4.1 INTRODUCTION
Interest in persulfate began in earnest around 2000–2002 when work on persulfate began
to appear regularly in conference proceedings and in presentations at major remediation
meetings. Because of the relatively short period of time that persulfate has been used for
in situ chemical oxidation (ISCO) and the fact that persulfate is a less commonly used oxidant
in industrial processes and water treatment than hydrogen peroxide, permanganate, or ozone,
there is less information available on persulfate. As a result, there is less known about
persulfate reaction chemistry, activation methods, contaminant treatability, and subsurface
transport. However, the scientific understanding of persulfate for use in ISCO is increasing
rapidly and will undoubtedly grow and be refined with time and experience.
4.2 CHEMISTRY PRINCIPLES
To understand the use of persulfate for ISCO and the reasoning behind proper implementation
of this technology, it is important to understand the basics of reaction chemistry.
Persulfate reaction chemistry is complex, including free radical chain reactions involving
initiation, propagation and termination steps; radical scavenging; competing and nonproductive
reactions; and oxidation of organic contaminants.
4.2.1 Physical and Chemical Properties
Persulfate, known more formally in the chemistry literature as peroxydisulfate, is a
strong oxidant and anion with the formula S2O8
2
. The peroxydisulfate label differentiates
this oxidant from peroxymonosulfate, another strong oxidant with the formula SO5
2
.
However, peroxymonosulfate is not presently a major ISCO oxidant; for the sake of
simplicity, the term persulfate will be used in this volume to refer only to peroxydisulfate.
Some important physical and chemical properties of sodium persulfate, the most commonly
used form for ISCO, are given in Table 4.1. Persulfate molecular structure is shown in
Figure 4.1.
Persulfate is most commonly supplied as a solid sodium salt (Na2S2O8). Ammonium
persulfate and potassium persulfate solutions are also available but are undesirable for
4.1 INTRODUCTION
Interest in persulfate began in earnest around 2000–2002 when work on persulfate began
to appear regularly in conference proceedings and in presentations at major remediation
meetings. Because of the relatively short period of time that persulfate has been used for
in situ chemical oxidation (ISCO) and the fact that persulfate is a less commonly used oxidant
in industrial processes and water treatment than hydrogen peroxide, permanganate, or ozone,
there is less information available on persulfate. As a result, there is less known about
persulfate reaction chemistry, activation methods, contaminant treatability, and subsurface
transport. However, the scientific understanding of persulfate for use in ISCO is increasing
rapidly and will undoubtedly grow and be refined with time and experience.
4.2 CHEMISTRY PRINCIPLES
To understand the use of persulfate for ISCO and the reasoning behind proper implementation
of this technology, it is important to understand the basics of reaction chemistry.
Persulfate reaction chemistry is complex, including free radical chain reactions involving
initiation, propagation and termination steps; radical scavenging; competing and nonproductive
reactions; and oxidation of organic contaminants.
4.2.1 Physical and Chemical Properties
Persulfate, known more formally in the chemistry literature as peroxydisulfate, is a
strong oxidant and anion with the formula S2O8
2
. The peroxydisulfate label differentiates
this oxidant from peroxymonosulfate, another strong oxidant with the formula SO5
2
.
However, peroxymonosulfate is not presently a major ISCO oxidant; for the sake of
simplicity, the term persulfate will be used in this volume to refer only to peroxydisulfate.
Some important physical and chemical properties of sodium persulfate, the most commonly
used form for ISCO, are given in Table 4.1. Persulfate molecular structure is shown in
Figure 4.1.
Persulfate is most commonly supplied as a solid sodium salt (Na2S2O8). Ammonium
persulfate and potassium persulfate solutions are also available but are undesirable for
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