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Lecture #49Redox Chemistry: Predominance Diagrams;

spanning the range of pe(Stumm & Morgan, Chapt.8 )

Benjamin; Chapter 9

David Reckhow CEE 680 #49 1

Updated: 29 April 2020 Print version

Chlorine Predominance Diagram Features

Oxidation state Higher oxidation states (HOCl/OCl-) in upper region Middle oxidation state (Cl2) in middle at low pH range Chloride in lower region

pH divisions Vertical lines at pKa values

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Constants

Conversions

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[ ] )(059.01log1 voltsEK

nppe o

Hoo ==≡ ε

FRT )10ln(059.0 =

Chlorine species +I, 0 and -I

oxidation states

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Stumm & Morgan, 1996; Fig. 8.11, pg. 463

A highly oxidized system

Chlorine Predominance Diagram Features

Oxidation state Higher oxidation states (HOCl/OCl-) in upper region Middle oxidation state (Cl2) in middle at low pH range Chloride in lower region

pH divisions Vertical lines at pKa values

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From Soil Science Literature Pyrite is FeS2

Goethite is FeO(OH)

Jarosite is KFe3+

3(OH)6(SO4)2

Iron phases

Iron redox system Ferrous – Ferric

hydroxides

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Stumm & Morgan, 1996; Fig. 8.8, pg. 461

Iron (cont.)

FeT = 10-5 M No carbonates

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From: Aquatic Chemistry Concepts, by Pankow, 1991 (pg 535)

Iron (cont.)

Same as previous, but pH axis limited to 14

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From: Aquatic Chemistry Concepts, by Pankow, 1991 (pg. 536)

Iron (cont.)

FeT = 10-5 M 10-3 M carbonates

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From: Aquatic Chemistry Concepts, by Pankow, 1991

Multi-system

ST = 10-3 M

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From: Aquatic Chemistry Concepts, by Pankow, 1991 (pg 543) FeT = 10-5 MCT = 10-3 M

Fully oxygenated to anaerobic

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From: Aquatic Chemistry Concepts, by Pankow, 1991

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From: Aquatic Chemistry Concepts, by Pankow, 1991

Multi-system

ST = 10-3 M

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From: Aquatic Chemistry Concepts, by Pankow, 1991 (pg 543) FeT = 10-5 MCT = 10-3 M

Other redox systems Phosphorus Nitrogen Sulfur carbon

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Stumm & Morgan, 1996; Fig. 8.9, pg. 461

To next lecture

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DAR