Indian Journal of Chemistry Vol. 38A. September 1999, pp.966-968 The reaction of barium manganate with acids and their precursors Liszlo Kotai, Agnes Keszler, Janos Pato . Sandor Holly Chemical Research Cente r, Institute of Chemistry. Hungarian Acad emy of Sciences H-1025, Budapest, Pusztase ri u. 59-67, Hunga ry and Kalyan K Banerji ' Department of Chemistry, J N V Universi ty, Jodhpur 342 005, India Received 30 November 1998; revised 4 Mal' 1999 A simpl e and easy preparative route to obtain permangani c ac id and perma nga nate salts from barium manganate and sulphuric ac id is described. Sulphuri c ac id reacts with bari um manganate to produce sparingly soluble bariulll sulphate and well-soluble permanganic ac id or bari ulll permanganate, these in turn can be usee! to prepare ot her metal perm anga nates. Perman ga nates are wide ly used in organic sy ntheses as se lective oxidizing agentsl . Barium permanganate is su itable for selective o xid at ion itsclf2-6 and can be used as starting materi a l for the synthesis of seve ral other metal pe rmanganates als0 7.X• The reaction o f permallganic aci d with oxides, hydroxides or carbonate' yields a lot of cIeri vati ves') . Synthesis of barium pennanganate starts from bari um man ganate which itse lf is o btain ed in pure form from potassi um perman ganate and water soluble barium salts . Reported meth ods for the conversion of barium man ganate to the corresponding permanganare are comp l icated procedures. In thi s note, the synthesi s of permanganic acid and barium permanganate and their use in the synthes is of several other metal permanganates are reported . Experimental Analytical grade reagents (A ldrich) and double-distilled water were used throughout. The IR spectra were obtained in nujolmull with NICOLET 205 FT-IR spectrometer and by diffu se reflectance tec hni que in KBr with NICOLET 170SX spectrometer in the range of 400-4000 c m· l. rcp measurements we re made with Atomscan 25 (Thermo Jarral Ash) spectrome ter. X-ray powder dif- fraction data were collected on a Phillips PW 3710 diffractometer, with a Cu monochromator. Synthesis oj barium manganate (VI) KMn04 (15.8 g) was dissolved in 300 ml of water, then BaCI 2 .2Hp (24.9 g dissolved in 100 ml of wate r), KOH (56 g dissolved in 100 ml of water) and KI (2.0 g di sso lved in 20 ml of water) were added with vigorous stirring. The mixture was boiled for 15 min, cooled, filtered, and washed. The permanganate-free product was dried at 105° C for I h, then the traces of water were removed by azeotropic distillati on with benzene (yield - 100%). Analysis (found/calc. fo r BaMn0 4 ): Ba 53.69/ 53 .59%; Mn 21.40121.44 %. Synthesis ojperman ganic acid To barium manganate (2.56 g, 0 .0 I mol ) suspended in 50 ml of di stilled water, su lphuric acid ( 100 ml , 0 . 1 mol) was added with stirring. The stirrin g was continued for I h. Th e reaction mixture was filte red and perman ganic ac id was titrated with NaOH potenti ometrically usin g a g lass e lectrode (PH 5.5 ). Th e product, sodium permanganate trihydrate, was crystall ized and identifi ed by IR spectroscopy; yie ld - 100%. SYllthesis of barium permangana te Bariu m man ganate (2. 56 g, 0.01 mol ) was suspended in 100 ml of di still ed water. Then sulphuric acid (55 ml , 0 . 1 mol ) was added over I h with slow stirring and then refluxed for 15 min. The reaction mixtu re was filte red and concentrated while barium perman ganate c rysta llized (yi e ld: 0.7 g), analysi s [found/calc. for Ba(Mn04)2]: Ba 36.57/36.6 1% ; Mn 29.30129 .28 % . Reaction of barium l1Iangana fe with sodium hydrogen carbonate Barium manganate (2.56 g, 0.0 I mol) was suspended in 100 ml distilled water and calcul ated amounts of NaHC01 (Ba:Na = I :0.75, I: I , I: 1.34 mol) was added . The mixture was slowly stirred for I h a nd then refluxed for 30 min . The reaction mixture was filtered and crysta lli zed. According to TR spectroscopy a nd X-ray diffractometry, th e prod uct s con tai ned Ba(Mn0 4)2' NaMn04 and Na 2CO, in di fferent ratios. NOTES Reaction of barium manganate with ammonium sulphate To barium manganate (2.56 g, 0.01 mol), suspended in 100 mol distilled water, was added ammonium su lphate (1.24 g, 0.0 I mol). The reaction mixture was stirred for I h and then refluxed for I h. The mixture turned dark violet and intense odor of ammonia was obtained . The reaction mixture was filtered , concentrated and crystallized. According to IR spectroscopy the water-soluble product was ammonium permanganate. Even if 2/3 amount of ammonium su lphate used, the on ly product formed, under simi lar conditions, was ammonium permanganate. Results and discussion Synthesis of barium manganate in alkalin e medium from potassium permanganate and barium chloride in the presence of an alkali iodide is a well-known reaction (I) . It results in the fornlation of insoluble barium manganate, which can be obtained in dry form after azeotropic distillation of water with benzene. 6 KMnO, + 6BaCI 2 + 6 KOH + KI ~ BaMn04 + 12 KCI + KIO, + 3 Hp .. ..( 1) Unstable manganic acid is formed when barium manganate is treated with sulphuri c or carbonic acid (2) . It disproportionates to permanganic ac id and mangan ese dioxide (3) . ... (2) where X = S04 or CO, .. . (3) 967 Table 1- Comparison of effecti ve charge values and acidity of some inorganic oxoacids '4 8,,1 Oxoacid 811 HlS04 +0.38 HMn04 HlMnO.j· +0.37 +0.37 HlCO J +0.39 8,/ 8x -0.46 -0.36 +0.88 1.125 -0.53 -0.46 +1 .56 1.114 -0.52 -0.42 +1.42 1.106 -0.50 -0.42 +0.67 0.965 <jl • Our calculation sulphuric acid. The ionic character of the hydroxy Is (8i8o) are nearly similar in manganic and permanganic acids but the polarizing effect of the central atom is higher in permanganic acid . Consequently manganic ac id is easily formed from barium manganate and sulphuric acid due to the hi'gh acidity of su lphuric acid as well as the insolubility of barium su lph ate. Carbonic acid being weaker than manganic acid, the main driving force of the reaction is the formation of insoluble barium carbonate. However, it is an equilibrium process and dissolution of barium carbonate in manganic acid takes place. Manganic acid disproportionates to permanganic acid and manganese dioxide (3). This reaction (log K = 58) takes place comp lete ly in acidic, neutral or slightly alkaline media" . Due to these facts permanganic acid is formed quickly from barium manganate and SUlphuric acid via disproportionation of manganic acid (5). Thus this method is suitable for the preparation of permanganic acid . 3 BaMn04 + 3 H2S04 ~ 2 HMn04 + 3 BaS04 + Mn02 + 2 Hp .. . (5) . Dissociation constant of manganic acid has not been determi ned so far. In order to explain the mechani sm of these reactions, the relative strengths of the acids mu st be known. To estimate them , a method published earli er has been used l4 . Effective charges of the atoms of manganic acid and <p constants which characterize the acid strength IS were calculated using relation (4) . .. . (4) where <p means the acid strength, 8H' 80 and 8x mean the relative charges of the H,O, and X(S,C or Mn) atoms respectively. The results are presented in Table I . The data showed that manganic acid is a stronger acid than carbonic acid but is weaker than permanganic or Permanganic acid being a relatively strong acid re·acts easily with metal oxides, hydroxides or carbonates. This method can be used to synthesize any permanganate. T he analogous reaction between barium manganate, water and carbon dioxide yield on ly very small amount of manganic acid as expected from the relative strength of the acids. Consequently longer time is required to obtain a sign ificant amount of permanganic acid. Barium carbonate is soluble in permanganic acid (latter be ing a stronger acid) and this reaction has been reported as a method of preparation of barium permanganate lO. 12 but this method is less favourable than the new meth od reported here. 968 INDIAN J CHEM, SEC. A , SEPTEMBER 1999 To understand the reaction of barium manganate with carbonic acid (2), it was considered essential to study its reaction with sodium hydrogencarbonate. NaHCO, generates carbonic acid in boiling solutions which can form barium permanganate as per reaction (2) ... (6) While NaHCO, is a source of carbonic acid at slightly alkaline pH, ammonium sulphate behaves as a slightly acidic sulphuric acid precursor (8). .. . (8) The reaction of sulphuric acid and BaMn04 results in the formation of permanganic acid. The e nd product of the reaction of permanganic acid and ammonium hyd roxide is ammonium permanganate. Equiv a lent amounts of ammonium s ulphate and barium manganate yield 2/3 mol ammonium permanganate while ammonia is evolved. Using 2/3 mol of ammonium sulphate, the ex pected product is barium permanganate (in analogy with sulphuric aci d) but in practi ce ammonium permanganate was the product. P ro bably, manganic ac id reacts rapidly w ith am moni a before anything e lse ca n happe n. Alternative ly, a mm onium manganate mi ght be formed as an intermedi ate foll owed by its disproportionati on. Sodium carbonate can be detected by IR spectroscopy. The reaction of barium permanganate and sodium carbonate yields barium carbonate and sodium permanganate trihydrate. When the mo lar ratio of the reactants is I : I , the main product is barium permanganate and a small amount of sodium permanganate trihydrate is formed. Similar results are obtained when an excess of barium manganate is used. However, an excess of NaHCn, ( I: 1.34) enhances the reaction bet ween barium permanganate and sodium hydroge ncarbonate and th e main product is sodium permanganate trihydrate while barium permanganate is the min or by-p roduct. Since permanganic acid is stronger acid than man ganic ac id , in the presence of less than one equiva lent of sulp huri c acid , permanganic ac id form ed reacts with barium man ganate to produce barium permallganate and man gani c acid. The latte r disproportionates to manganese dioxide and permanga nic ac id . Barium perma nganate is formed [reaction (7)] in the presence of2/3 equivalent of sul phuri c acid. Therefore, pure barium pe rmanga nate can be obtained by treatin g sul phuric acid with an excess of barium manganate . Unreacted barium l11anganate can be easily removed by fi ltration . 4 . .. (7) 5 6 7 Due to extr~ln~ insolubility of barium sul phate when bariu m permanganate reac ts with metal sul pha te:-. , th e exchange reac ti on result s in th e formati on of metal permanganates. The so lubility produ ct or some of the hi ghl y insolubl e sulph ates is: BaSnl' 1.07 x 10-1°; Pb50. 1.82 " x IO-~ ; Sr504 , 3.44 x 10-7 ; Ag}S04' 1.20 x 10 ' and CaSn , l 5 6. 10 x 10- . It can be see n that even lead sulph ate is almost 100 times more soluble than barium sulphate. Consequently, the exchange reacti on in each case is practicall y complete. .. (9) 3 (NH)!MnO. --7 2 N H. MnO. + 2 Hp + M n02 + 4 NI-! , ... ( 10) References I 2 3 8 9 10 II 12 13 !4 15 Fatiadi J. Sm thesis. (19R7) 85. 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