Lesson 8 The Chemistry of Natural Waters

Chapter 13 is probably the hardest chapter in the Baird book. It represents an extension,
rather than an application of the principles learned in general chemistry. For the serious student
of the chemistry of the environment, it is a must. For the dilettante, it would probably be better
to skip this chapter. Before beginning to read this chapter, I would advise carefully rereading the
sections of your general chemistry book dealing with redox and acid-base chemistry.
The development of this subject material is, of necessity, mathematical in nature. The
concepts are not advanced but the algebra is detailed and challenging. Most advanced treatments
of environmental chemistry, assume one is familiar with this material. While many of the
calculations for real world systems are done by computer models, it is very important to
understand the underlying basic principles. The trick is to become familiar enough with the math
to see beyond it, to develop an intuition about the effect of certain changes upon a system.
I append a more rigorous approach to the subject material of this chapter that we have
used in the past for this course.
Fundamentals of Aquatic Chemistry
Focus on Acid/Base Reactions

Concept

pH vs acidity
pH [H+]

acidity: capacity of water to donate protons

(for potable H2O, CA(eq/L) = 2H2CO3+HCO3- + H+-OHCO2 in H2O
!"! !" + !! ! !! !"!
!!" =
!!"! =

!! !"!
!"!
!! !"!
!"#!

= 2.6!10!! !"#$ !"! !"# !! !"!

= 10!!.!"

can be written as

!"! + !! ! !"#!! + !!
!"!! = 6.35 !!! =

!"#!! ! !
!"!

= 4.45!10!! = 10!!.!

!"#!! !"!! + !!
1

!"!! = 10.33 !!! =

! ! !"!!
!"#!!

= 4.68!10!!! = 10!!".!

Can solve these equations:

can solve these for H+

!! =

!!"! !! !!"!
!"#!!

Define total carbonate

!! = !! !"! + !"#!! + !"!!
!"!! =

!!
!!

!"#!! =

!! !!
!! !!

!! !"! =

!! !! !
!! !! !!

!! ! !!
!!"! !! =
+
+1
!! !!
!!

TABLE 5.2 Values of !! from pH to 12 at 25C

pH
log !!
pH
log !!
2
12.68
8
2.34
3
10.68
9
1.35
4
8.68
10
0.497
5
6.70
11
0.0841
6
4.84
12
0.00919
7
3.42
If we define
Alkalinity = !! !! , !! = !! !"! + !"#!! + !"!! total carbonatetotal
dissolved inorganic C
For this system, alk = !"! !! + !"#!! + 2 !"!! !"# !" < 7.

Suppose Alk = 6!10!! !" ! !" = 7.5

!! =? (6.4!10!! )
If

!! = 3.2!10!! , !!" !" = 10.2

3

For basic solution:

alk = !"#!! + 2 !"!! + !"!

Alkalinity can be measured (by titration)

!"#!" !"#$%& !" = 4

!!"!"#!!"#$% !" = 10
alk = !"!!

Alkalinity / Solubility relations

Define solubility = !"! + !"#!!
If alk = 0
If atm = 350 ppm !"! , !"! = 1.146!10!!
!!! =

!! !"#!!
!! !
=
= 4.45!10!!
!"!
1.146!10!!

!! = !"#!! =

1.146 10!! 4.45 10!!

= 2.25!10!!

Solubility = 1.146!10!! + 2.25!10!! = 1.371!10!!

Now, if alk = 10!! !" ! 10!! ! !"!
!"! !" + !"! !"#!!
!=

!!! 4.45!10!!
!"#!!
=
=
= 4.45!10!
!"! !"!
!!
10!!"

If !"! = 10!! !"#!! = 10!!

Solubility = 1.146!10!! + 10!! = 1.01!10!! !
Metals in !! !
Cations exist as hexaquo complexes.
!! (!! !)!!!
!! !" !! !
!
!!! = 8.9!10!!

!!
!

+ !!

Solutions of metal ions are acid.

!"!#! , +!"#$%&'! !"!

(a)

!"!"! !"!! + !"!!

!!" = !" + + !"!! = 4.47!10!!

If only this reaction, solubility of CaCO3=[Ca++]=[CO2-3]

S2=4.47x10-4
S=6.8x10-5

(b)

!"!"! + !"! !" + !! ! !"!! + 2!"!!!

!=

!!!! !"#!! !
!"! !"

!!" !!!
!!!

= 4.24!10!!

If !"! !" = 1.146!10!! ! , !"# !"#!.

!"#!! = 9.98!10!!
!"!! = 8.96!10!!
[!"!! ] = 4.99!10!! !
!! = 5.17!10!! !
pH = 8.29
!"!! !"#!! !
= 4.24!10!!
!"!
!"#!! ! = 4.24!10!! 1.146!10!! =

!=

!"!!
Rxn says
!! !"! + !"! + !! ! !"!! + 2!"#!!

If !"!! = !
!(2!)! =
! = 4.99!10!! !"!!
!! !"#!! = 9.98!10!!
!! =

!"!
!"#!!

!"!! =

4.45!10!! = 5.17!10!!

!.!"!!"!!
!!!!

!.!"!!"!!

= !.!!!!"!! = 8.96!10!!

TABLE 5.3 Some important processes and reactions that control the !"! content of surface- and
groundwaters and, therefore, their pH
5

Note: !"! ! represents organic matter.

Other reactions that lead to carbon fixation may involve species of S and N (cf. Morel & Hering
1993; Stumm and Morgan 1996).
Humic and Fulvic Acids
Most organic metal in soils + water are "humic substances."
No specific cpd. !" = 10! 10! .
ground water 0.03 - 0.1 mg C/L
seawater
0.06 - 0.6 mg C/L
rivers + lakes 0.5 - 4.0 mg C/L
fulvic acid (acid/base sol) 12-60% DOC
humic acid (base sol)

pH of natural waters

pH controls
1. A/B eq., hydrolysis, polymerization
2. Adsorption: protons compete for sites
3. Metal - liquid complex formation: "
4. Redox rxns
5. Solubility of minerals
Activity Coefficients of Dissolved Species
In various eq. expressions, we really should use activities instead of concentrations.
Activities can be thought of as "effective concentrations."
!! = ! ! !
ai=activity
i=activity coefficient
mi=concentration

 is a function of the ionic strength of solution, I

1
!=
(!! !!! )
2
can be calculated from a number of prescriptions, depending on I.
Complex: cation/anion or neutral association
Importance of complexes
1. Increase solubility of minerals in water
2. Some species mostly complexed !"!! , !"!! , !" !! , !" !!! , ! !!
3. Complexing affects adsorption properties U carbonate
4. Toxicity depends on complexation Hg
Outer sphere + inner sphere complexes
Complexes are classified as outer or inner sphere depending on water associated with
cation.
Outer sphere:

cation surrounded by tightly held water anion forms transient association

(via long range forces) with hydrated cation

+1, +2 cations + simple anions !" ! , !"!! , !"!! , !"#

!!"#$%&'"( < 10!
Inner sphere

direct cation/znion contact [covalent bonding] ex. aquo complexes

! !! !

+ ! !" !! !

Math of Complexation
metal mass balance
! = ! + !" + !"! + !"! = ! +

!
!!! !"!

ligand mass balance

! = ! + !" + 2!"! + ! !"! = ! +

!
!!! !"#!

average ligand number !

!=

!!!
!

Have stepwise formation constants, K

8

!!!

+ !! !

!! =
!! =
!! =

!"
! !
!"!
!" [!]
!"!
!"!!! [!]

Have cumulative formation constants,

!! = !! =

!"
! !
!"!

!! = !! !! =
!! =

!"!
! !!

! [!]!

= !!

can rewrite mass balance

! = [!] !! [!]!
! = ! + ! !! [!]!
Chelation + Complexation
A/B behavior in terms of Lewis acids / bases.
electron acceptor + electron donor complex
electron donor liquids

chelates multi dintate liquids

Chelates of interest
EDTA

NTA

10

Figure 3.8. Binding of a metal ion, !!! , by humic substances (a) by chelation between carboxyl
and phenolic hydroxyl, (b) by chelation between two carboxyl groups, and (c) by complexation
with a carboxyl group.
Polyprotic Acids
NTA is a polyprotic acid with 3 exchangeable hydrogens
Have dissociation eq.
!! ! !! + !! ! ! !! = 2.18!10!!
!! ! ! !! + !! ! ! !! = 1.12!10!!
!! ! !! + ! !! = 5.25!10!!!
with result

Figure 3.6. Plot of fraction of species !! as a function of pH for NTA species in water.
Consider the dissolution of Pb from pipe by this strong chelating agent at pH = 8. At pH8,
dominant species is !" ! .
!"(!")! ! + !" ! !"# ! + !"! + !! !
!!" !! !!
!"# ! !"!
!=
=
= 2.1!10!!
!" !
!!
What is the lead concentration?
!"# !
!
2.07!10!!
=
=
= 20.7
!" !
!"!
10!!
So
!"# ! !"#
If NTA = 9.7!10!! !
!"# ! 9.7!10!! !

11

= 9.7!10!! 200 10! !" !

= 19.4 !" !
= 19.4 !!"
Suppose you now make this problem tougher by introducing carbonate into the system. Get
NTA equilibria + carbonate equilibria together. The relevant equilibria is
!"#$! + !" ! !"# ! + !"#!!
Calculation (book) shows Pb cone same [at !"#!! 10!! ].
Further calculation (book) shows that throwing !"!! into solution reduces !!" ! because
!"!! competes with !" !! for ! .
Redox Chemistry
Introduction
Redox rxns involve ! ! transfer (gain or loss)
Concept of half rxns
!" !! + !" !" !! + !"
!" !! + 2! ! !" !"#$ !" ! ! , !"#$%&'()
!" !" !! + 2! ! !"## !" ! ! , !"#$%&#!'
Half Rxn not artificial. Can run rxn in two separate beakers

Significance of Redox Chemistry

Oxidation of organic material affects available !!
!"! ! + !! !"! + !! !
What is being oxidized? Reduced?
Dissolution of metals
!" !" ! ! + 3!! + ! ! !" !! + 3!! !
Discussion based upon analogy with A/B rxns. ( lewis definition)
!" !"
!" log!" ! !
low pE, high ! ! , reducing consumes protons
high pE, low ! ! , oxidizing releases protons

12

Natural example: stratified lake

Figure 4.1. Predominance of various chemical species in a stratified body of water that has a
high oxygen concentration (oxidizing, high pE) near the surface and a low oxygen concentration
(reducing, low pE) near the bottom.
Importance of kinetics
conc. of species may not be equilibrium. concs. many redux rxns are slow. dynamics are
important.
Importance of biology
many redox rxns depend on biota + biological activity.
Review of Basics
Oxidation state (Number)
reduction reduce oxid. number
oxidation increase "
"
Table 8.1. Oxidation State
Rules for Assigning Oxidation States:
(1) The oxidation state of a monoatomic substance is equal to its electronic charge.
(2) In a covalent compound, the oxidation state of each atom is the charge remaining on the atom
when each shared pair of electrons is assigned completely to the more electronegative of the
twon atoms sharing them. An electron pair shared by two atoms of the same electronegativity is
split between them.
(3) The sum of oxidation states is equal to zero for molecules, and for ions is equal to the formal
charge of the ions.
Examples:

13

Practice: Determine the oxidation shifts of (a) nitrogen in nitrate (b) sulfur in !! ! (c) carbon in
chloroform !"!#!
Using Half-rxns to write/balance a complete reaction.
(a) Need to know pdts/reactants beforehand.
(b) balance ! ! on both sides
(c) Table of half rxns (notes, gen-chem. book)
Practice:
(a) write balanced equation for
!!!! + !"#! !"#!! + !" !!
(b) !! + !! !!! + !! !! !!! + !! !
Half cells written as SRP.
!"#!! + 8!! + 5! ! !"!! + 4!! !
!"#! (!) + 4!! + 2! ! !" !! + 2!! !
X2
X5

!"!! + 4!! ! !"#!! + 8!! + 5! !

!"#! ! + 4!! + 2! ! !" !! + 2!! !
2!"!! + 8!! ! 2!"#!! + 16!! + 10! !
5!"#! ! + 20!! + 10! ! 5!" !! + 10!! !
2!"!! + 8!! ! + 5!"#! + 20!! + 10! ! 2!"#!! + 16!! + 10! ! + 5!" !! +

10!! !
2!"!! + 4!! + 5!"#! 2!! ! + 5!" !! + 2!"#!!

!! !!! + 2! ! 2!! !!!

!! + 4!! + 4! ! 2!! !

14

2!! !!! !! !!! + 2! !

!! + 4!! + 4! ! 2!! !
4!! !!! 2!! !!! + 4! !
!! + 4!! + 4!! !!! 2!! !!! + 2!! !

X2

TABLE 11.1 Oxidation states of some important elements as they occur in natural waters and
mineral systems.
Element

Symbol

Aluminum
Antimony
Arsenic
Barium
Beryllium
Bismuth
Boron
Bromine
Cadmium
Calcium
Carbon
Chlorine
Chromium
Cobalt
Copper
Fluorine
Gold
Hydrogen
Iron
Iodine
Lead
Lithium
Magnesium
Manganese
Mercury
Nickel
Nitrogen
Oxygen
Phosphorus
Platinum
Potassium
Radium
Selenium
Silicon

Al
Sb
As
Ba
Be
Bi
B
Br
Cd
Ca
C
Cl
Cr
Co
Cu
F
Au
H
Fe
I
Pb
Li
Mg
Mn
Hg
Ni
N
O
P
Pt
K
Ra
Se
Si

Number of protons
(atomic number)
13
51
33
56
4
83
5
35
48
20
6
17
24
27
29
9
79
1
26
53
82
3
12
25
80
28
7
8
15
78
19
88
34
14
15

Oxidation states
3+
3+, 5+
3+, 5+, (0)
2+
2+
3+, (0)
3+
1-, 0
2+
2+
4+, (0), 4-, 216+, 3+
2+, (3+)
2+, 1+, (0)
1-, 0
3+, 1+, (0)
1+, 0
3+, 2+
5+, 0, 12+, (4+), (0)
1+
2+
2+, (3+), (4+)
2+, 1+, (0)
2+, (3+)
5+, 3+, 0, 32-, 0
5+
4+, 2+
1+
2+
6+, 4+, (0), 24+

Silver
Sodium
Strontium
Sulfur
Thorium
Tin
Titanium
Tungsten
Uranium
Vanadium
Zinc

Ag
Na
Sr
S
Th
Sn
Ti
W
U
V
Zn

47
11
38
16
90
50
22
74
92
23
30

Note: Values in parentheses are found in mineral systems only.

Standard Reduction Potentials at 25C

Half-Reaction
!! ! + 2! ! 2! !
!! !! + 2!! !! + 2! ! 4!! !
!"#! ! + !"!!! + 4!! !! !"#$! ! + 6!! !
!"! + ! ! !"(!)
!"#!! + 4!! !! + 3! ! !"#! ! + 6!! !
!"#$! + 2!! !! + 2! ! !"#$ + 3!! !
1
!"#$ + !! !! + ! ! !"! ! + 2!! !
2
!" !! + ! ! !" !! (1 ! !"#! !"#$%&"')
2 !" ! + 2 !! !! + 2! ! !! ! ! + 3!! !
1
!"#!! + 6!! !! + 5! ! !"! ! + 9!! !
2
!"!! + ! ! !"!!
!"#!! + 8!! !! + 2! ! !" !! + 6!! !
1
!"#!! + 6!! !! + 5! ! !"! ! + 9!! !
2
!
!
!"#! ! + 4!! ! + 2! !" !! + 6!! !
!"!! + 3! ! !"(!)
!"! ! + 2! ! 2!" !
!"! !!!! + 14!! !! + 6! ! 2!" !! + 21!! !
!! ! + !! ! + 2! ! !! + 2!"!
!! ! + 4!! !! + 4! ! 6!! !
!"#! ! + 4!! !! + 2! ! !"!! + 6!! !
!"#!! + 2!! !! + 2! ! !"#! + 3!! !
!"! ! + 2! ! 2!" !
!"!! + 4!! !! + 3! ! !" ! + 6!! !
16

E (volts)
2.87
1.776
1.685
1.68
1.679
1.64
1.63
1.61
1.59
1.52
1.51
1.491
1.47
1.46
1.42
1.3583
1.33
1.24
1.229
1.208
1.19
1.065
0.96

1+, (0)
1+
2+
6+, 4+, 0, (1-), 24+
4+
4+
6+
6+, 4+
5+, 4+, 3+
2+

2!"!! + 2! ! !"!!!
!"! + ! ! !"(!)
!"!!! + 2! ! 2!"(!)
!" !! + ! ! !" !!
!! ! + 2!! !! + 2! ! !! !! + 2!! !
!"#!! + 3!! ! + 6! ! !" ! + 6!"!
!"#!! + 2!! ! + 3! ! !"#! ! + 4!"!
!! ! + 2! ! 2! !
!"! + ! ! !"(!)
!! ! + 2!! ! + 4! ! 4!"!
!"!! + 2! ! !"(!)
!"#! ! + !! ! + 2! ! !"# ! + 2!"!
!"! !"! ! + 2! ! 2!" ! + 2!" !
!"#$ ! + ! ! !" ! + 2!" !
!"!!! + 4!! !! + 2! ! !! !"! + 5!! !
!"!! + ! ! !"!
!! !!!! + 2! ! 2!! !!!!
!"!! + !! ! + 2! ! !"!! + 2!"!
2!! !! + 2! ! !! ! + 2!! !(!)
!" !! + 2! ! !"(!)
!"!! + 2! ! !"(!)
!" !! + 2! ! !"(!)
!" !! + 2! ! !"(!)
!"#$! ! + 2! ! !" ! + !"!!!
!"(!")! ! + ! ! !"(!")! ! + !"!
!" !! + 2! ! !"(!)
!" !! + 2! ! !"(!)
!" !! + ! ! !" !!
!" !! + 2! ! !"(!)
!"(!")! ! + ! ! !" !" ! (!) + !"!
!"# ! + !! ! + 2! ! !" ! + 2!"!
2!"!!! + 3!! ! + 4! ! !! !!!! + 2!"!
!"(!")! ! + 2! ! !" ! + 2!"!
!"(!")! ! + 2! ! !" ! + 2!"!
!" !! + 3! ! !"(!)
!"!! + 2! ! !"(!)
2!! ! + 2! ! !! ! + 2!"!
!"!!! + !! ! + 2! ! !"!!! + 2!"!
!"!! + 2! ! !"(!)
!"(!")! ! + 2! ! !" ! + 2!"!
!" !! + 3! ! !"(!)
!" !! + 3! ! !"(!)
!" !! + 3! ! !"(!)
!"!! + 3! ! !"(!)

0.905
0.7996
0.7961
0.770
0.682
0.61
0.588
0.535
0.522
0.401
0.3402
0.28
0.2682
0.2223
0.20
0.158
0.0895
0.01
0.000 exactly
-0.1263
-0.1364
-0.23
-0.28
-0.356
-0.40
-0.4026
-0.409
-0.41
-0.557
-0.56
-0.576
-0.58
-0.66
-0.73
-0.74
-0.7628
-0.8277
-0.92
-1.029
-1.47
-1.706
-2.08
-2.335
-2.37
17

!"!! + 2! ! !"(!)
!"(!")! ! + 2! ! !" ! + 2!"!
!"! + ! ! !"(!)
!"!! + 2! ! !"(!)
!"!! + 2! ! !"(!)
! ! + ! ! !(!)
!" ! + ! ! !"(!)

-2.375
-2.69
-2.7109
-2.76
-2.90
-2.925
-3.045

All voltages are standard reduction potentials (relative to the standard hydrogen electrode) at
25C and 1 atm pressure. All species are in aqueous solution unless otherwise indicated.
Concept of E
Can run half rxns in separate beakers. If [ ] = 1M, T = std = P
measure E as voltage vs SHE.
SHE 2!! + 2! ! !!

E = 0.00

In Table of SRP, strong oxidizing agents at top, strong reducing agents at bottom.
Electron Activity and pE
In A/B chemistry, we use pH where
!" = log!" !! = log!" !! !
In redox chemistry, we use pE where
!" = log!" ! ! = log!" !! !
But how do we measure/define !! ! ?
Consider a rxn:
!" !!! + !! ! !" !! + 2!!
!!
can write half rxns
!" !!! + ! ! !" !!
!!
!
!
!! ! 2! + !
!!
Assign !! = 1 (equivalent to saying E=0.0)
!! = !! !! =

!" !!!
!" !!! ! !

!" = log ! !
log !! = log

!" !!
!" !!!

log ! !
18

!" !!!

!" = log !! + log

!" !!

Define !" = log !!

!" = !" + log

!" !!!
!" !!

Can generalize this to a reaction involving n electrons as:

!

!" = !" + ! log

!! [!"]!!

!
!! [!"#] !

for
!"!! + 3!! ! + 6! ! ! ! + 6!"!
!"!!

!" = !" + ! log

!!

!" ! !

So ---- we have reduced problem of pE to one of determining pE.

!

Define !" = !.!"!!"# = !.!"# (!" 25)

Thus if we further note that E = Eh
!

!" = !.!"!!"# = !.!"#

then we just have Nernst equation restated
N.E.
!! = ! = ! +

2.303!"
0.059
log!" ! = ! +
log!" !
!"
!

re-write as
!" = !" +

0.059
log!" !
!

Tables of SRP's become pE tables as well.

Table 8.3. Equilibrium Constants and Standard Electrode Potentials for Some Reduction HalfReactions
Reaction
Log K at 25C Standard Electrode
pE
Potential (V) at 25C
-46
-2.71
-46
!!! + ! ! = !"(!)
19

!"!! + 2! ! = !"(!)
!"!! + 2! ! = !"(!)
!" !! + 2! ! = !"(!)
!" !! + 2! ! = !"(!)
! !! + ! ! = ! !!
2!! + 2! ! = !! (!)
! ! + 2!! + 2! ! = !! !
!"!! + ! ! = !"!
!"#$ ! + ! ! = !" ! + !" !
!"!! + 2! ! = !"(!)
!"! + ! ! = !"(!)
!" !! + ! ! = !" !!
!"! + ! ! = !"(!)
!"(!")! ! + 3!! + ! ! = !" !! + 3!! !
1
!"!! + 6!! + 2! ! = !! ! + 3!! !
2
!"#! ! + 4!! + 2! ! = !"!! + 2!! !
!"! ! + 2! ! = 2!" !
!" !! + ! ! = !" !!

-79.7
-26
-14.9
-9.5
-4.3
0.0
+4.8
+2.7
+3.7
+11.4
+8.8
+13.0
+13.5
+17.1
+104

-2.35
-0.76
-0.44
-0.28
-0.26
0.00
+0.14
+0.16
+0.22
+0.34
+0.52
+0.77
+0.80
+1.01
+1.23

-39.7
-13
-2.45
-4.75
-4.30
0
2.4
2.7
3.7
5.7
8.8
13.0
13.5
17.1
20.8

+43.6
+46
+31

+1.29
+1.36
+1.82

21.8
23
31

So ---- let's be sure we can calculate pE values ( calculations first, understanding 2nd? )
Calculate pE for
a) acid solution 10!! ! = !" !!! , !" !! = 10!! !
b) natural water, pH = 7.5 in equilibrium with O2 (PO2=0.21 atm)
c) natural water, pH = 8, !"#! ! !" !". with !"!! = 10!! !
!" !!! !" !! + ! !
!" = !" + log

!"
!"#

= 13 + log

!"!!
!"!!

= 11.

!! ! + 4!! + 4! ! 2!! !
E=1.229
!

!" = !" + ! log

!"
!"#

!.!!"

= !.!"# + ! log

!
! ! ! !"!

20.83 - 7.67 = 13.2

!"#! + 4!! + 2! ! !"!! + 2!! ! ! = 1.208
!

!" = !" + ! log

!"
!"#

!.!"#

= !.!"# + ! log

!! !
!"!!

= 20.5 - 13.5 = 7.0

20

E, pE, pH in natural waters

What are the limits on pH, E in water?
Upper limit ( water + !! )
4!! + !! ! + 4! ! = 2!! !
!! = ! +

!.!"#
!

log !!! !!

from table E = 1.23

!!! = 1 bar
!! = 1.23 0.0592!"
Lower limit ( water + !! )
!! = 0.059!"
SHE

Figure 11.2 The stability field of water as a function of Eh and pH at 25C and 1 bar pressure.
Contours showing partial pressures of hydrogen and oxygen at intermediate Eh values have been
computed with Eqs. (11.17) and (11.23). The crosshatched area is the locus of Eh values
computed assuming the reaction 4!! + !! ! + 4! ! = 2!! ! is at thermodynamic equilibrium
!"
and dissolved oxygen is at or above a detection limit of 5 ! .
Natural systems show the following loci on this diagram.

21

Figure 11.3 Locus of measured Eh values. After L.G.M. Baas-Becking at al., Limits of the
natural environment in terms of pH and oxidation-reduction potentials, J. Geol. 68:243-84.
Copy-right 1960 by The University of Chicago Press. Used by permission.

Figure 11.4 Approximate position of some natural environments in terms of Eh and pH. the
dashed line represents the limits of measurements in natural environments, as reported by BaasBecking et al, (1960) and shown in Fig. 11.3. The crosshatched area defines theoretical
conditions under which waters are calculated to contain dissolved oxygen at or above a detection

22

limit of 5 !g/L. Modified after R.M. Garrels and C.L. Christ (1965). Solutions, minerals and
equilibria. Copyright (1965) by Freeman, Cooper and Company. used by permission.
So what? What the hell do we care about pE, pE?
The answer comes in out connection to Nernst equation
We said NE =
!

!" = !" + ! log

!"
!"#

Consider the reaction

!"!! + !" !" + !" !! !" = 7.84
Eq. const.
!=

!" !!
!"!!

Can relate K to pE
!

!"

!"#
!

!" = !" + ! log

!" = !" + ! log !

But previously (gen. chem) we showed that

!=

!!!
!"

!!!

!" = !.!"!!"#

At eq G = 0 pE= 0
!" =

!"# !
!

Relation of pE to real world environment

(Caveat: remember pE refers to equilibrium situation.)

23

FIGURE 2-19 The ecological redox sequence. In an organic-rich environment that becomes
isolated from the atmosphere, bacteria, after first consuming any available oxygen, utilize
alternative oxidants in the sequence shown from left to right. As each oxidant is being utilized,
the pE (and Eh) of the system lies in the approximate range shown on the vertical axis. The
broad and indefinite range of pE and Eh associated with each oxidant is intended to reflect both
variation in the oxidant and reductant concentrations and the fact that while pE and Eh are
calculated on the basis of equilibrium, natural redox systems are usually not at equilibrium.
The same chart viewed "chemically"

24

Figure 3.23 Sequence of redox reactions in aqueous environment. O2 in natural waters at 20C is
sufficient to oxidize about 3.4mg of organic carbon (shown here as CH2O) per liter of water.
When the rate of replenishment of O2 from the atmosphere is slower than the rate of oxidation of
Ch2O, oxygen is depleted and microbes will select the next most energetic oxidant in the
sequence shown. For simplicity, only major products and their valence states are shown. See
Table 3.7 for balanced equations. Source: W.M. Stigliani (1988). Changes in valued capacities
of soils and sediments as indicators of nonlinear and time-delayed environmental effects.
Environmental Monitoring and Assessment 10: 245-307. Copyright 1988 by Kluwer,
Academic Publishers. Reprinted with permission of Kluwer.
Saying the same thing in another way.

Figure 11.10 The theoretical Eh (mV) of some important oxidation-reduction couples at equal
molar ion concentrations except as indicated below, at pH = 7 and 25C. Cross-hatched area
gives Eh's for !! (!") !! !, where !! (!") ranges from 8.25 to 0.01 mg/L. Other conditions
are: !"!! !! (!") at !! (!") = 14 mg/L (atmospheric !! = 0.80 bar), !"!! = 62 mg/L;
!"#! (!"#$%&'()* !"!! at !"!! = 1 mg/L; !"(!")! !" !! at !" !! = 1 mg/L assuming !!"
for !"(!")! = 10!!".! ; !"!!! !"#! (!"#$%&) at !" !! = 1 mg/L and !"!!! = 96 mg/L; and
!(!"#$%& !"#$%&) !! !(!") at !! !(!") = 108 mg/L 10!!.! !"# ! . After D. Langmuir,
25

Physical and chemical characteristics of carbpnate water. In Guide to the hydrology of carbonate
rocks, ed. P. E. Lamoreaux, B. M. Wilson, and B. A. memeon. Copyright 1984 by UNESCO.
Used by permission.
What are the general controls on the redox state of natural waters?
atmospheric !! is the major oxidant
organic matter is the major reductant
Comments:
!! rich environment (high pE)
oxidize organic matter
!"! ! + !! !"! +!! !
oxidation capability of water limited
Solubility of !! in water = 9 mg/L (20C) (~0.3x10!! moles)
To oxidize 1 mg organic carbon, need 2.7 mg !!
, at 20C, 3.4 mg !"! ! can be oxidized by !! dissolved in a liter of water.
Industrial waste has a carbon content that greatly exceeds this number!
TABLE 3.6 TYPICAL BODS FOR VARIOUS PROCESSES
Type of discharge
BOD (mg !! /liter wastewater)
Domestic sewage
165
All manufacturing
200
Chemicals and allied products
314
Paper
372
Food
747
Metals
13
Other oxidants can operate when !! concentration falls so that aerobic bacteria cannot survive.
5 molecules control this regime.
!"!! , !"#! , !"(!")! , !"!! , !"!
This gives rise to the following processes:
Denitrification
2!"!! + 12!! + 10! ! !! + 6!! !
!"#! Reduction
!"#! + 4!! + 2! ! !"!! + 2!! !
Iron Reduction
!"(!")! + 3!! + ! ! !" !! + 3!! !
26

Sulfate Reduction
!"!! + 9!! + 8! ! !" ! + 4!! !
!"! methane
!"! + 8!! + 8! ! !"! + 2!! !
pE can be thought of as a "chemical selector" that determines how oxidation is carried out by
micro-organisms. The following table summarizes the situation.
TABLE 3.7 REDOX REACTIONS, PRODUCTS, AND CONSEQUENCES
Redox Reaction
Reaction Products/Consequences
1. !! + !"! ! !"! + !! ! The aerobic condition, characterized by the highest redox
potential, occurs when there is an abundance of !! , and the
relative absence of organic matter owing to oxic decomposition
by aerobic micro-organisms. Two examples are the aerobic
digestion of sewage wastes, and the decomposition of organic
matter near the surface of well-aerated soils. The end products,
!"! and water, are nontoxic.
When molecular oxygen is depleted from the soil or water
2. 4 5 !"!! + !"! ! +
!
column, as would be the case, for example, in waterlogged soils
4 5 ! !"! +
and wetlands, available nitrate is the most efficient oxidant.
2 5 !! + 7 5 !! !
Denitrifying bacteria consume nitrate and release !! . !! !, a
greenhouse gas, is also released as a side-product. In
agricultural soils, denitrification can lead to losses of nitrogen
fertilizer amounting to as much as 20% of inputs. Denitrifying
bacteria are also very active in heavily polluted rivers, or in
stratified estuaries where organic matter accumulates. In some
estuary systems, denitrification may significantly affect the
transfer of nitrogen to the adjacent coastal waters and to the
atmosphere.
In anaerobic environments where nitrates are in low
3a. 2!"#! + !"! ! +
!
!!
concentration and manganese and ferric oxides are abundant,
4! 2!" + 3!! ! +
the metal oxides are a source of oxidant for microbial oxidation.
!"!
This may be the case in natural soils, and in the sediments of
lakes and rivers. The environmental significance of these
metals , deleterious organic compounds, phosphates, and gases.
When the metal oxides are reduced, they become water-soluble
and lose their binding ability. This loss may result in the
release of toxic materials.
' ' ' '
3b. 4!"(!")! + !"! ! +
!
!!
8! 4!" + 11!! ! +
!"!
Sulfidic conditions are brought about almost entirely by the
4a. 1 2 !"!!! + !"! ! +
bacterial reduction of sulfate to !! ! and !" ! accompanying
!! 1 2 !! ! + !! ! +
organic matter decomposition. Sulfate reduction is very
!"!
common in marine sediments because of the ubiquity of organic
27

matter and the abundance of dissolved sulfate in seawater. In

fresh water, such reactions are important in areas affected by
acidic deposition in the form of sulfuric acid. !! ! is an
extremely toxic gas. Sulfides are also important in scavenging
heavy metals in bottom sediments.
4b. !"! + 7 2 !! +
Conversion of a heavy-metal sulfide (!"! ) to sulfate may also
occur when anaerobic sediments are exposed to the atmosphere,
!! ! !!! + 2!"!!! +
!
as in the case of the raising of dredge spoils. It may also occur
2!
when wetlands contianing pyrites (!"#! ) are drained for
agriculture, or in coal mining areas as acid-mining drainage.
One consequence may be an increase in acidification from the
generation of sulfuric acid; another might be the release of toxic
metals.
Under anaerobic conditions at a redox potential of about -200
5. !"! ! + !"! ! !"! +
mV and in the presence of methogenic bacteria as may be found
!"!
in swamps, flooded areas, rice paddies, and the sediments of
enclosed bays and lakes, partially reduced carbon compounds
can disproportionate to produce methane as well as !"! . This
reaction is more typical in freshwater systems because sulfate
concentrations are much lower than in marine environments,
averaging about one one-hundredth the concentration in
seawater. Methane is a critical gas in the determination of
global climate. Since the early 1970s, global atmospheric
methane levels have been increasing at a rate of 1% per year.
Although the reasons for this increase are still under
investigation, the expansion of rice paddy cultivation in
southeast Asia has been cited as a contributing cause. See
discussion, PArt II, pp, 123-125.
Source: W.M. Stigliani(1988). Changes in valued capacites of soils and sediments as indicators
of nonlinear and time-delayed environmental efects. Environmental Monitoring and Assessment
10: 245-307
Recap
Before going further into the use of pE, pE, etc to discuss the environment, we need to
rewind ourselves that there are 4 quantities that really define redox couples K, G, pE(pE),
EH
!

! !

!" = !.!"# 25 = ! log ! = !!.!!"

! = !" ln !
On the next pages, I append an "environmental redox table" that shows redox couples for several
things not found (easily) in standard tables.
Before beginning the use of this table, please note the similarities (once again) between A/B and
redox rxns.

28

!" !! + !!
!" !! ! ! + !" !!!
Caveat: "!! " exists, "! ! " does not, A/B fast, redox slow, Kredox very large, KA/B small
What is pE of an environmental system?
Answer: pE of dominant redox couple
TABLE 7.1 Half Redox Reasctions
pE=logK
!

! +! =
!
! !
! !
!
! !
! !
!
!!
! ! !

Hydrogen

!
! (!)
! !

+ !! + ! ! =
+ !! + ! ! =

0.0
!
! !
! !
!
!!
! !

Oxygen
!
+ !!! !

+35.1
+20.75

+ !! + ! ! = !! !
(Note also !"!! + !! = !! !; log ! = 11.6)
Nitrogen
!
!
!"! + 2!! + ! ! = !!! !! ! + !! !
(Note also !! !! ! = 2!"! ! ; log ! = 0.47)
!
!
!
!"!! + !! + ! ! = !!"!! + !!! !
!
(Note also !"!! + !! = !"#! ; log ! = 3.35)
!
!
!
!
!"!! + !!! + ! ! = !!"(!) + !!! !
!
!
!"!!
!
!
!"!!
!
!
!"!!
!

+ !!! + ! ! = !!! ! ! + !!! !

!

+18.9

+4.85

+16.15

-1.65

+6.03

(Note also !!! !. !"#. = !!! !. !"#. ; log ! = 0.6)

!
!"
!
!"
!"!!! + !"!! + ! ! = !"!!!! + !"!! !
!"
!

+14.15

+14.9

+ !!! + ! ! = !"!!! (!. !"#. ) + !!! !

!
!"!!!
!"

+13.6

+21.05

+ !!! + ! ! = !"!! ! + !!! !

+ !!! + ! ! = !!"!! + !!! !

Sulfur
!
!
!
!!
!!
!
!
!"! + ! + ! = !!"! + !!! !
!
(Note also !"!!! + !! = !"#!!! ; log ! 7
!
!
!
!
!"!!! + !!! + ! ! = !!! !!!! + !!! !
!
!
!"!!!
!

+30.0

+ !!! + ! ! = !"!!!! + !!! !

(Note also !!!! + !! = !"!! ; log ! = 6.1 and
!"!! + !! = !! !! ; log ! = 3.5)
!
!"
!
!
!"!!! + !"!! + ! ! = !"!!!! + !"!! !
!"

+5.40
+5.88

+5.12

29

(Note also !!!! + !! = !"!! ; log ! = 7.0 and

!"!! + !! = !! !! ; log ! = 3.8)
!
!
!
!
!"!!! + !!! + ! ! = !!! ! !" + !!! !
!
(Note also !! ! ! = !! ! !" ; log !! = 1.0, and
other acid-base, coordination, and precipitation
reactions)
Carbon
Inorganic
Carbon monoxide
!
!
!
!"! ! + !! + ! ! = !!" ! + !!! !
!
Graphite
!
!
!
!"! ! + !! + ! ! = !! ! + !!! !
!
Organic-C.1
Formate!
!
!
!"! ! + !!! + ! ! = !!"##!
!
Formaldehyde
!
!
!
!"! ! + !! + ! ! = !!"!# !" + !!! !
!
Methanol
!
!
!
!
!
!"
!
+
!
+
!
=
!"
!"
!"
+
!!
!
!
!
!
! !
Methane
!
!
!
!"! ! + !! + ! ! = !!"! ! + !!! !
!
Organic-C.2
Oxalate2!
!"! ! + ! ! = ! !""! !
Acetate
!
!
!
!
!"! ! + !!! + ! ! = !!"! !""! + !!! !
!
Acetaldehyde
!
!
!
!"! ! + !! + ! ! = !"!"! !"# ! + !"!! !
!
Ethanol
!
!
!
!"! ! + !! + ! ! = !"!"! !"! !" !" + !!! !
!
Ethane
!
!
!
!"! ! + !! + ! ! = !"!! !! ! + !!! !
!
Ethylene
!
!
!
!"! ! + !! + ! ! = !"!! !! ! + !!! !
!
Acetylene
!
!
!
!"! ! + !! + ! ! = !"!! !! (!) + !!! !
!
Organic-C.3
Pyruvate!
!
!
!
!"! (!) + !"!! + ! ! = !"!"! !"!""! + !"!! !
!"
30

+5.13

-1.74
+3.50

-5.22
-1.20
+0.50
+2.86

-10.7
+1.27
+0.99
+1.52
+2.41
+1.34
-0.86

+0.05

Lactate!
!!
!"! ! + !"!! + ! !
!

+0.68

= !"!"! !"#"!##! + !!! !

Glycerol
!
!"! ! + !! + ! !
!"

+0.21

= !"!"! !"#"!"#"! !" + !"!! !

Alanine
!
!
!!
!"! ! + !"!"!! + !"!! + ! !
!
=

!
!"! !"##! !"!!
!"

+0.84
+

!
!!
! !

Organic-C.4
Succinate2!
! !
!
!
!
!
!"
!
+
!
+
!
=
!"
!""
+
!!
!
!
!
!
!
!"
! !
Organic-C.6
Glucose
!
!
!
!"! ! + !! + ! ! = !"!! !!" !! + !!! !
!
Halogens
!
!
!
!" ! + ! = !"
! !
!
!"#$
!

+ !!! + ! ! = !!" ! + !!! !

(Note also !"#$ = !! + !"#! ; log ! = 7.50
!
!
!
!
!"! + !!! + ! ! = !"!! ! + !!! !
! !
!
!
! !

!
!"! !!
!

+23.0
+25.3

+9.05

Trace Metals
Cr
!
!
!
!
!"#$!! + !!! + ! ! = !!" !! + !!! !
!
(Note also !"#$!! = !!!"! !!!! + !!!! !, log ! =
1.5; !"#$!! = !! + !"#!!! , log ! = 6.5
Mn
!
!
!
!
!"#!! + !!! + ! ! = !!"!! + !!! !
!
!

! + 2!! + ! ! = !!"!! + !! !

Fe
!" !! + ! ! = !" !!
!
!
!" !! + ! ! = !!"(!)
!

-0.20

+20.1

! + ! ! = !!

!
!"#!
!

+0.77

+20.2

+25.5
+20.8
+13.0
-7.5

+16.6

! + 4!! + ! ! = !!" !! + 2!! !

Co
!"(!")! ! + 3!! + ! ! = !" !! + 3!! !
!
!
!"! !! ! + 4!! + ! ! = !!" !! + 2!! !
!
Cu
!"!! + ! ! = !"!

+29.5
+31.4
+2.6
31

!
!"!!
!

+5.7

+ ! ! = !!"(!)

Se
!
!
!
!"#!!! + 2!! + ! ! = !!! !"#! + !!! !
!
!
!
! !"#! + !! + ! ! = !!" !
! !
!
!
!" ! + !! + ! ! = !!! !"
!

+19.4

+12.5

+ !!! !

-6.7

(Note also
!! !" = !! + !"# ! , log ! = 3.9; !! !"#! =
!! + !"#$!! , log ! = 2.4; !"#$!! = !! +
!"#!!! , log ! = 7.9; !"#!!! + !! =
!"#$!! , log ! = +1.7)
Ag
!"#$ ! + ! ! = !" ! + !" !
!"! + ! ! = !"(!)
Hg
!
!
!"!! + ! ! = !!"(!)
!

+3.76
+13.5
+14.4

+15.4

!"!! + ! ! = !!"!!!
Pb
!
!
!"#! + 2!! + ! ! = !!" !! + !! !
!
(Note many other reactions for Mn, Fe, Co, Cu, Se,
Ag, Hg, and Pb)

+24.6

pE vs pH (Pourbaix diagrams)
Consider two limiting reactions of H2O
oxidation
a) 2!! ! !! + 4!! + 4! !
reduction
b) 2! ! + 2!! ! !! + 20!!
Applying NE
!

!" = !" + ! log

!!.!!"

+ ! log !!! !!

a)

!" =

b)

!" = 20.83 + log !!! ! !! = 20.83 !"

!" = !" + log !! = !" = !"

!.!"#

Boxed:

32

!"
!"#

Figure 4.4. Simplified pE-pH diagram for iron in water. The water maximum soluble iron
concentration is 1.00x10!! M.

Other Pourbaix diagrams of interest

Anoxic waters (!"!! ! ! system)

33

Other diagrams can be very complicated. Let us follow the text book example of how these
diagrams are calculated, using the iron system as an example.
Rxns:

!" !!! + ! ! !" !! !" = +13.2

!"(!")! ! + 2!! !" !! + 2!! !
"Ksp" =

!" !!

!! !

= 8.0!10!"

!"(!")! ! + 3!! !" !!! + 3!! !

"Ksp" =

!" !!!
!! !

= 9.1!10!

Have "water boundaries" for diagram

pE = 20.25-pH
pE = -pH

very acidic conditions (pH<3)

!" !! = !" !! !"#$
34

!" = 13.2 + log

!" !!!
= 13.2
!" !!

For pE > 13.2 , as pH increases (OH- increases), get pptn of !" !!! as !"(!")!
!!

!" !!!
10!!
=
!
!!"
9.1!10!!

pH = 2.99

Can establish !" !! , !"(!")! boundary

!

! !

!" !!
10!!
=
=
!!"
8!10!"

pH=8.95
What about !" !! !"(!")!
Earlier we said
!" !!!

pE = 13.2 + log
!
!" !!! = !!"
!

pE = 13.2 + log

!" !!
! !

! !! !
!!"

!" !!

pE = 13.2 - 3pH

35

!"(!")! !"(!")! boundary

!
!!"
!!
!" = 13.2 + log
!" !!

!
!!"
!!
= 13.2 + log!"
!!" !!

!
!

pE = 4.3 - pH
Result

Figure 4.4. Simplified pE-pH diagram for iron in water. The water maximum soluble iron
concentration is 1.00x10!! M.

36