Bulk chlorine uptake by polyamide active layers of thin-film composite membranes upon exposure to free chlorine-kinetics, mechanisms, and modeling

Environ Sci Technol. 2014;48(5):2741-9. doi: 10.1021/es4047632. Epub 2014 Feb 19.

Abstract

We studied the volume-averaged chlorine (Cl) uptake into the bulk region of the aromatic polyamide active layer of a reverse osmosis membrane upon exposure to free chlorine. Volume-averaged measurements were obtained using Rutherford backscattering spectrometry with samples prepared at a range of free chlorine concentrations, exposure times, and mixing, rinsing, and pH conditions. Our volume-averaged measurements complement previous studies that have quantified Cl uptake at the active layer surface (top ≈ 7 nm) and advance the mechanistic understanding of Cl uptake by aromatic polyamide active layers. Our results show that surface Cl uptake is representative of and underestimates volume-averaged Cl uptake under acidic conditions and alkaline conditions, respectively. Our results also support that (i) under acidic conditions, N-chlorination followed by Orton rearrangement is the dominant Cl uptake mechanism with N-chlorination as the rate-limiting step; (ii) under alkaline conditions, N-chlorination and dechlorination of N-chlorinated amide links by hydroxyl ion are the two dominant processes; and (iii) under neutral pH conditions, the rates of N-chlorination and Orton rearrangement are comparable. We propose a kinetic model that satisfactorily describes Cl uptake under acidic and alkaline conditions, with the largest discrepancies between model and experiment occurring under alkaline conditions at relatively high chlorine exposures.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Chlorine / chemistry*
  • Filtration / instrumentation
  • Filtration / methods
  • Halogenation
  • Hydrogen-Ion Concentration
  • Kinetics
  • Membranes, Artificial*
  • Models, Theoretical
  • Nylons / chemistry*
  • Osmosis
  • Seawater / chemistry
  • Spectrum Analysis / methods
  • Water Purification / instrumentation

Substances

  • Membranes, Artificial
  • Nylons
  • Chlorine