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Chemical Equilibria and Rates of Manganese 'Oxidation R-I JOHN D

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Chemical Equilibria and Rates of Manganese 'Oxidation R-I JOHN D Chemical Equilibria and Rates of Manganese 'Oxidation r-i JOHN D. HEM CHEMISTRY OF MANGANESE IN NATURAL WATER GEOLOGICAL SURVEY WATER-SUPPLY PAPER 1667-A UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON : 1963 UNITED STATES DEPARTMENT OF THE INTERIOR STEWART L. UDALL, Secretary GEOLOGICAL SURVEY Thomas B. Nolan, Director CONTENTS [The letters in parentheses designate separately published chapters] (A) Chemical equilibria and rates of manganese oxidation, by John D. Hem. (B) Deposition and solution of manganese oxides, by John D. Hem. (C) Intracellular and extracellular concentration of manganese and oil <?r ele­ ments by aquatic organisms, by Eugene T. Oborn. (D) Reduction and complexing of manganese by gallic acids, by John D. Hem. o UNITED STATES DEPARTMENT OF THE INTERIOR STEWART L. UDALL, Secretary GEOLOGICAL SURVEY Thomas B. Nolan, Director For sale by the Superintendent of Documents, U.S. Government I-intlng Office Washington 25, D.C. CONTENTS Page Abstract-_______________________________________________________ Al Aims and organization of study____.________________________________ 1 Occurrence and chemical properties of manganese____________________ 2 Nature and significance of stability-field diagrams-____________________ 3 Chemical-equilibrium computations._____________________________ 5 Location of stability boundaries-________________________________ 10 Laboratory studies of manganese-oxidation equilibria-_________________ 14 Composition of precipitated oxides_____________________________ 16 Manganese equilibria involving bicarbonate___________________________ 19 Fixed bicarbonate activity_--____-___-_-_-_---_-_-______________ 19 Fixed carbon dioxide partial pressure___________________________ 23 Laboratory studies___________________________________________ 25 Manganese equilibria involving sulfate_______________________________ 26 Laboratory studies___________________________________________ 29 Soluble manganese complexes-- _____________________________________ 30 Manganese bicarbonate complex_______________________________ 31 Laboratory studies_________________________________________ 31 Determination of equilibrium constant-__________________ 35 Calculation of free energy of the complex_________________ 38 Effect of the complex on manganese equilibria_______________ 38 Stability field of bicarbonate complex.___________________ 39 Manganese sulfate ion pair_____________________________________ 43 Comparison of strength of complexes____________________________ 43 Combined effects of bicarbonate and sulfate complexes on manganepe equilibria. _ _________________________________________________ 46 Other inorganic complexes______________________________________ 49 Organic complexes____________________________________________ 51 Rates of chemical reaction..,_______________________________________ 52 Kinetics of mangan ese oxidation and precipitation _________________ 53 Effect of sulfate____________________________ 54 Effect of bicarbonate_____________________________________ 56 Factors that may increase reaction rate______________________ 57 Summary__ _____________________________________________ 59 Coprecipitation of manganese with ferric hydroxie_____________________ 59 Coprecipitation of manganese and other elements_____________________ 61 General conclusions._______________________________________________ 62 Literature cited-__________________________________________________ 62 in IV CONTENTS ILLUSTRATIONS Page FIGURES 1-6. Stability fields of manganese species: 1. In the absence of bicarbonate and sulf ate _________ A9 2. In presence of 100 ppm HCOa~ and natural rhodo- chrosite_ __________________________________ 20 3. In presence of 100 ppm HCOa~ and precipitated MnCO3-_-_-_____----_-____________-_- ______ 22 4. At a partial pressure of COz^3.8X10~* atmosphere. 24 5. In presence of 10 ppm HCO3~ and 1,000 ppm SO4-2_ 28 6. In presence of 2,000 ppm HCO3-________________ 40 7. Proportions of manganese complexed at various bi­ carbonate and sulfate activities ________________ 44 8. Stability fields of manganese species in presence of 2,000 ppm HCO3- and 2,000 ppm S04-2_______ 47 9. Rate of consumption of OH~ during manganese oxi­ dation at different pH levels___________-_____-_ 55 10. Rate of oxidation of manganese as affected by pH and sulfate_-_______-________________________ 56 11. Rate of oxidation of manganese as affected by pH and bicarbonate..___________________________ 58 TABLES Page TABLE 1. Free energy of formation (25°C) of crystalline, liquid, and dissolved substances considered in stability-field diagrams. A7 2. Equilibrium constants utilized in constructing stability-field diagrams-___________________________________________ 8 3. Oxidation of dissolved Mn+2_________________ 16 4. Experimental data on manganese bicarbonate con?plex______ 37 5. Coprecipitation of manganese with ferric hydroxi<?e________ 60 CHEMISTRY OF MANGANESE IN NATURAL WATER CHEMICAL EQUILIBRIA AND RATES OF MANGANESE OXIDATION By JOHN D. HEM ABSTRACT The relationships between manganese in solution, Eh, pH, and the actrdties of bicarbonate and sulfate ions are shown by means of seven stability-field diagrams. The behavior of manganese in laboratory experiments is in general agreement with predictions of the diagrams. In distilled water, with an Eh near 0.55 volts and a pH of 7.0, manganese has a solubility of about 1.0 ppm (parts per million). An increase in pH or in Eh tends to lower the solubility. Bicarbonate species in equilibrium with manganese carbonate may control manganese solubility in some systems. Increased bicarbonate activity decreases manganese solubility. Relationships between manganese and sulfate activities are related to solution of manganese sulfide with oxidation of the sulfur. Manganese forms soluble complexes with bicarbonate and sulfate. The association constant for MnHCOs+ ion was determined to be 63. The solubility of manganese in natural water, especially that which contains large amounts of bicarbonate or sulfate, is influenced by complexing. In a solution where the total dissolved manganese is 1.0 ppm, the activity of sulfate is 250 ppro, and bicarbon­ ate activity is 470 ppm, half the manganese present will be in the complexes. The rate at which divalent manganese is oxidized and precipitated from aerated solutions is sharply increased by increasing the pH. The rate is dirrinished when sulfate and bicarbonate ions are present. Experimental data suggest that the reaction may be first order with respect to manganese concentration initially, but the rate increases as the reaction proceeds, probably because of autocr.talysis. Manganese coprecipitates with ferric hydroxide when the pH is greater than 6.7. AIMS AND ORGANIZATION OF STUDY Although manganese is a minor constituent of natural water, even small concentrations of the element constitute an undesirable impurity in water to be used for domestic and for many industrial purposes. The U.S. Geological Survey is conducting research in the chemical behavior of manganese and other hydrosolic metals. These elements are readily soluble under some of the chemical conditions common to natural water, but under some others, also common to natural water, they form oxides and hydroxides of very low solubility. Al A2 CHEMISTRY OF MANGANESE IN NATURAL WATER The research work includes systematic description and evaluation of the factors affecting solubility of manganese under conditions of chemical equilibrium and study of some factors affecting reaction rates. The effects of macrobiota and microbiota are also considered, together with factors more directly related to inorganic chemical behavior. This report is the first of a series describing the results of research on the chemistry of manganese. The research work described in this report was done in laboratories of the U.S. Geological Survey in Denver, Colo. The author was as­ sisted in the laboratory work by M. J. Fishman. Helpful suggestions in the course of the study and in review of the manuscript were furnished by colleagues of the author in the Geological Survey and by Professor R. M. Garrels, Department of Geological Sciences, Harvard University. OCCURRENCE AND CHEMICAL PROPEPTIE8 OF MANGANESE The element manganese is number 25 in the periodic table. It is classified as a transition element and displays some chemical char­ acteristics, such as multiple valency, that are typical of that group of elements. Only one isotope of the element, Mn55, exists naturally, although nuclides of higher and lower mass number, all radioactive, have been produced artificially. Manganese is located adjacent to iron in the periodic table, and the two elements have some chemical resemblances. The two elements are often considered together, par­ ticularly in the technology of water supply and treatment, because they cause similar problems and both may need to be removed. Be­ cause the chemistry of manganese is different from that of iron in several important respects, manganese is much more difficult to remove from water than iron. It is generally agreed that the amount of manganese present in the rocks of the earth's crust averages about 0.10 percent. This contrasts with a concentration of nearly 5.0 percent for iron. T' x us, the abun­ dance data suggest that manganese should be much less common in solution in natural water than is iron, and, in general, tHs expectation is realized. In many places the rarity or absence of manganese- containing minerals may prevent saturation of the natural water. In such places the solubility
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