If you are experiencing problems downloading PDF or HTML fulltext, our helpdesk recommend clearing your browser cache and trying again. If you need help in clearing your cache, please click here . Still need help? Email help@ingentaconnect.com

Monitoring the Speciation of Aqueous Free Chlorine from pH 1 to 12 with Raman Spectroscopy to Determine the Identity of the Potent Low-pH Oxidant

$29.00 plus tax (Refund Policy)

Buy Article:

Abstract:

The speciation of aqueous free chlorine above pH 5 is a well-understood equilibrium of H2O + HOCl OCl + H3O+ with a pKa of 7.5. However, the identity of another very potent oxidant present at low pH (below 5) has been attributed by some researchers to Cl2 (aq) and by others to H2OCl+. We have conducted a series of experiments designed to ascertain which of these two species is correct. First, using Raman spectroscopy, we found that an equilibrium of H2O + H2OCl+ HOCl + H3O+ is unlikely because the "apparent pKa " increases monotonically from 1.25 to 2.11 as the analytical concentration is increased from 6.6 to 26.2 mM. Second, we found that significantly reducing the chloride ion concentration changed the Raman spectrum and also dramatically reduced the oxidation potency of the low-pH solution (as compared to solutions at the same pH that contained equimolar concentrations of Cl and HOCl). The chloride ion concentration was not expected to impact an equilibrium of H2O + H2OCl+ HOCl + H3O+, if it existed. These observations supported the following equilibrium as pH is decreased: Cl2(aq) + 2H2O HOCl + Cl + H3O+. The concentration-based equilibrium constant was estimated to be approximately 2.56 × 10−4 M2 in solutions whose ionic strengths were ∼0.01 M. The oxidative potency of the species in low pH solutions was investigated by monitoring the oxidation of secondary alcohols to ketones. These and other results reported here argue strongly that Cl2 (aq) is the correct form of the potent low-pH oxidant in aqueous free-chlorine solutions.

Keywords: FREE CHLORINE; HYPOCHLOROUS ACID; OXIDATION; RAMAN SPECTROSCOPY; SPECIATION

Document Type: Research Article

DOI: http://dx.doi.org/10.1366/000370206777887062

Affiliations: U.S. Environmental Protection Agency, National Exposure Research Laboratory, 960 College Station Rd., Athens, Georgia 30605

Publication date: July 1, 2006

More about this publication?
Related content

Tools

Favourites

Share Content

Access Key

Free Content
Free content
New Content
New content
Open Access Content
Open access content
Subscribed Content
Subscribed content
Free Trial Content
Free trial content
Cookie Policy
X
Cookie Policy
ingentaconnect website makes use of cookies so as to keep track of data that you have filled in. I am Happy with this Find out more