Chemical Oxidation and Reduction

PIERO M. ARMENANTE NJIT

Oxidation State and Oxidation Number

The oxidation state of an atom in a reactant is associated with the electronic structure of the atom resulting from the chemical bond in which it is involved In ionic bonds each atom is clearly associated with a net charge due to the acquisition or loss of electrons during the formation of the bond (e.g., in NaCl the sodium ion has an electron which it received from the chlorine atom)

PIERO M. ARMENANTE NJIT

Oxidation State and Oxidation Number

In covalent bonds the charge is shared by the atoms involved in the bond. However, since each atom will have a different level of affinity for electrons (electronegativity) it is conventionally assumed that the electrons involved in the bond reside with the most electronegative atom in the bond The oxidation number or (electro)valence is the number of electrons that the atom in the bond has gained or lost during the formation of the bond
PIERO M. ARMENANTE NJIT

Oxidation State and Oxidation Number

In each non-ionized molecule the total sum of the formal charges must be zero The same element can have different oxidation number in different molecules

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Examples of Oxidation Numbers of Atoms in Different Molecules

Chemical Species HNO3 HNO2 NH3 HCN CH4 CO2 C2H5OH
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Valence H=+1; N=+5; O=-2 H=+1; N=+3; O=-2 H=+1; N=-3 H=+1; C=+2; N=-3 H=+1; C=-4 C=+4; O=-2 H=+1; C=-4; O=+2

Oxidation and Reduction Reactions

Oxidation and reduction reactions, or redox
reactions, are those chemical reactions in which the oxidation state of the reactants changes during the reaction

Two types of reactions are always simultaneously

involved in every redox reactions: - oxidations, i.e., the loss of electrons by a chemical species (which increases its oxidation number) which becomes oxidated - reductions, i.e., the acquisition of electrons by a chemical species (which decreases its oxidation number) which becomes reduced
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Oxidation and Reduction Reactions

Since the total number of electrons during a reaction must remain constant the number of electrons gained by the molecules containing the oxidising species (which becomes reduced) must equal the number of electrons lost by the molecules containing the reducing species (which becomes oxidated)

PIERO M. ARMENANTE NJIT

Oxidation and Reduction Reactions

Example: in the reaction a H2S + b HNO3 c H2SO4 + d NO2 + e H2O S has changed oxidation state from -2 to +6 losing 8 electrons N has changed oxidation state from +5 to +4 gaining 1 electron Hence it must be that: a/b = 1/8 The balanced reaction is: H2S + 8 HNO3 H2SO4 + 8 NO2 + 4 H2O
PIERO M. ARMENANTE NJIT

Oxidation and Reduction Reactions in Wastewater Treatment

A number of wastewater pollutants can undergo redox reactions with the appropriate addition of a oxidizing or reducing agent to the wastewater The result of such reaction it typically the precipitation of contaminants (especially in the case of inorganic pollutants such as heavy metals) or their conversion to a much less toxic form (e.g., an organic waste mineralized to CO2 and H2O)
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Common Oxidation Agents Used in Wastewater Treatment

The following strong oxidants find application in waste treatment: Sodium hypochlorite ...................... NaClO Calcium hypochlorite ..................... Ca(ClO)2 Chlorine ........................................... Cl2 Potassium permanganate .............. KMnO4 Hydrogen peroxide ......................... H2O2 Ozone............................................... O3 Oxygen............................................. O2
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Common Reduction Agents Used in Wastewater Treatment

The following strong reducing application in waste treatment: agents find Sulfur dioxide .................................. SO2 Sodium bisulfite .............................. NaHSO3 Ferrous sulfate ................................ FeSO4

PIERO M. ARMENANTE NJIT

Chlorine as an Oxidation Agent

Chlorine gas dissolves in water where it hydrolyzes according to the reaction: Cl2 + H2O HOCl +H+ + Cl Hypochlorous acid is a weak acid which dissociates forming: HOCl H+ + OCl The equilibrium equations are:

Kh

b g di4. 5 10 HOCl di H Cl = = bg Cl
+ 2

M2

di i2.7 10 H d OCl K = = b g HOCl

+ i

PIERO M. ARMENANTE NJIT

Sodium Hypochlorite and Calcium Hypochlorite as Oxidation Agents

Sodium hypochlorite and calcium hypochlorite also hydrolyze when placed in solution: NaOCl Na++ OClCa(OCl)2 Ca+++ 2 OClH+ + OCl- HOCl partially reforming the undissociated acid. The sum of the (OCl-) and (HOCl) concentration is called the free available chlorine. The distribution of the ionic species in equilibrium is a strong function of pH
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Ozone as an Oxidizing Agent

Ozone is a gas at normal pressure and temperature. Its solubility in water is a function of its partial pressure and temperature Ozone is generated by high voltage discharge in air or oxygen Ozone is unstable and tends to react to form: O3 + H+ + e- O2 + H2O Ozone is a very strong oxidizing agent Ozone is very effective as a decoloration agent and as a oxidant of organic material
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Hydrogen Peroxide as an Oxidizing Agent

Hydrogen peroxide (H2O2) is a colorless water (30 - 70 % solution) which in the presence of a catalyst (such as iron) reacts to form: H2O2 +2 H+ + 2 e- 2 H2O Hydrogen peroxide is a strong oxidant typically used in the treatment of cyanides and wastewaters containing organic materials

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Oxygen as Oxidizing Agent in Wet Oxidation

Wet oxidation is a process in which oxygen dissolved in the wastewater under pressure is used as an oxidizing agent at high temperature and pressure Typical temperatures and pressures are 150 - 325 oC and 2000 to 20,000 kPa (gauge pressure), respectively The process is extremely effective in oxidizing organic materials, organic sulfur, cyanides, pesticides, and other toxic compounds with removal efficiencies of the order or 99+%
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Wet Oxidation Flow Diagram

After Freeman, Standard Handbook of Hazardous Waste Treatment and Disposal, 1989, p. 8.78 PIERO M. ARMENANTE NJIT

Typical Applications of Redox Reactions to Wastewater Pollutants

Inorganic Pollutants - heavy metals - cyanides - sulfides Organic Pollutants - phenol and chlorophenols - pesticides - ammonia nitrogen and amines - sulfur-containing organic compounds (e.g., mercaptans)
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Cyanide Removal from Wastewaters

Cyanide (CN-) is a common pollutant found in many industrial applications, especially metal plating Because of its extreme toxicity even at low concentrations cyanides must be removed prior to wastewater discharge Chemical treatment of cyanide typically involves its oxidation with a strong oxidizing agent to cyanate (CNO-), followed by the oxidation of the cyanate to carbon dioxide, nitrogen, water and NaCl
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Oxidation Reactions for the Conversion of Cyanide to Cyanate

Oxidizing Agent Sodium hypochlorite Calcium hypochlorite Chlorine Reaction 2 NaCN + 5 NaOCl + H20 N2 + 2 NaHCO3 + 5 NaCl 4 NaCN + 5Ca(OCl)2 + 2 H20 2N2 + 2 Ca(HCO3)2 + 3 CaCl2 + 4 NaCI 2 NaCN + 5 CI2 + 12 NaOH N2 + 2 Na2CO3 + 10 NaCI + 6 H20

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Oxidation Reactions for the Conversion of Cyanide to Cyanate

Oxidizing Agent Potassium permanganate Hydrogen peroxide Ozone Reaction NaCN + 2 KMnO4 + 2 KOH 2 K2MnO4 + NaCNO + H20 NaCN + H2O2 NaCNO + H2O NaCN + O3 + H20 NaCNO + O2

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Mineralization of Cyanide with Chlorine or Hypochlorite

Mineralization (i.e., conversion to CO2, H2O and N2) is carried out sequentially in two steps. Reaction time = 10 - 30 min.

Step 1: Cyanide conversion to cyanate (pH = 9 -11)

NaCN + 2 NaOH + Cl2 NaCNO + 2 NaCl + H2O using chlorine, or NaCN + NaOCl NaCNO + NaCl using hypochlorite

Step 2: Cyanate mineralization with Cl2 (pH = 8.5)

2 NaCNO + 4 NaOH + 3 Cl2 N2 + CO2 +6 NaCl + H2O
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Removal of Iron and Manganese from Wastewater

Soluble ferrous (Fe2+) and manganous (Mn2+) ions are removed by precipitation as Fe(OH)3 and MnO2, respectively via oxidation The reaction rate is a function of pH, alkalinity, and impurities that can act as catalyst As oxidation agents oxygen (O2), chlorine (Cl2), or permanganate (MnO4-)are typically used

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Oxidation Reactions Involved in the Removal of Iron and Manganese

With oxygen (pH = 7 for Fe; pH = 10 for Mn; 10 - 20 min):
2 Fe2+ + 1/2 O2+ 5 H20 = 2 Fe(OH)3 + 4 H+ Mn2+ + 1/2 O2+ H20 = MnO2 + 2 H+

With Cl2 (fast reaction):

Fe2+ + 1/2 CI2 + 3H20 = Fe(OH)3 + Cl- + 3 H+ Mn2+ + Cl2 + 2 H20 = MnO2 + 2 Cl- + 4 H+

With KMnO4 (pH = 6 - 9; very fast reaction):

3 Fe2+ + MnO4- + 7 H20 = 3 Fe(OH)3 + MnO2 + 5 H+ 3 Mn2+ + MnO4- + 2 H20 = 5 MnO2 + 4 H+
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Removal of Residual Nitrogen (as Ammonia) via Chlorination

Ammonia nitrogen can be chemically removed via reaction with chlorine according to the reaction: 2 NH3 + 3 HOCl N2 3 H2O + 3 HCl The reaction pH is typically in the range 6 - 7

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Oxidation of Organic Material in Wastewater

The BOD or COD of wastewater can be chemically reduced using oxidation agents such as Cl2 or ozone. The typical dosage to be used for chemical oxidation of organic material is: Dosage (lb/lb removed) Chemical Chlorine Ozone Use BOD5 Reduction COD Reduction Range 0.5 - 2.5 1.0 - 3.0 2-4 3.0 - 8.0 Typical 1.75 2.0 3.0 6.0

After Metcalf and Eddy, Wastewater Engineering, 1991, p. 755 PIERO M. ARMENANTE NJIT

Additional Information and Examples on Chemical Oxidation and Reduction in Wastewater

Additional information and examples can be found in the following references:

Sundstrom, D. W. and Klei, H. E., 1979, Wastewater

Treatment, Prentice Hall, Englewood Cliffs, NJ, pp. 368 - 384.

Wentz, C. W., 1989, Hazardous Waste Management,

McGraw-Hill, New York, pp. 152 - 153.

Corbitt, R. A. 1990, The Standard Handbook of

Environmental Engineering, McGraw-Hill, New York, pp. 9.27 - 9.28.

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Additional Information and Examples on Chemical Oxidation and Reduction in Wastewater

Metcalf & Eddy, 1991, Wastewater Engineering:
Treatment, Disposal, and Reuse, McGraw-Hill, New York, pp. 739 - 740; 755.

Weber, W. J., Jr., 1972, Physicochemical Process for

Water Quality Control, Wiley-Interscience, John Wiley & Sons, New York, pp. 363 - 411.

Freeman, H. M. (ed.), 1989, Standard Handbook of

Hazardous Waste Treatment and Disposal, McGrawHill, New York, pp. 7.41 - 7.76.

Eckenfelder, W. W., Jr., 1989, Industrial Water

Pollution Control, McGraw-Hill, New York, pp. 300 311.
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