KMnO4 & Dichromate

41.13 | CHROMATE AND DICHROMATE Preparation 4FeCr,O, + 8Na.CO, +70. es 8Na,CrO, +2Fe,0,7 + 8CO,7 (chromite ore) eR re ae obtained solid alter cooling Discoke in i Titer Filterate ~~ Residue Fe 7 Na.C1O, Lime (CaO) is added with Na,CO, which keeps the mass porous so that air becomes accessible to all parts of reaction mixture and prevents fusion. Then, chromate is converted to dichromate using sulphuric acid, 2Na,CrO, +H,SO, +Na,SO, +Na,Cr,0; +H,0 ‘The solubility of Na,SO, increasesup to 32°C and then decreases, Hence, a suitable temperature is to be employedto crystallize out Na,SO, first. Then Na,Cr,0, iscrystallized outas Na,C1,0, -2H,0 (red crystals) on evaporation. Potassium dichromate is obtained by double decomposition reaction using hot concentrated Na,Cr,O, solution and potassium chloride Na,CnO, + KC] tts + K, 01,0, + 2NaCl K,Cr,0, and NaCl both are water soluble and hence fractional crystallization is carried out.NaCl crys- tallizes out first and is filtered off. Then K,Cr,O, is crystallized out further.Properties The important properties of CxO} and C1,07° such as solubility and chemical reactivity towards different reagents have been discussed in Chapter 7 (Section 7.12). Hexavalent chromium shows similarities in properties with hexavalent sulphur compounds because both the elements have the same number of valence shell electrons. These similar properties are listed as follows, 1, $0, and CrO, are both acidic 2, § forms $0},$,0} and similarly Cr forms Cr0;",C,0;, 3, K,CrO, and K,S0, are isomorphous. 4, $0,C1, 805 and €10,01, “cro5. Tests utilizing the oxidizing property of CrO?/Cr,07- radicals: There are several tests in which the colour of CrO} or Cr,05" is decolorized due to its oxidizing property. Some such tests are: crOy or Cr,0? +80 /s0, $07 + Cr" +H,0 +H,S/s Hs L +Cr* +H,0 + Fe™ sre 4cr + + Br /P 5B, /1, +r" +H,0 + C1 (salt) 5¢,,0,C1, 7 +H,0 +HCl(conc.) > Cl, T+Cr* +H,0 + CH,OH 5 [CH,CHO]-> CH,CO,H+ Cr +H,0 + NO; solutions NO; + Cr +H,0 +H,S0, (conc, 40, 14Cr* +H1,0 +H,80, (conc), Cr0,1 +H,0 dark red crystals11.14 | MANGANATE AND PERMANGANATE Preparation L K amo, 8. vinoe a OPNWOH, Prroltsite jes in presence of air OERNOGUFKEIO, | cole + Green solution water line alla green fymed from ine the reactions ond, +4ROW +O, > 2RMnU, + 2H) MnO, +2KOH+KNO, — K.MnO,+KNO,+4,0 3MnO,+ OKOH + KGIO, > 3K.MnO,+ KCL+ 31,0 K.Mn0, (isomorphous witht K,80,) if kOU or if NaOH A» NayMnO 1O0H,0 (isomorphous with Na.SO-10H,0) This reaction is faster in the presence of KCIO, and KNO, because these on decomposition provide oxygen easily in all parts of the reaction mixture,2, Manganate is also obtained when KMnO, is boiled with conc. KOH. SKMa0, 4KOH ME 4K MnO, +2H,0+0, The above green solution is quite stable in alkali, but decomposes in pure water and in the presence of acids, depositing MnO, and giving a purple solution of permanganate. 3K.Mn0,+2H,0 = 2KMn0,+ MnO, + +4KOH purple dark brown This reaction is also a method of preparation of KMnO,, {n this reaction one-third of Mn is lost as MnO, but when oxidised either by C1, or by O., unwanted MnO, is not formed. 2K,MaO, +Cl, + 2KMn0, +2KC} or 2K,MnO, +0, + H.0-92KMnO, +2KOH40,a Ihismota primary standard Since it is dificult to got it in a high degree of purity and free from traces of MaQ,. b, Tis slowly educed tong, Cepecialy in te presente of light or ai. ANNO +411 4MnO., 42,0410, Oxidizing properties of KMn0, in alkaline medium: The reactions involved are 2Mu0, +201" 2M! 41.040, IMO; +2H,0-+2Mn0, 40H 429 Some examples, a. 2KMnO, +H.0+K} 3 2Mn0, 42KOH+ KIO, ) 2KMn0, +3H1C0.K 2MnO, + KHCO,#2K.C0, +H.0 . IKMnO, +310, + 2KOH+2Mn0, +2H 0430,3, Oxidizing properties of KMnO, in neutral or weak acide mediums The reaction in neutral medium is KMn0, + Mn" +2H,0-5Mn0, +408 For example, 2KMn0, + 3Mas0, +2H,0~ »5MnO, +K$0, +H,80, Zn" or Za) In absence of Zn” ions, some of Mn** ions imay escape oxidation through the formation of insoluble manganous permanganate Mn'[Mn"O,). The reaction in weak acidic medium is 8KMnO, +3Na,8,0, +H,09 8Mn0, +3Na,$0, +3842KOH 4, Heating effect: The effect of heating on KMnO, is discussed in Chapter 7 (Section 7. 13). 2KMaO, 49K, MnO,+Mn0, +0. green black K,MnO, is soluble in water and obtained as green filtrate. MaO, is insoluble in water and obtained as black residue.2. Tests using the oxidizing property of MnO, : There are several tests of MnO, which are not shown by MnO}, because MnO? is stable in solution only above pH = 12. For example, the purple colour of MnO; is discharged by several reducing agents as is evident in the following reactions: MnO; +8" JH,S—#4Mn* +81 +H,0 +$0}'/S0, Mn" +S0} +H,0 + Fe Mn + Fe +H,0 +1 —Loon® +1, +H,0 +NO; 25Mn** +NO; +H,0 +C,07 Mn? +00, 1 +H,0 +P (salt) 5 No reaction +conc, HC] > Ma’ +Cl, +H,0 +H,0, —2Mn™ +0, 1 +H,0

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