUSE H., PFEIL G., Z.aagew.Bader -u.Klimaheilk.

200 399

23, 1976, 5,436 _e Water used to fill the spa pool ·

Chlorine, hypochlorite and other reagents can also be used to oxidize iodides. The disadvantage of most reagents is their toxicity, hazardous handling, especially in medical management, and the risk of allergic cakes.

The aim of the new solution of the treatment of natural iodine mineral waters for their non-therapeutic use was to eliminate the addition of foreign substances and its adverse effect on the patient, the possibility of regulating the concentration of elemental iodine and automatisaoe process, performing mime balneotherapy and without human intervention.

The present invention provides a method for treating natural medicinal iodine mineral waters for balneotherapeutic purposes by releasing elemental iodine from iodides by anodic oxidation.

From the chemical composition of mineral water it is theoretically possible to determine what processes may occur in its electrolysis * The decisive factors are chloride, iodide and bromide ions in anodic oxidation and sodium and hydrogen ions in cathodic reduction *

The anode potential is controlled by the respective electrode reaction of the halides

Xg + Ze » 2 X (1) and equations apply to equilibrium ^{E E} ° Xg x - ^RI 1 «ZP X ^and X 2 (2) They have standard potentials at 25 ^° C values ^e j ₂ , J ~ at 0,62 V ^E Br ₂ , Br ~ with 1,066 V ^ Ig.Cl - 1,359 V

According to these standard potentials, halogens will be excreted in the same order ie iodine, bromine, chlorine.

In addition to the anodic oxidation of halides, it is also necessary to consider the oxidation of the science in which oxygen is released on the electrode:

0 ₂ + 4 H + + 40 - 2 HgO (3) whose equilibrium potential is given by (25 ® C)

B - 1.229 - 0.059 pH + g P,

Which or which electrochemical reactions take place in electrolysis and indifferent electrodes is determined by its potential, driven by the concentration (activity) of the halonium and hydrogen ion, and by the respective concentration and activation overvoltage and current magnitude.

In a neutral environment, the equilibrium potential of reaction (2) decreases (e.g., pH 7 is B »0.80 V), so that oxygen is preferable to be excreted after bromine and chlorine after iodine. In fact, oxygen is excreted at a more positive potential due to oxygen overvoltage simultaneously with chlorine.

The reaction product on the inert cathode is hydrogen gas, which is eliminated by reducing water while releasing hydroxide ions, so that the initially neutral science becomes alkaline at the cathode.

H2® ² ° (5)

In the electrolysis of aqueous halide solutions, secondary chemical processes occur, in particular the reaction of the formed halogens with hydroxide ions from the water or a cathode formed according to the reaction (5.).

Dissolved halogen undergoes hydrolysis and disproportionates to low-dissociated haloanenoic acid and very strongly dissociated hydrogen halide acid according to the equation

Ϊ2 + HgO --- H ⁺ + X + HXO

The dispersion is controlled by an equilibrium constant at a given temperature.

/ H ⁺ / - / X '/ ./ HXO /

K - (-) - (7) (X ₂ ). / h ₂ o /

If the H ⁺ concentration in the solution is kept constant (pH buffer) and the X "concentration is large, then the change in the H ⁺ and X" concentration resulting from the reaction can be left.

By substitution of the material balance condition, where / X ₂ / * is the original halogen concentration before disproportionation / Xg - - / Xg / + / HXO / (8) into equation (7) we obtain the relation / HXO / K ~~ - “.—- - (δ) / N ⁺ / / X ~ / + K from which the degree of dispreporation can be calculated (eg as a percentage) if we put the concentration X “after the concentration, eg 0.1 M.

For

K ² * ⁰ ( CI ₂ H ⁺ + Cl + HC10 )  4,5. 10 ' ² 5 ° Κ ( Br ₂ + HjjO. H ⁺ + Br + HBrO ) - 5,2. 10 ’ « ⁰ ( J ₂ + - - H ⁺ + J " + HJO ) «3.6 · 10 ’·

the degree of dispersion is recorded in Table 1.

Table 1. pH Dispreoionation of halogens in percent depending on chlorine brem iodine 0 9.5 1 4.3 2 31.0 3 81.8 4 97.8 5 99.8 0.5 6 5.2 7 34.2 8 83.9 9 98.1 0.4 10 99.8 3.5 11 99.9 26.5 12 78.2 13 97.3 14 99.7

It is apparent from the table that one of the usual pH values of 7-8 hydrolysis is virtually not subject to and will be stable in the mineral water flow.

In addition to the primary reactions expressed by equations (6), other processes can take place.

Acids? hypochlorous ions and e-mannate ions formed by dissociation of chromic acid can react together to form

2 HC10 + CIO ”- CIO” + · 2 H ⁺ + 2 Cl ' (10) or based on the total chlorine-based reaction 3 Cl ₂ + 3 1 ^ 0 - CIO ” + · 6 H ⁺ '* + 5 Cl ” Italy (11) The equilibrium constant of this equation is ® ²³ ®. ₅ , 9 . 10 ” ¹²

The course and rate of reaction depends on the pH of the solution.

In the acid solution, the concentrations of hypochlorite and chloric acid are low and the rate of reaction is very low.

Similarly, for the formation of bronate and iodate, the equilibrium constants are given by values.

'7.3 _β io ³⁴

K ²⁵ * - 2.8. 10 ^'46

The last step, associated with the largest loss of free enthalpy, is the breakdown of haloes and innards into free oxygen and halide

OX ”

21 '+ 0 ₂

This reaction proceeds more slowly than the formation of halothenates, but can be catalysed by some oxides, such as cobalt, nickel, copper, iron, etc., or platinum, black, resulting in rapid consumption of halides and no halogenates are formed.

The principle of the anodic oxidation treatment method for ballast therapy according to the invention consists in electrolysis by a direct current © of 0.9-40 V between electrodes of a mineral water-resistant material under operating conditions. The optimal course of anodic oxidation depends on the concentration and composition of the naturally treated iodine mineral water. It consists in the choice of temperature, quality, dimension, shape and spatial arrangement, electrodes, method and intensity of mixing, possibly water circulation, electrode distance, applied voltage and current density per unit area of the electrode surface.

The basic process tends to release elemental iodine according to reaction 2 J --— J ₂ + 2 e “

Side, undesired and suppressed reactions lead to oxidation of iodides to the negotiated and higher oxidation stage - iodates, depending on the reaction

J ”+ 6 OH” ——— JO ^ + 3 HgO + 6 e “and for the electrolysis of water to hydrogen and oxygen.

The higher efficiency of said method of treating natural medicinal iodine mineral waters by the anodic oxidation of iodides is that no foreign chemical agents are added in the medicinal water to release elemental iodine. The whole treatment process can be carried out in a closed cycle with the possibility of selecting the final concentration of elemental iodine in water according to the requirement in a wide range. The adjustment method allows full automatisaoi process.

According to the invention, iodine mineral water flows between the electrode system, one part of which is connected to the positive pole of a 1.8 to 24 V DC power supply, the other part to the negative pole of the source. Iodine mineral water flows around the electrodes one or more times until the desired concentration of electromagnetic iodine in the water is reached.

The oxygen and hydrogen gases produced by electrolysis at the electrodes are preferably used to remove possibly present desirable organic substances, in particular of diesel origin, from the poison water.

Claims (1)

An example of an embodiment of the invention in practice is a method of releasing elemental iodine in balaeotherapy for the preparation of baths from natural iodine-bromine mineral water of the following composition (shown in the form of the chemical composition formula common in balneology) 324 Cl ”80 HCO ~ 19 J ”39.4 Br“ 35.4 HBOg 128 M ---- 10436 Na ⁺ 90 _M (mval%) Oxidation can basically be carried out in two basic ways A - in a stirred solution into which the electrodes are immersed B - electrodes are inserted into the housing through which the mineral water flows unidirectionally once or repeatedly * at 6.8 T 11.9 ⁰ 0 = eelk.raineralisations in mg. I ^-1 and mval. I ” ¹ Example results » Way Embedded Voltage (V) Intensity (mA. Om “ ¹ ) Duration (sec ·) Kenoo.element * J ₂ (mg J ₂ .l “ ¹ ) AND 1,8 11 30 1.3 AND 15.0 680, 30 32.8 (B) 5.0 110 300 3.8 (B) 5.0 110 600 11.8 (B) 9.8 450 30 2.4 (B) 9.8 450 150 16.55 (B) 9.8 450 270 25.2 (B) 24 400 3.5 21.95 PŘE B ME ME OF THE INVENTION Process for treating natural medicinal iodine mineral waters for balneotherapeutic purposes by releasing elemental poison from iodides by anodic oxidation, characterized in that iodine mineral water is treated with a direct electric current of voltage from 1.8 to 24 V, while the poison mineral water around the electrodes is kept in constant intense movement.