Effects of pH and catalyst concentration on photocatalytic oxidation of aqueous ammonia and nitrite in titanium dioxide suspensions

Environ Sci Technol. 2005 May 15;39(10):3784-91. doi: 10.1021/es0485715.

Abstract

Batch experiments were conducted to study the effects of titanium dioxide (TiO2) concentration and pH on the initial rates of photocatalytic oxidation of aqueous ammonium/ ammonia (NH4+/NH3) and nitrite (NO2-) in UV-illuminated TiO2 suspensions. While no simple kinetic model could fit the data at lower TiO2 concentrations, at TiO2 concentrations > or = 1 g/L, the experimental data were consistent with a model assuming consecutive first-order transformation of NH4+/NH3 to NO2- and NO2- to nitrate (NO3-). For TiO2 concentrations > or = 1 g/L, the rate constants for NO2 photocatalytic oxidation to NO3 were far more dependent on TiO2 concentration than were those for NH4+/NH3 oxidation to NO2-, suggesting that, without sufficient TiO2, complete oxidation of NH4+/NH3 to NO3- will not occur. Initial NH4+/NH3 photocatalytic oxidation rates were proportional to the initial concentrations of neutral NH3 and not total NH3(i.e., [NH4+] + [NH3]). Thus, the pH-dependent equilibrium between NH4+ and NH3, and not the pH-dependent electrostatic attraction between NH4+ and the TiO2 surface, is responsible for the increase in rates of NH4+/NH3 photocatalytic oxidation with increasing pH. Electrostatic adsorption, however, can partly explain the pH dependence of the initial rates of NO2- photocatalytic oxidation. Initial rates of NO2- photocatalytic oxidation were 1 order of magnitude higher for NO2- versus NH4+/NH3, indicating thatthe rate of NH4+/NH3 photocatalytic oxidation to NO3- was limited by NH4+/NH3 oxidation to NO2- under our experimental conditions.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Ammonia / chemistry
  • Ammonia / radiation effects*
  • Catalysis
  • Hydrogen-Ion Concentration
  • Nitrites / chemistry
  • Nitrites / radiation effects*
  • Oxidation-Reduction
  • Photolysis
  • Titanium / chemistry*
  • Ultraviolet Rays
  • Water Pollutants, Chemical / radiation effects*
  • Water Pollution / prevention & control
  • Water Purification / methods*

Substances

  • Nitrites
  • Water Pollutants, Chemical
  • titanium dioxide
  • Ammonia
  • Titanium