<?xml version="1.0" encoding="UTF-8"?><!DOCTYPE article  PUBLIC "-//NLM//DTD Journal Publishing DTD v3.0 20080202//EN" "http://dtd.nlm.nih.gov/publishing/3.0/journalpublishing3.dtd"><article xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink" dtd-version="3.0" xml:lang="en" article-type="research article"><front><journal-meta><journal-id journal-id-type="publisher-id">AMPC</journal-id><journal-title-group><journal-title>Advances in Materials Physics and Chemistry</journal-title></journal-title-group><issn pub-type="epub">2162-531X</issn><publisher><publisher-name>Scientific Research Publishing</publisher-name></publisher></journal-meta><article-meta><article-id pub-id-type="doi">10.4236/ampc.2015.54014</article-id><article-id pub-id-type="publisher-id">AMPC-55858</article-id><article-categories><subj-group subj-group-type="heading"><subject>Articles</subject></subj-group><subj-group subj-group-type="Discipline-v2"><subject>Chemistry&amp;Materials Science</subject><subject> Physics&amp;Mathematics</subject></subj-group></article-categories><title-group><article-title>
 
 
  Effect of Degree of ClO&amp;oline; Hypochlorite on the Wet Synthesis of Ferrate (VI)
 
</article-title></title-group><contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>bdellatif</surname><given-names>El Maghraoui</given-names></name><xref ref-type="aff" rid="aff1"><sup>1</sup></xref></contrib><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Abdelaziz</surname><given-names>Zerouale</given-names></name><xref ref-type="aff" rid="aff1"><sup>1</sup></xref></contrib><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Mustapha</surname><given-names>Ijjaali</given-names></name><xref ref-type="aff" rid="aff1"><sup>1</sup></xref></contrib></contrib-group><aff id="aff1"><addr-line>Laboratory of Chemistry of Condensed Mater (LCMC), Faculty of Sciences and Technology, Sidi Mohammed Ben Abdellah University, Fez, Morocco</addr-line></aff><pub-date pub-type="epub"><day>22</day><month>04</month><year>2015</year></pub-date><volume>05</volume><issue>04</issue><fpage>133</fpage><lpage>139</lpage><history><date date-type="received"><day>13</day>	<month>December</month>	<year>2014</year></date><date date-type="rev-recd"><day>accepted</day>	<month>19</month>	<year>April</year>	</date><date date-type="accepted"><day>22</day>	<month>April</month>	<year>2015</year></date></history><permissions><copyright-statement>&#169; Copyright  2014 by authors and Scientific Research Publishing Inc. </copyright-statement><copyright-year>2014</copyright-year><license><license-p>This work is licensed under the Creative Commons Attribution International License (CC BY). http://creativecommons.org/licenses/by/4.0/</license-p></license></permissions><abstract><p>
 
 
  This work is a result of previously done studies on the synthesis of A
  <sub>2</sub>Fe
  <sup>VI</sup>O
  <sub>4</sub> wet ferrate (VI) formula, using chlorine as an oxidant. The major problem of these ferrates is related to their stability over time. This brings us to identify and optimize the critical parameters influencing the prepara
  tion of the Na<sub>2</sub>FeO<sub>4</sub> at room stable phase with acceptable performance. The use of water bleach (hypochlorite ClO&amp;oline;) at a chlorometric degree of 50&#176;F in the synthesis of the Na<sub>2</sub>FeO<sub>4</sub> ambient stable phase promotes the oxidation of iron (II) iron to (VI) in a concentrated NaOH alkaline medium. The synthesis reaction is in the presence of FeSO<sub>4</sub> 7H<sub>2</sub>O hydrated iron sulfate at a temperature of about 55&#176;C in order to simplify the synthesis process, to enhance the production of the Fe (VI) and to meet the growing demand of ferrates (VI) for their interest in the treatment of water. Monitoring the degradation of synthesized Na<sub>2</sub>FeO<sub>4</sub> shows its stability up to 12 months, which facilitates storage and transportation. The phases obtained were characterized by IR spectroscopy, and RX by UV spectrophotometer, measuring the optical density at 507 nm.
 
</p></abstract><kwd-group><kwd>Ferrates</kwd><kwd> Bactericides</kwd><kwd> Antioxidant</kwd><kwd> Flocculant</kwd><kwd> Coagulant</kwd><kwd> Wet</kwd><kwd> Water Treatment</kwd></kwd-group></article-meta></front><body><sec id="s1"><title>1. Introduction</title><p>The ferrate (VI) is a supercharged iron compound in which the iron is in the oxidation state +6. It is known under the name of iron (VI). The ferrate is extremely powerful, can provide multiple treatments from a single application, does not create disinfection by-products, is environmentally friendly, and solves the difficult treatments which represents the challenges of other oxidants can’t touch. The Ferrate treatment option is often the least expensive and most effective.</p><p>The synthesis of ferrate (VI) has been studied by many authors [<xref ref-type="bibr" rid="scirp.55858-ref1">1</xref>] -[<xref ref-type="bibr" rid="scirp.55858-ref11">11</xref>] to be simpler and more suitable methods with a higher yield and stable phases. Despite improvements, the results remain limited.</p><p>Ockerman et al. [<xref ref-type="bibr" rid="scirp.55858-ref12">12</xref>] and Scheryer et al. [<xref ref-type="bibr" rid="scirp.55858-ref13">13</xref>] show that the precipitation washing and drying protocols are required to achieve a stable and solid outcome.</p><p>Publications and patents for K<sub>2</sub>FeO<sub>4</sub> synthesis modes recommend the use of a ferric salt [<xref ref-type="bibr" rid="scirp.55858-ref14">14</xref>] [<xref ref-type="bibr" rid="scirp.55858-ref15">15</xref>] .</p><p>In 1950, Hrostowski and Scott [<xref ref-type="bibr" rid="scirp.55858-ref16">16</xref>] proposed a method to prepare ferrate with a purity of 97% of ferric chloride by oxidation with sodium hypochlorite in a concentrated sodium hydroxide solution at temperatures ranging between 50˚C and 55˚C. Now, for the environment in which operate Hrostowski et al. [<xref ref-type="bibr" rid="scirp.55858-ref16">16</xref>] is highly NaOH concentrated. Na<sub>2</sub>FeO<sub>4</sub> is assumed very soluble, whereas NaCl has precipitated in the solution [<xref ref-type="bibr" rid="scirp.55858-ref17">17</xref>] , which then makes a separation by filtration possible.</p><p>El Maghraoui et al. [<xref ref-type="bibr" rid="scirp.55858-ref18">18</xref>] achieved the synthesis of ambient stable Na<sub>2</sub>FeO<sub>4</sub> by the oxidation of iron (II) to iron (VI) by electrochemical means.</p><p>The wet method is considered the most practical but remains very expensive.</p><p>The aim of this work is to synthesize compounds based on stable Iron (VI), particularly Na<sub>2</sub>FeO<sub>4</sub>, at room temperature, to determine the effect of the degree bleach on the synthesis and monitoring of the degradation of Iron (VI) over time.</p></sec><sec id="s2"><title>2. Material and Method</title><p>First, the hydrated iron sulfate FeSO<sub>4</sub>, 7H<sub>2</sub>O and ClO<sup>−</sup> bleach (50˚F) are mixed in a NaOH alkaline medium. The mixture is stirred for one hour at a temperature of 55˚C until the mixture becomes red purple characterizing the presence of iron (VI).</p><p>Recovering Na<sub>2</sub>FeO<sub>4</sub> is performed by vacuum filtration in order to dry the product at a temperature of 120˚C for 12 hours. Then, the product is dried in a desiccator for at least one hour before grinding to prevent moisture problem [<xref ref-type="bibr" rid="scirp.55858-ref12">12</xref>] .</p><p>The obtained final product is analyzed and stored at room temperature in order to monitor its degradation over time.</p><p>The synthesis reaction is as follows:</p><disp-formula id="scirp.55858-formula58"><graphic  xlink:href="http://html.scirp.org/file/1-1510337x5.png"  xlink:type="simple"/></disp-formula></sec><sec id="s3"><title>3. Results</title><p>The results obtained are shown in <xref ref-type="fig" rid="fig1">Figure 1</xref> and <xref ref-type="fig" rid="fig2">Figure 2</xref>. These show that the yield of the oxidation of iron (II) to iron (VI) varies, depending on the degree of ClO<sup>−</sup> bleach and the drying time.</p><p>According to these results (<xref ref-type="fig" rid="fig1">Figure 1</xref> and <xref ref-type="fig" rid="fig2">Figure 2</xref>), we noticed that the increase in the chlorometric degree of ClO<sup>−</sup> bleach water led to higher yields of the reactions but with a maximum at 50˚F, this shows the significant</p><fig id="fig1"  position="float"><label><xref ref-type="fig" rid="fig1">Figure 1</xref></label><caption><title> iron oxidation yield (II) to iron (VI) according to the degree of ClO<sup>−</sup> bleach to a drying time of 12 hours and at a temperature of 120˚C</title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/1-1510337x6.png"/></fig><p>effect of the degree of bleach water on the oxidation of iron (II) to iron (VI). The optimal drying time to achieve a yield of 70% iron (VI) is stable at ambient for 12 hours.</p></sec><sec id="s4"><title>4. Characterization</title><sec id="s4_1"><title>4.1. Infrared Spectroscopy</title><p>The appearance of an infrared spectrum is related to the symmetry of the molecule or group studied. It is expected to <inline-formula><inline-graphic xlink:href="http://html.scirp.org/file/1-1510337x7.png" xlink:type="simple"/></inline-formula> tetrahedral structure to find:</p><p>Fundamental characteristic bands of symmetry τd: either υ<sub>3</sub>, υ<sub>4</sub> bands and from the two degenerate modes of vibration: the symmetrical angular elongations and deformations within the tetrahedron resulting in inactive modes in infrared absorption, bands and the υ<sub>1</sub>, υ<sub>2</sub> must be absent from the spectra [<xref ref-type="bibr" rid="scirp.55858-ref19">19</xref>] . Similarity between infrared spectrum isomorphic series [<xref ref-type="bibr" rid="scirp.55858-ref20">20</xref>] .</p><p>The presence of the υ<sub>1</sub> band and a triplet for υ<sub>3</sub> (elongation of the tetrahedron) led Griffith (1966) to consider a lower symmetry τd, very close to τ<sub>S</sub> for <inline-formula><inline-graphic xlink:href="http://html.scirp.org/file/1-1510337x8.png" xlink:type="simple"/></inline-formula> anion [<xref ref-type="bibr" rid="scirp.55858-ref21">21</xref>] . IR spectroscopy is a quantitative method for the determination of Iron (VI) compounds in ferrates. The shape of the spectra is due to the symmetry of the molecule or <inline-formula><inline-graphic xlink:href="http://html.scirp.org/file/1-1510337x9.png" xlink:type="simple"/></inline-formula> groups (tetrahedral structure). The IR spectrum of the obtained Na<sub>2</sub>FeO<sub>4</sub> (user 820 and 770 cm<sup>−</sup><sup>1</sup>) (<xref ref-type="fig" rid="fig3">Figure 3</xref>) showed an identical appearance to that obtained in the high frequency domain [<xref ref-type="bibr" rid="scirp.55858-ref22">22</xref>] .</p><p>Comparing the outgoing strip 820 cm<sup>−</sup><sup>1</sup> and 770 cm<sup>−</sup><sup>1</sup> IR spectrum (<xref ref-type="fig" rid="fig3">Figure 3</xref>) of the phase with that of Na<sub>2</sub>FeO<sub>4</sub>, Weichun et al. [<xref ref-type="bibr" rid="scirp.55858-ref5">5</xref>] observed a similarity of these spectra with light bands of travel Na<sub>2</sub>FeO<sub>4</sub> which may be due to the conditions of preparation and crystallization.</p><fig id="fig2"  position="float"><label><xref ref-type="fig" rid="fig2">Figure 2</xref></label><caption><title> iron oxidation yield (II) to iron (VI) according to the product of the drying time at a temperature of 120˚C and the degree of ClO<sup>−</sup> bleach 50˚F</title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/1-1510337x10.png"/></fig><fig id="fig3"  position="float"><label><xref ref-type="fig" rid="fig3">Figure 3</xref></label><caption><title> Spectrum infra-red prepared Na<sub>2</sub>FeO<sub>4</sub></title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/1-1510337x11.png"/></fig><p>The bands 1140 cm<sup>−</sup><sup>1</sup> and 620 cm<sup>−</sup><sup>1</sup> are characteristic of <inline-formula><inline-graphic xlink:href="http://html.scirp.org/file/1-1510337x12.png" xlink:type="simple"/></inline-formula> group, while those at 950 cm<sup>−</sup><sup>1</sup>, 930 cm<sup>−</sup><sup>1</sup> and 860 cm<sup>−1</sup> can be assigned to an intermediate compound between Na<sub>2</sub>SO<sub>4</sub> and Na<sub>2</sub>FeO<sub>4</sub> form of a solid solution of the formula Na<sub>2</sub>Fe<sub>x</sub>S<sub>1</sub><sub>−</sub><sub>x</sub>O<sub>4</sub>: sulfate-ferrate [<xref ref-type="bibr" rid="scirp.55858-ref23">23</xref>] .</p></sec><sec id="s4_2"><title>4.2. X-Ray Diffraction</title><p>The XRD spectrum obtained for Na<sub>2</sub>FeO<sub>4</sub> powdered compound (<xref ref-type="fig" rid="fig4">Figure 4</xref>) to verify the crystal structure of this phase [<xref ref-type="bibr" rid="scirp.55858-ref24">24</xref>] [<xref ref-type="bibr" rid="scirp.55858-ref25">25</xref>] and demonstrate the existence of an isomorphism with K<sub>2</sub>FeO<sub>4</sub> and BaFeO<sub>4</sub> found by Licht et al. [<xref ref-type="bibr" rid="scirp.55858-ref3">3</xref>] . Dropoff window Diffraction RX is one of the means used to verify the presence of ferrate (VI).</p><p>Na<sub>2</sub>FeO<sub>4</sub> the spectrum obtained shows similarity with that of isomorphous compounds including K<sub>2</sub>FeO<sub>4</sub> [<xref ref-type="bibr" rid="scirp.55858-ref8">8</xref>] .</p><p>There is a duplication of lines corresponding to the planes (102), (202), (013), (200), (002), (004,) (105), (226), (114), (205), (412), (006), (026), (008), (301) [<xref ref-type="bibr" rid="scirp.55858-ref3">3</xref>] [<xref ref-type="bibr" rid="scirp.55858-ref5">5</xref>] [<xref ref-type="bibr" rid="scirp.55858-ref6">6</xref>] [<xref ref-type="bibr" rid="scirp.55858-ref8">8</xref>] [<xref ref-type="bibr" rid="scirp.55858-ref26">26</xref>] - [<xref ref-type="bibr" rid="scirp.55858-ref29">29</xref>] .</p><p>We note the existence of the lines in the X-ray diffractogram of Na<sub>2</sub>FeO<sub>4</sub> not observed in that of K<sub>2</sub>FeO<sub>4</sub>. These lines can be assigned to an intermediate between Na<sub>2</sub>FeO<sub>4</sub> and Na<sub>2</sub>SO<sub>4</sub> formula Na<sub>2</sub>Fe<sub>x</sub>S<sub>1</sub><sub>−</sub><sub>x</sub>O<sub>4</sub> and the most intense peak at 2θ = 27˚ (<xref ref-type="fig" rid="fig4">Figure 4</xref>), corresponds to the XRD spectrum of Na<sub>2</sub>SO<sub>4</sub>.</p></sec></sec><sec id="s5"><title>5. Monitoring the Degradation of the Ferrate over Time</title><p>Spectrophotometry is a quantitative analytical method of measuring the absorbance or optical density of a given chemical substance, generally in solution. The more concentrated the sample is, the more it absorbs light in the proportionality limits set by the Beer-Lambert law.</p><disp-formula id="scirp.55858-formula59"><graphic  xlink:href="http://html.scirp.org/file/1-1510337x13.png"  xlink:type="simple"/></disp-formula><p>The optical density of samples was determined by a spectrophotometer previously calibrated on the absorption wavelength of the test substance.</p><p>According to Sapin et al. [<xref ref-type="bibr" rid="scirp.55858-ref28">28</xref>] , measuring the optical density of the solution of ferrate (VI) is at a wavelength of 507 nm with a pH greater than 10.</p><p>The iron of the characteristic peak (VI) exits this wavelength.</p><p>The results of calculating the rate of degradation between the month and the state of the production ferrate VI and the different months of storage from the measured optical density is given by the following table.</p><p>The relation used to calculate the percentage of degradation of Iron (VI) is given by the following formula:</p><disp-formula id="scirp.55858-formula60"><graphic  xlink:href="http://html.scirp.org/file/1-1510337x14.png"  xlink:type="simple"/></disp-formula><p>D.O<sub>i</sub>: Optical densities of the iron (VI) respectively in the initial state;</p><p>D.O<sub>f</sub>: Optical densities of iron (VI) in the final state.</p><fig id="fig4"  position="float"><label><xref ref-type="fig" rid="fig4">Figure 4</xref></label><caption><title> RX diffractogram prepared Na<sub>2</sub>FeO<sub>4</sub></title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/1-1510337x15.png"/></fig><table-wrap id="table1" ><label><xref ref-type="table" rid="table1">Table 1</xref></label><caption><title> Optical density of the solution of ferrate (VI) Phase Na<sub>2</sub>FeO<sub>4</sub> synthesized according to the degradation rate between the initial state of the production and storage of ferrate VI during different months (%) and based on the degradation rates between months storage of ferrate VI (%)</title></caption><table><tbody><thead><tr><th align="center" valign="middle" >t (months)</th><th align="center" valign="middle" >The rate of deterioration from baseline in the production and storage of different month ferrate VI (%)</th><th align="center" valign="middle" >The monthly rate of degradation ferrate VI (%)</th></tr></thead><tr><td align="center" valign="middle" >1</td><td align="center" valign="middle" >0.7</td><td align="center" valign="middle" >0.7</td></tr><tr><td align="center" valign="middle" >2</td><td align="center" valign="middle" >1.7</td><td align="center" valign="middle" >1.07</td></tr><tr><td align="center" valign="middle" >3</td><td align="center" valign="middle" >3.57</td><td align="center" valign="middle" >1.81</td></tr><tr><td align="center" valign="middle" >4</td><td align="center" valign="middle" >6.42</td><td align="center" valign="middle" >2.96</td></tr><tr><td align="center" valign="middle" >5</td><td align="center" valign="middle" >7.5</td><td align="center" valign="middle" >1.14</td></tr><tr><td align="center" valign="middle" >6</td><td align="center" valign="middle" >9.64</td><td align="center" valign="middle" >2.31</td></tr><tr><td align="center" valign="middle" >7</td><td align="center" valign="middle" >29.28</td><td align="center" valign="middle" >2.17</td></tr><tr><td align="center" valign="middle" >8</td><td align="center" valign="middle" >36.78</td><td align="center" valign="middle" >10.60</td></tr><tr><td align="center" valign="middle" >9</td><td align="center" valign="middle" >38.21</td><td align="center" valign="middle" >2.25</td></tr><tr><td align="center" valign="middle" >10</td><td align="center" valign="middle" >62.5</td><td align="center" valign="middle" >3.93</td></tr><tr><td align="center" valign="middle" >11</td><td align="center" valign="middle" >73.21</td><td align="center" valign="middle" >28.57</td></tr><tr><td align="center" valign="middle" >12</td><td align="center" valign="middle" >81.42</td><td align="center" valign="middle" >30.66</td></tr></tbody></table></table-wrap><p>According to our results (<xref ref-type="table" rid="table1">Table 1</xref>), the synthesized iron (VI) may be ambient stable during up to 12 months of storage at room temperature, and the iron degradation rate (VI) in the first six months does not exceed 9.64%.</p><p>Note that the rate of degradation of iron (VI) remains variable in function of time and varies differently from one month to the other during storage. Climate change plays a very important role in the degradation rate of ferrate (VI) due to changes in humidity.</p></sec><sec id="s6"><title>6. Discussion</title><p>The optimal degree of ClO<sup>−</sup> bleach or hypochlorite used for the synthesis of ambient stable Na<sub>2</sub>FeO<sub>4</sub> is of the order of 50˚F. This rate plays an important role in iron (VI) synthesis yield.</p><p>This is comparable to the studies already made by Hrostowski and Scott [<xref ref-type="bibr" rid="scirp.55858-ref18">18</xref>] Thus, to obtain a strong and stable product requires a drying time of about 12 hours at a temperature of 120˚C [<xref ref-type="bibr" rid="scirp.55858-ref12">12</xref>] [<xref ref-type="bibr" rid="scirp.55858-ref18">18</xref>] .</p><p>According to the results, we found out that the duration of 12 months of storage is an important progress in the field of synthetic ambient stable iron (VI) to meet the growing global demand for it to get an industrial plant for the manufacture of this superoxydant and disinfectant [<xref ref-type="bibr" rid="scirp.55858-ref29">29</xref>] .</p></sec><sec id="s7"><title>7. Conclusions</title><p>This manuscript reviews the effect of the degree of bleach water (ClO<sup>−</sup> hypochlorite) on the yield of the synthesis of iron (VI) and its stability over time. This level is of the order of 50˚F with a drying time of 12 hours at a temperature of 120˚C.</p><p>Comparing stable Na<sub>2</sub>FeO<sub>4</sub> synthesis results with the bibliography, we note that we have obtained for the first time wet ambient stable ferrates VI with quite a yield of 70% for a period of 12 months. This result represents a significant advance in the field of synthetic iron (VI) at a laboratory scale. This result is very encouraging for mass production of ferrate (VI) on an industrial scale.</p></sec></body><back><ref-list><title>References</title><ref id="scirp.55858-ref1"><label>1</label><mixed-citation publication-type="other" xlink:type="simple">Hoy, G. and Corson, M. (1980) Critical Slowing Down of Spin Fluctuations in K2FeO4. Journal of Magnetism and Magnetic Materials, 15, 627.</mixed-citation></ref><ref id="scirp.55858-ref2"><label>2</label><mixed-citation publication-type="other" xlink:type="simple">Menil, F. 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