This method was .used for the determination of F â ion in water and toothpaste and compared with the results obtained with fluoride ion-selective electrode using statistical treatments. Academia.edu is a platform for academics to share research papers. 11. The variation in the color intensity of the paper-sensor with the contaminant loading was found linearly varying with the resistance of the LDR. If we add ferric chloride solution to the deep red-coloured solution containing ferric ions, thiocyanate ions and ferric thiocyanate complex, the concentration of ferric ions increases. . Repeat the titration with 100 mL samples of the cheese extract solution until you obtain concordant ; Analyst, ... C.1 and C.2 sum up some of them specific for iron(II) or iron(III), respectively. When potassium chloride is added to the red solution, concentration of K+ ions increases. Kinetics of complex formation between hexacyanoferrate(III) ions and iron(III) to form FeFe(CN)6 (Prussian brown). When concentration of any species involved in the eqâ¦ complex formed by the ferric ion with the thiocyanate anion, at 3â that time thought to have the structure Fe(CNS)^ , they suggested an analogous structure for the iron(lll)-phenol complexes : Fe(ArO)^ The increase in the intensity of the colour around the anode during the electrolysis of a mixture of phenol and ferric chloride was Capillary electrophoresis was used to quantitatively follow the cellobiose degradation and the formation of glucose. and Dutcher H.A. Iron content was determined using two modified spectrophotometric methods. Arrange the test tubes in a test tube stand [Fig. Cellobiose, a dimer of glucose wearing a glycosidic bond as in cellulose, was used as model molecule to understand the chemical degradation pathways taking place in iron gall inks impregnated papers. NCERT Solutions for Class 6, 7, 8, 9, 10, 11 and 12, Chemistry Lab ManualNCERT Solutions Class 11 Chemistry Sample Papers, When a system in equilibrium is suddenly disturbed, it will respond in some way until equilibrium is re-established. Ruzicka J.,Stewart J.W.B.and Zagatto ions increases. Thiocyanate is a pseudohalide anion obtained by deprotonation of the thiol group of thiocyanic acid. All rights reserved. These inks consist of a mixture of iron(II) sulphate, tannins and gum Arabic, and are therefore acidic and iron-rich. ascorbic acid and antioxidant activities in, are often not too serious. The system is fully computerized and able to monitor thiocyanate in samples at 24 samples per hour with a relative standard deviation of <1.20% for samples and standards with thiocyanate concentrations above 10.0 mg lâ1. This results in decrease in concentration of SCN– ions which in turn shifts the equilibrium (7.2) in the backward direction. The thiocyanatoiron (III) complex absorbs radiation at 447 nm. Nevertheless, even if some oxidation of the sugar molecules occurs, the predominant pathway of cellobiose decomposition is found to be acid-catalyzed hydrolysis due to the high acidity of the medium generated from the oxidation and precipitation of iron. A deep red colour is obtained due to complex formation [Fe(SCN)]2+ (aq). 1. The kinetic parameters of the individual (first order) steps were determined as follows: (i)s0â10â2 Â± 0.5 (sticking coefficient into the molecular state); (ii) with vâ1 = 1010 Â± 1sâ1E1 = 7.5 kcl/mole (desorption of N2,ad); (iii) , with v2â107sâ1, (dissociation of N2,ad into 2Ns). Metal-thiocyanate reactions, Colorimetric Determination of Traces of Metals, Comparative spectropho-tometric determination of the total iron content in varous white and red Greek wines, Spectrophotometric determination of thiocyanate by sequential injection analysis. 1980,105,674-678. Test tubes, test tube stand, droppers, glass rod, beakers, weight box, measuring flask and measuring cylinders. An improvement in the problem of stability of the complex has also been achieved by creating an oxidizing medium using 9.5x10 -4 M KMnO 4 , to prevent the inner redox reaction between SCN â¦ A two-stage aging process was observed at and below 31Â°C. Actually, this is a characteristic test for the presence of ferric ions and for thiocyanate ions. For a particular reaction the value of K is constant at a particular temperature. concentrations. 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To reach this pH, localized iron spots have to be present in the paper as was indeed confirmed by the STXM nano-imaging technique that allowed mapping the distribution of ink components and gelatin within a paper fiber. complexing with a thiocyanate anion (SCNâ) to form the iron(III) thiocyanate complex, Fe(SCN)2+ (Equation 1). hexacyanoferrate (III) and thiosulphate E.A. ; Analytica Chimica Acta, 1976, 81(2), Ferric ionsâthat is, $\text{Fe}^{3+}$ ionsâreact in aqueous solution with thiocyanate ionsâthat is, $\text{SCN}^{-}$ ionsâto form a dark red colored complex of iron thiocyanate. Rating: Source: UW Card Catalog. Access scientific knowledge from anywhere. S.;Talanta,1976,23(6),449-454. Regular on-spot monitoring of water quality has become mandatory wherein diverse classes of materials such as organic, inorganic, heavy metals, or biological wastes are detected employing standard protocols. caused by the effect of fluoride ion was exploited for its indirect determination down to 0.019ppm F â .This concentration can be lowered even more than that obtained with fluoride ion selective electrode if standard addition method was used. Our channel. Depending upon the thiocyanate concentration and solvent medium, some researchers believe that a series of complexes described by the general formula [Fe(SCN) n ] (3Ãn)+ , where n = 1-6, is formed, while others suggest that in dilute solutions only one product is formed and that is [FeSCN] 2+ (Below et al., 1958; Yoshimura K., Waki H. and Ohashi where [Fe(SCN)]2+, [Fe3+] and [SCN–] are the equilibrium concentrations of the respective species while K is the equilibrium constant. the determination of Iron(III) in 1853[1]. While for the creatinine sensor the papers were coated with alkaline picrate solution leading to a lemon-yellow coloration of the surface. The absorbance, results are plotted between A and volume of, less than the tabulated value of 3.182. NCERT Solutions for Class 10 Science Chapter 1, NCERT Solutions for Class 10 Science Chapter 2, Periodic Classification of Elements Class 10, NCERT Solutions for Class 10 Science Chapter 7, NCERT Solutions for Class 10 Science Chapter 8, NCERT Solutions for Class 10 Science Chapter 9, NCERT Solutions for Class 10 Science Chapter 10, NCERT Solutions for Class 10 Science Chapter 11, NCERT Solutions for Class 10 Science Chapter 12, NCERT Solutions for Class 10 Science Chapter 13, NCERT Solutions for Class 10 Science Chapter 14, NCERT Solutions for Class 10 Science Chapter 15, NCERT Solutions for Class 10 Science Chapter 16, CBSE Previous Year Question Papers Class 12, CBSE Previous Year Question Papers Class 10. Organic compounds containing the functional group SCN are also called thiocyanates. The encoded protein is localized to the mitochondria and catalyzes the conversion of thiosulfate and cyanide to thiocyanate and sulfite. The effect of the reagent concentration and nitric acid concentration (in the reagent solution and carrier stream, respectively), were also studied. It is shown in these two figures. For increased accuracy in the measurement of samples of widely varying chloride content, the sample is split in the reagent stream so that the relevant absorbance of the split sample zones varies from 1:2 to 1:10 allowing expansion of the analytical range without loss of accuracy. DOI: 10.1021/ja01022a012. For this purpose, initially, the sensors were characterized and calibrated with known concentrations of contaminates before successful validations with real samples. Thus, increase in the concentration of SCN– ions shifts the above equilibrium in the forward direction. Degradation of paper by iron gall inks (IGI) is a challenging issue for written heritage conservation. 2- My first book is completed and already typed now, I started my second book which is on: Analytical Instrumentation also in Kurdish Language. Ion-Selective electrodes construction for Drug or metal analysis will be a good help for quick and easy applications. An improvement in the problem of stability of the complex has also been achieved by creating an oxidizing medium using 9.5x10 -4 M KMnO 4 , to prevent the inner redox reaction between SCN -and CNS -. Main Content. Thereafter, the sensors were illuminated with a light emitting diode from one side while the transmitted rays passing through the sensor was captured by a light dependent resistor (LDR) from the other side. 2. So at this wavelength, Beerâs Law can be rewritten as: A = ab[FeSCN2+ ] (Eqn. Consider the equilibrium between ferric ions and thiocyanate ions: It is a conjugate base of an isothiocyanic acid and a thiocyanic acid. Ferric chloride reacts with sodium thiocyanate to produce ferric thiocyanate complex. Fe3+ (aq) + SCN (aq) Fe(SCN)2+ (aq) Equation 1 . In 0.01 M HClO4 xenon difluoride oxidizes water with a first-order rate constant of 4.2 Ã 10-4 sec-1 at 25Â°, and with ÎHâ¡ = 19.6 kcal/mole and ÎSâ¡ = -8.1 eu. Put 10 ml of 0.1 M FeCl3 solution in it by using a measuring cylinder. 7.1]. The intensity of the transmitted rays, passing through the sensors, was found to vary the electrical output of the LIS monotonically with the loading of the total protein or creatinine in the analyte. It has a role as a human metabolite. In qualitative inorganic analysis, the presence of ferric ion can be detected by the formation of its thiocyanate complex. Increase in concentration of either of the reactants (Fe3+ ions or SCN– ions) shifts the equilibrium ‘ in the forward direction (towards right), on the other hand decrease in concentration of any of the reactants shifts the equilibrium in the backward direction (towards left). Common derivatives include the colourless salts potassium thiocyanate and sodium thiocyanate. These react with the Fe3+ ions to form a blood-red coloured complex: Fe3+ (aq) + SCNâ (aq) â [FeSCN]2+ (aq) By comparing the intensity of â¦ In 1855, the nature of a chemical reaction was still being hotly debated amongst chemists. 2. The thiocyanate ion is colorless. Foster M.D. Hence, the colour intensity of red-solution increases. The second stage is ascribed to conventional interstitial bulk diffusion. Iron content in a satisfactory number of bottled and non-bottled white, rosÃ© and red Greek wines has been determined in this work. Effect of increasing the concentration of potassium ions. The pale orange color of the resulting solution is caused by the iron hexaquo complex. Reaction of xenon difluoride with water and with xenon trioxide, Hydrogenation of propylene over group VIII metals, Contribution of snoek rearrangement to strain aging. The stepwise mole ratio complexation between them has been carefully confirmed. Dispensing protein (creatinine) solution of known concentration on the respective sensors led to the conversion of chrome-yellow to bluish-green coloration (lemon-yellow to orange coloration) for the total protein-sensor (creatinine) sensor. Take four test tubes and label them as A, B, C and D. Add 10 ml of the deep red solution to each of the four test-tubes. of SCN -with 8 x 10 -4 M. Fe(III) in 1 ml conc.HCl. (a) Effect of increasing concentration of ferric ions. The rather old and well known Fe(III)-thiocyanate system has been restudied. 0.012 and 0.36M, iron(III) 1.16 ppm in 0.1 M HCl. consumed per molecule of XeF2 varies from zero to 1, depending on the initial ratio of concentrations. Â© 2008-2021 ResearchGate GmbH. The following information should allow you to develop a research plan for evaluating the equilibrium constant of the iron (II) thiocyanate ion in aqueous solution. We report the development of a point-of-care (POC) kidney function test (KFT) kit, which is composed of a paper-based PCR sensor, an opto-electrochemical measurement unit, a display, and a facility to transfer data to a smartphone. Cyanide ions are nowhere directly involved in the formation of ferric(III) thiocyanate. (b) Chemicals. The sensor was then translated into a specific, stable and user friendly POCT device, which enabled inexpensive spot detection of pollutants in drinking water. Ferric thiocyanate is Fe(SCN) 3. Ferric chloride (Iron(III) chloride) Ferric oxide â¦ The product is red, while the reactants are yellow or colorless, allowing for shifts in equilibrium to be observed visually. The well-known colorimetric determination of the equilibrium constant of the iron(III)âthiocyanate complex is simplified by preparing solutions in a cuvette. The intermediate formed N2.ad is characterized by an adsorption energy of 7.5 kcal/mole and by a dipole moment of â¼0.4 D of the adsorbate complex, the negative charge being located at the nitrogen molecule. Another type of ROS was detected in higher quantity, but correlated more to oxidation of iron leached species rather than to paper decay itself. As a result, more thiocyanate ions combine with ferric ions to increase the [Fe(SCN) 2+ ] complex and therefore the colour intensity of the red solution increases. Join ResearchGate to find the people and research you need to help your work. Ammonium thiocyanate react with iron(III) chloride to produce ammonium hexathiocyanatoferrate(III) and ammonium chloride. Traces of HOâ were identified on some samples, but their presence was not consistent with paper damage. It affects the equilibrium between potassium and thiocyanate ions. -Optimization of SCN -concentrations. When ferric chloride solution is added to the red solution containing ferric ions, thiocyanate ions and ferric-thiocyanate complex, concentration of ferric ions increases and therefore, the concentration of thiocyanate ions should decrease or that of [Fe(SCN)]2+ should increase so as to keep concentration quotient equal to equilibrium constant at a given temperature. The reaction between propylene and hydrogen over pumice-supported metals of the eighth group has been investigated in a constant volume reactor for a wide range of temperature and reactant ratios. 8. The reaction is a classic school experiment to demonstrate Le Chatelier's principle: [Fe(H 2 O) 6] 3+ + SCN â â [Fe(SCN)(H 2 O) 5] 2+ + H 2 O See also. Consider the equilibrium between ferric ions and thiocyanate ions: The equilibrium constant for the above reaction can be written as where [Fe(SCN)]2+, [Fe3+] and [SCNâ] are the equilibrium concentrations of the respective species while K is the equilibrium constant. The physical parameters (flow rate, sample and reagent volumes, holding coil and reaction coil internal diameter and length) which influence dispersion in a SIA system were optimized. NaSCN between 0.012 and 0.36M, iron(III) 1.16 ppm in 0.1 M HCl. 10.Smith O>M. R. G. Walker, Kenneth O. Watkins. Take a 250 ml beaker thoroughly washed and clean. [provided by RefSeq, Jul 2012] 3. Hence, paper degradation by IGI is often attributed to a combination of acid hydrolysis and of iron-catalyzed oxidation involving hydroxyl radicals (HOâ) formed by Fenton reaction. 1. The variations in the color-intensities of the paper sensors with the variation in the concentration of fluoride (Fâ»), lead (PbÂ²âº), and pH were converted into electronic signals to enable the development of a point-of-care-testing (POCT) device. Shake all the tubes well. The number of XeO3 molecules. Stability of ferric thiocynate and cobalt thiocyanate complex was also studied. It is the conjugate base of thiocyanic acid. When the ferric thiocyanate complex was allowed to equilibrate longer than 2 h, consistent increase in the absorbance was observed for the complex of polysorbate 80 with lower (0.0005%) concentration. Total iron has been determined in water and drugs down to 0.06ppm Fe 3+ with r 2 = 0.9997 ,recovery of 99.1-102% and precision of 0.13%. Construction of New Ion Selective Electrodes. ISE /, prevent Fe(III) hydrolysis, therefore the, three salts mentioned before, and the results, Fig (1): Effect of HCl medium concentratio, and (3). 3. Kinetics of the Formation of the Ferric Thiocyanate Complex BY JOHN F. BELOW, JR., ROBERT E. CONNICK AND CLAUDE P. COPPEL RECEIVED NOVEMBER 2, 1957 An apparatus for rapidly mixing two solutions has been developed and applied to a study of the kinetics of the reaction: Fe+++ 4- SCN- = Fe(SCN)++ in aqueous solution. The dissociative adsorption of nitrogen on a clean Fe(111) surface proceeds via with a very small overall sticking coefficient and a slightly negative activation energy: ; (at zero coverage). Description: A solution containing red iron thiocyanate complex is divided into three parts. Next. Experiments were carried out in liquid phase at 80 Â°C to study the effects of pH and of the presence of iron and oxygen on the cleavage of the glycosidic bond. Intermediates in the reaction oxidize benzenesulfonic acid and reduce XeO3. Thiocyanate ammonium - concentrated solution. Therefore, ferric ion. The Figure 2(a) illustrates the UV-visible spectra of the interaction between iron (iii) thiocyanate and fluoride. Therefore, increase in concentration of ferric ions results in more of thiocyanate ions combining with ferric ions to give more of [Fe(SCN)]2+ complex and therefore, the colour intensity of red-solution increases. In addition, the protein interacts with 5S ribosomal RNA and facilitates its import into the mitochondria. 4. The ferric ion is yellowish. Thus increase in concentration of K+ ions shifts the above equilibrium in the backward direction. (a) Apparatus. The iron (III) cyanato complex, on the other hand, is a deep red. Previous. The reaction is catalyzed by bases and by substances with affinity for fluoride ion. Add 1 mL of saturated ferric ammonium sulfate solution as indicator. The proposed methods are rapid, accurate, simple, relatively inexpensive and can be used for all types of wine (white, rosÃ© and red). The pH of the final solution was 6. was selected as the most suitable catalyst for thiocyanate oxidation. (b) Effect of increasing concentration of thiocyanate ions. determination (stability constant of 2.3 (Charlot 1961; ... Thiocyanate anion forms a complex with iron (III) cation to form a blood red iron (III) thiocyanate complex ion. We will be studying the reaction that forms the reddish-orange iron (III) thiocyanate complex ion, $$\ce{Fe(H2O)5SCN^{2+}}$$ (Equation \ref{2}). The second method, involved the use of the compound 2-(5-nitro-2-pyridylazo)-5-[N-n-propyl-N-(3-sulfopropyl)-amino]-phenol disodium salt (Nitro-PAPS, C17H19O6N5SNa2), known for its highly sensitive reaction with Fe(II). 1955. This is also supported by the detailed study of the respective effects of iron, oxygen and pH towards degradation of cellobiose taken as a model molecule. When concentration of any species involved in the equilibrium is disturbed, the concentration quotient. Add 5 ml of distilled water to test tube A; 5 ml of 0.1M FeCl3 solution to test tube B ; 5 ml of 0.1 M KSCN solution to test tube C and 5 ml of 0.1 M KC1 solution to test tube D. Structure, properties, spectra, suppliers and links for: ferric thiocyanate. A sequential injection analysis (SIA) system was developed for the spectrophotometric determination of thiocyanate as Fe(SCN)2+. The first stage attributed to Snoek-Schoeck-Seeger rearrangement of interstitials about, The kinetics of oxidation of thiosulphate by hexacyano-ferrate (III) in an aqueous Effect of HCl medium concentration with different ratio of Fe(III) / SCN -. Contents. 10. The intensity of the red colour corresponds to concentration of complex [Fe(SCN)]2+ and if the concentration of this ion increases, the colour intensity will also increase. Alternative splicing results in multiple transcript variants. perchloric acid medium has been studied spectrophotometrically by stopped flow method at Investigating Iron Thiocyanate Revised: 4/28/15 3 [SCNâ]eq = [SCNâ]i â [FeNCS2+]eq (4) Knowing the values of [Fe3+]eq, [SCNâ]eq, and [FeNCS2+]eq, the value of Kc, the equilibrium constant, can be calculated. ; Ind.Eng.Chem.Anal.Edu.;1934,6,61. Rao T.P., and Ramakrishna T.V. Oxidation of thiosulphate by hexacyanoferrate (III) in aqueous perchloric acid medium--A kinetic and... Kinetics of nitrogen adsorption on Fe(111). This was done after a theoretical study of the relationship between the amount of metal ion and thiocyanate as ligand in the metal-thiocyanate complex reaction systems. Nevertheless, which of these two mechanisms prevails on cellulose depolymerisation remains a largely open question, which is addressed in the present work. The difference in the stability of the cobalt and the ferric thiocyanate â¦ A hypsochromic shift from 480 to 410 nm. 11. Therefore, they may be used for the iron assay in routine wine analyses, as an alternative to the AAS method. The calibration graph is linear from 2.0 to 150.0 mg lâ1 with a 3Ï detection limit of 1.1 mg lâ1. Effect of increasing concentration of ferric ions. Ferric chloride (0.1 M), potassium thiocyanate (0.1 M) and potassium chloride (0.1 M). Find another reaction. It is a pseudohalide anion and a sulfur molecular entity. 2+ eq 3+ [Fe(SCN) ] K [Fe ][SCN ] Equation 2 . Dilute solutions of thiocyanate should be used. Ferric thiocyanate complex. Addition of thiocyanate salts to the solution gives the intensely red 1:1 complex. using persulfate. 5. Reagent consumption was effectively reduced by introducing the reagent as a zone into the nitric acid carrier stream, compared to flow injection analysis where the reagent itself is the carrier stream. Year or vol: page: Keywords: ferric chloride, iron (III) chloride, ammonium thiocyanate, hydrochloric acid To make the presence of these ions in solution visible, thiocyanate ions (SCNâ) are added. The determination of depolymerisation kinetics at different temperatures led, on inked papers, to activation energies only slightly below those obtained on acidic papers, suggesting a dominant acid hydrolysis mechanism with a limited catalytic effect of iron. For this stage the following has been found: (a) a t2 3 relationship is obeyed, (b) the yield point return data agree with interstitial jump time, (c) the maximum value of the yield stress increment is a constant of 0.7 Â± 0.1 kg/mm2 and is independent of time and temperature, (d) positive intercepts at zero aging time are observed, and (e) there is close agreement between the activation energies determined by Hartley analysis (14.5 kcal/mole) and Arrhenius equation (15.5 kcal/mole). The intensity of colour of a solution should be compared by keeping it and reference side by side and then observing from top. 54,4464. Mechanisms are proposed invoking XeO and XeO2 as intermediates. The present study has attempted to find out, be added the last after which measurement is, error. This serves as your reference standard to observe the effect of adding different substances. at 480nm, All figure content in this area was uploaded by Fadhil M.Najib, All content in this area was uploaded by Fadhil M.Najib on Apr 21, 2016, The rather old and well known Fe(III)-thiocya, about 47 mins. The apparent activation energies for Ni, Fe, Co, Pt, Using the yield point return technique the strain aging kinetics of annealed Ferrovac E iron (0.01% C, 0.0002% N) has been studied in the temperature range of 0Â° to 100Â° C. Aging was performed while the specimen was subjected to tensile stress. They drew upon the concept of âchemical affinityâ to explain why substance A might react with substance B, but not substance C, in that A had a stronger affinity for B, than it did for C, or was more strongly attracted to B than to C. The linearity of the standard calibration graph for the spectrophotometric flow injection determination of chloride, based on its displacement of thiocyanate from mercury(II) thiocyanate and the subsequent reaction of the thiocyanate with iron(III), was extended by the addition of nickel(II) and copper(II) to the standard reagent solution. Download PDF: Sorry, we are unable to provide the full text but you may find it at the following location(s): https://escholarship.org/uc/it... (external link) The catalytic activity of the metals are in the sequence: Rh > Ir > Ru > Pt > Pd > Ni > Fe > Co > Os. Note the color of the solution and record this information in your laboratory notebook. You will also need to generate a standard curve for iron (II) thiocyanate and it might be helpful to review the last time we used a standard curve (Lab 4) and why. Contamination of water bodies due to the disposal of natural and anthropogenic pollutants is one of the major global concerns in the recent times. The simple manifold allows a routine sampling rate of 300 samples/hour, and evidence is presented that 500 samples/hour are possible. In other words, some of the [Fe(SCN)]2+ complex dissociates to give Fe3+ ions and SCN– ions. This approach gave evidence that acidification of the solution during iron oxidation is the driving force for osidic bond cleavage. Its equilibrium expression is as shown in Equation 2. From the results, it is concluded that, ferrate. One is treated with excess iron (III), and the other with excess thiocyanate. Lâ1 potassium thiocyanate solution. Use tubes of almost identical diameter. the formation of the ferric thiocyanate bloody red complex solution. Thus, increase in concentration of Fe3+ ions shifts the above equilibrium in the forward direction. ; J.Amer.Chem.Soc., 1932, Add 10 ml of 0.1 M KSCN solution with the help of measuring cylinder. The first step was to look at reactive oxygen species (ROS), especially HOâ, by trapping reactions coupled with ESR and HPLC. Further, the sensors were employed for the on-spot detection of the unknown PCR in the real human urine samples. (c) Effect of increasing the concentration of potassium ions. Due to decrease in concentration of [Fe(SCN)]2+ the intensity of red colour decreases. However, most of the existing laboratory techniques are either costly and/or time consuming owing to the process involving the expert driven sophisticated analysis techniques. If Keq is a large number (>1), then the chemical equilibrium favors the formation of product Explanation: Addition of Fe (NO 3 ) 3 increases the reactant (Fe +3 ), disturbing the system. 4. The recovery of F â ion was between 105-95%, with C.V. 2%. I am on pension now, therefore I can be ready give procedures and follow it up. The wines analyzed were from various regions of Greece. The rapid determination of chloride in water samples based on spectrophotometric measurement of iron(III)thiocyanate has been adapted to Flow Injection Analysis. The active ingredients are normally, solutions was taken, iron (II) was oxidize, For concentrations of Fe (III) less than 0.06, with D.W. and mixed well.