Formate ion decomposition in water under UV irradiation at 253.7 nm.
Formate ion (HCO2-) occurs in natural waters as a result of photooxidation of humic substances. Under UV irradiation, as applied in water purification (253.7 nm), formate ion decomposed following split-rate pseudo-zero-order kinetics (k1 and k2 are initial and final rate constants, respectively). In the presence of dissolved oxygen (DO), it was found that (a) k1 < k2, (b) k1 and k2 increased with initial formate ion concentration ([HCO2-]0 = (1.73-38.3) x 10(-5) mol L(-1)) and absorbed UV intensity (Ia = (1.38-3.99) x 10(-6) mol quanta L(-1) s(-1)), and (c) k1 and k2 were relatively insensitive to initial pH (pHo = 5.41-8.97) in buffer-free solutions. Both rate constants decreased with increasing carbonate alkalinity ((0-1.0) x 10(-3) mol L(-1)) and k1 was virtually unchanged in phosphate buffer at pH0 between 5.25 and 9.92. Carbonate buffer lowered the rate of formate ion decay, possibly due to scavenging of OH* radicals. Initial rate constant k1 slightly increased with temperature (15-35 degrees C), while k2 remained unchanged. The reaction pH increased rapidly during irradiation of buffer-free NaHCO2 solution to approach an equilibrium level as [HCO2-] reached the method detection level (MDL). The pH profile of buffer-free formate ion decay was estimated using closed-system equilibrium analysis. DO utilization during UV irradiation was 0.5 mol of O2/mol of HCO2-, while nonpurgeable organic carbon (NPOC) measurements on kinetic samples closely followed the HCO2- profile, thus strongly suggesting the transformation of HCO2- -C to CO2 in the presence of DO. In DO-free water, k1 > k2 was observed. Furthermore, k(1,DO FREE) > k(1,DO) (k(1,DO) = k1) and k(2,DO FREE) < k(2,DO) (k(2,DO) = k2). The effect of dual acid solutions on HCO2- decay was examined in a mixture of NaHCO2 and sodium oxalate (Na2C2O4). HCO2- decomposed readily until [HCO2-] approximately equal to MDL but at a lower rate than in buffer-free HCO2- solutions, while C2O4(2-) remained virtually unchanged. C2O4(2-) decay commenced following near complete conversion of HCO2-.
Department of Civil Engineering, City College of New York, and the Graduate Center of the City University of New York, Convent Avenue at 138th Street, New York, New York 10031, USA.
Gonca F
GF
Talu
Vasil
V
Diyamandoglu
D005561:Formates / Q000032:analysis* / Q000528:radiation effects*; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D008956:Models, Chemical; D010070:Oxalates / Q000032:analysis / Q000528:radiation effects; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D010777:Photochemistry; D014466:Ultraviolet Rays
D005561:Formates; D010070:Oxalates; D010100:Oxygen