CHEMICAL OXIDATION

DEFINITION
Chemical oxidation in wastewater treatment typically involves the use of oxidizing agents such as ozone, hydrogen peroxide, permanganate, chloride dioxide, chlorine and oxygen, to bring about change in the chemical composition of a compound or a group of compounds.

FUNDAMENTALS
oxidation-reduction half reaction potentials reaction potentials equilibrium constants for redox reactions rate of oxidation-reduction reactions

Oxidation-Reduction Reactions Oxidation-reduction reaction (redox reaction) takes place between an oxidizing agent and a reducing agent. In oxidation-reduction reactions both electrons are exchanged as are the oxidation states of the constituents involved in the reaction. While an oxidizing agent causes the oxidation to occur, it is reduced in the process. Similarly, a reducing agent that causes a reduction to occur is oxidized in the process. Consider the Reaction:

Copper (Cu) changes from a +2 to zero oxidation state and the zinc (Zn) changes from a zero to a +2 state. Because of the loss and gain of electrons, the oxidation-reduction reactions can be separated into two half reactions. Half Reaction Potential Every half-reaction involving an oxidation or reduction has a standard potential associated with it. It can be used to predict or measure the tendency of a reaction to proceed as written. Of the many properties that can be used to characterize oxidation-reduction reactions, the electrical potential or emf of the half reaction is used commonly. Thus, every half reaction involving an oxidation or reduction has a astandard potential ( ) associated with it. The potentials for a number of half reactions are given in Table 1.

Table 1. Other Representative Half Reactions

Table 2. Half Reactions for disinfection process

Reaction Potential The half-reaction potentials can be used to predict whether a reaction comprised of two reactions will proceed as written. The tendency of a reaction to proceed is obtained by determining the for the entire reaction as given by the following expression.

where:

potential of the overall reaction potential of the reduction half reaction potential of the oxidation half reaction

The positive value for the is taken as an indication that the reaction will proceed as written. The magnitude of the value, as will be illustrated subsequently, can be taken as a measure of the extent to which the reaction as written will proceed.

Equilibrium Constants for Redox Equations The equilibrium constant for oxidation-reduction reactions is calculated using the Nernst equation.

where:

K = equilibrium constant n = number of electron exchanged in the overall reaction F = Faradays constant = 96,485 J (96.485 kJ) per volt gram equivalent = reaction potential
R = universal gas constant = 8.3144 J (abs)/mole-K T = temperature (in K)

Rate of Oxidation-Reduction Reactions Chemical oxidation reactions often require the presence of one or more catalyst for the reaction to proceed or to increase the rate of reaction. Transition metal cations, enzymes, pH adjustment, and a variety of proprietary substances have been used as catalyst.

APPLICATIONS
In the past, chemical oxidation was used most commonly to (1) to reduce the concentration of residual organics, (2) control odors, (3) remove ammonia, and (4) reduce the bacterial and viral content of wastewaters. Chemical oxidation is specifically effective for the elimination of odorous compounds. In addition to the applications mentioned above, chemical oxidation is now commonly used to (1) improve treatability of nonbiodegradable (refractory) organic compounds, (2) eliminate inhibitory effects of certain organic and inorganic compounds to microbial growth, (3) removal of BOD, grease, etc., (4) reduce or eliminate the toxicity of certain organic and inorganic compounds to microbial growth and aquatic flora. Other applications of chemical oxidation in wastewater management are summarized in Table 3.

Table 3. Typical applications of chemical oxidation in wastewater collection, treatment, and disposal.

Chemical Oxidation of BOD and COD

Biochemical oxygen demand (BOD)- is the amount of dissolved oxygen (DO) needed by aerobic biological organisms in a body of water to break down organic material present in a given water sample at certain temperature over a specific time period. Chemical oxygen demand (COD), in that both measure the amount of organic compounds in water. However, COD is less specific, since it measures everything that can be chemically oxidized, rather than just levels of biologically active organic matter.

Overall reaction for the oxidation of organic molecules compromising BOD

The multiple arrows are used to signify that a number are involved in the overall reaction sequence. Advanced Oxidation Systems have typically utilized ozone, peroxide or hydroxyl ions to decompose the more difficult species to break down. These systems may be coupled with ultraviolet (UV) light and potentially catalysts to enhance the oxidation rates. These systems are typically less in capital cost than biological systems but have a much higher operation cost. Note: When measuring the BOD or COD of enriched oxygen waters, especially in H2O2 treated wastewaters, it is important to determine the residual H2O2 concentration prior to analysis. This is because H2O2 will interfere with both of these analytical methods. In the standard BOD test, residual H2O2 in the sample will liberate oxygen over the test period, resulting in a "false low" BOD value. In the standard COD test, residual H2O2 will react with the potassium dichromate reagent, resulting in a "false high" COD value.
Removal of Ammonia
The chemical process in which chlorine is used to oxidize the ammonia nitrogen in solution to nitrogen gas and other stable compounds is known as breakpoint chlorination. Perhaps the most important advantage of this process is that, with proper control, all the ammonia nitrogen in the wastewater can be oxidized. However, it too has a lot of disadvantages which is in Table 4. Table 4. Breakpoint Chlorination Disadvantages DISADVANTGES OF BREAKPOINT CHLORINATION Buildup of acid (HCl) which will react with the alkalinity Buildup of total dissolved solids Formation of unwanted chloro-organic compounds To avoid the large chlorine dosages required when used alone, breakpoint chlorination can used following biological nitrification to achieve low levels of ammonia in effluent To optimize the performance and minimize the equipment cost, flow equalization is usually required

Table 5. Typical chemical dosages for the oxidation of organics in wastewatera.

The Breakpoint chlorination process can be used for the removal of ammonia nitrogen from treatment plant effluents, either alone or in combination with other processes.

[Insert your report here]

Control of Odours in Sewers, Pumps Stations, and Treatment Plants

The potential release of odours is a major concern of the public relative to modifying existing wastewater treatment facilities and constructing new facilities. Thus, the control of odours has become a major consideration in the design and operation of wastewater collection, treatment, and disposal facilities, especially with respect to the public acceptance of these facilities. Sources of Odours The principal sources of odours in wastewater management facilities and the relative potential for release of odour are presented in Table 6.

Table 6. Odour thresholds of odorous compounds and their characteristics associated with wastewater managementa

Chemical Additions to Wastewater for Odour Control Odours can be eliminated in the liquid phase through the addition of a variety of chemicals to achieve (1) chemical oxidation, (2) chemical precipitation, and (3) pH control. The most common oxidizing chemicals that can be added to wastewater include oxygen, air, chlorine, sodium hypochlorite, potassium permanganate, hydrogen peroxide, and ozone. While all of these compounds will oxidize

hydrogen sulphide (H2S) and other odorous compounds their use is complicated by the chemical matrix in which the odorous gases exist.

Chemical Oxidation of Nonbiodegrable Organic Compound

The dosages (see Table 5) increase with the degree of treatment, which is responsible when it is considered that the organic compounds that remain after biological treatment are typically composed of low-molecular-weight polar organic compounds and complex organic compounds built around the benzene ring structure. Because of the complexities associated with composition of wastewater, chemical dosages for the removal of refractory organic compounds cannot be derived from the chemical stoichiometry, assuming it is known.