Organics: Oxidation: Organic molecule  CO2, ,

   (complete mineralization)

 Require 54/11 per carbon

 :
 :
:

13.5 moles of oxygen needed to completely mineralize C11H10.

 Reduction of organics :-
 
(a) Chlorinated aliphatic compounds (b) Nitro aromatic compounds
 
Eg.: H+ + CCl4 + 2  CHCl3 + [reductive dichloro
derivative]
 Inorganic Reduction
 
8 + Cl+ 8H+  + 4H2O
Cl used in rocket propellents – very soluble injector, toxic, concerned, no water at present.
Cr + 3 + 5H+  Cr(OH)3(s) + H2O [Here Cr(VI) is used]
Prevents its
Toxic,soluble N
Non Toxic,Insoluble migration
 Oxidants
 
Biotic: Can use O2, , Fe(OH)3(s), anything whose EH is more than contaminant half reaction.
Abiotic: MnO2(s), Mn; H2O2, O3
(reactor + water generates few hydroxal radical)
HO- + e-  OH- , = +1.9V
HOCl-, Cl2(g)

Water treatment plants: Cl2 reagent with other organic species forms high
Reductants organic contaminants like chloroform.
S   [Adsorbed Fe(II)  adsorbed Fe(III)]
  -2 +4 +6

Zero valent metals, Fe0  Fe2+ + 2 , = ?

= (Fe2+) + 2 - (Fe0)
= -78.87 kJ/mol Free energy of
formation of Fe0 from
its original form
 Fe2+ + 2  Fe0 = 78.87 kJ/mol
 
= = -78.87/2 x 96,485 kJ/mol = -0.409 V

Q. What is EH for [Fe2+] = 10-6 M ?

A. EH = = -0.59 V
k
PH=7
Exploring perturbidity of oxidizing water, 2H+ + 2  H2(g) , = 0
Iron is a very strong reductor.
 
EH = = -0.059 V ; = 105.9 atm
pH of such systems go very high and hydrogen production.
 
It was also prepared for passive remediation batch. Iron filings dumped in a trench and let
ground water pass through it.

 
 No sulfate in after, no
O2 left, rust might clog
TCE Chlorinated passage
organic No Chlorinated
organic

Eg.:Reductive dechlorinator of TCE – most frequent observed contamination.

Rates of these reactions:

  = kPCE = 6 x 10-7 L/m2s

m2k/l

k
Mol/l

Longetivity of Fe0 for treatment of TCE:

EH – pH Diagrams:
Ox + n + nHH+  Red

EH

= = RT lnk = -2.303 RT logk

 
= 0.059 V
 Use :
Pe- = -log{e-} =

Eg: O2(g) + 4 + 4H+ 2H2O = 1.23 V

EH = 1.23 V

Upper stability limit = 1 atm (maximum oxidizing condition)

= 1.23 – 0.059 pH
 
2H+ + 2 = 0
 

EH = 0 (Lower stability limit)

= -0.059 pH

 
 
Procedure for diagram :-
 
(i) Draw stability limits for H2O
(ii) Consider pH effects on most oxidized species (eg.: solids – dissolved)
(iii)Consider pH effects on next oxidized species
(iv)Determine interactions between oxidized species

Eg.: Reactions: + 2 + 2H+

H3AsO4 H+ + H2 Ka1 = 10-2.24
H2 H + + H Ka2 = 10-6.76
H H+ + Ka3 = 10-11.5

H3AsO3 H+ + H2Ka4 = 10-9.23

H2 H + + H Ka5 = 10-12.16
H H+ + Ka6 = 10-13.41

log K =
 To get boundary between and :
(1) EH = = 0.156 – 0.059 pH = - 0.67
/:
+ 2 + 2H+ + H 2O --------(1)
+ 3H+
+ 3H+ + 2 + H2O
Now for (1), log K = n/0.059 = (2 x 0.156)/(0.059) = 5.29

= -log kov (-0.059)/n = (18.7 x 0.059)/(2) = 0.552 V

EH = 0.552

At = [] , EH = 0.552 – 0.089 pH --------(2)

Now, + 3H+ + 2 + H2O pK = 18.7

H+ + pK = 12.16
----------------------------------------------------------
+ 4H+ + 2 + H 2O K = 30.86
----------------------------------------------------------
 
  = = 0.909
 
At = [] ,
 
EH = 0.909 = 0.909 – [(0.059/2) x 4] pH
= 0.909 – 0.118 pH
 
Take the above last reaction :-
+ 4H+ + 2 + H2O pKa = 30.86
H+ + pKa = -11.5
------------------------------------------------------------
+ 3H+ + 2 + H2 O pKa = 19.3
------------------------------------------------------------
= = 0.569

EH = 0.569 = 0.589 – 0.089 pH