Building Quantitative Reasoning
CASE STUDY 2.1 Mastering Redox Chemistry: Energy, Redox Reactions and the
Development of Life
In order to sustain life on the planet, it is important
to develop an understanding of how life evolved and from
where the energy came that allowed it to prosper. To de-
velop an understanding of the coupling between energy at
the molecular level and the development of self sustaining
organisms it is essential that we explore the importance of
water as a medium that supports all life forms on Earth and
the relationship between water and molecular oxygen in the
chemical balance of life.
To this end we begin with the fact that life is sustained
by, is powered, by redox reactions. Nature has discovered how
to use the energy released when electrons are transferred to
or from atoms when reactant molecules are converted to
another molecular structure, i.e. product molecules. So lets
review oxidation-reduction reactions. When we treat an
electron transfer in an oxidation-reduction reaction, we
seek a convenient way to register the movement of electron
density in that chemical reaction. The accounting method is
to employ the oxidation state of each atom involved in the
reaction. In brief, an atoms oxidation state is a positive or
negative number designed to reflect electron density shifts
local to that particular atom relative to some standard state.
That standard state is an atom in elemental formthe form
that represents the electron distribution it would have in the
absence of another atom that may (or may not) have a great-
er ability to draw electron density to it when engaged in a
chemical bond. We can demonstrate both the redistribution
of electron charge, the oxidation state and the energy release
resulting from that redistribution of electron charge in the
following diagram for carbon monoxide, Figure CS2.1a. If
we begin with the carbon and oxygen a distance apart equal
Yellowstone Park A thermal pool in Yellowstone National Park contains beautifully
colored mats of bacterial communities that include thermophilic cyanobacteria. One of
many examples of the adaptability of bacteria to challenging conditions!
Two atoms in
elemental form
oxidation state
C 0
O 0
Electron shift
toward the
oxygen
Energy oxidation state
release e
C+2 e O2
Figure CS2.1a If two atoms in their elemental form are placed a
distance apart equal to the internuclear distance of a corresponding
molecule and then the electrons are allowed to delocalize toward the
atom with greater ability to attract electrons to it in a chemical bond,
the energy of the molecule so formed drops. This changes the oxida-
tion state of zero for the elemental form to a new oxidation state in
the molecule formed as shown.
to the bond length in CO, but with the atoms each in their el-
emental form (including the distribution of electron density
about each atom), they will both have an oxidation state of
zero, by definition. If we now allow the relative ability of each
atom to attract electron density to it in a chemical bond, elec-
tron density will move toward the oxygen, will delocalize
toward the oxygen, releasing energy as the electron density
shifts toward the oxygen, thereby reducing the energy of the
ensemble of atoms, in this case the two atoms in CO.
The oxidation state formalism takes a subtle shift in elec-
tron density and turns it into an all or nothing statement of
electron ownership. Just as in an election, if candidate A
receives just 51% of the vote and candidate B receives 49%
of the votes, candidate A is declared the win-
ner. So it is with a chemical bond. In the case of
CO, electron density shifts toward the oxygen
and it is deemed the winner of the electrons
and is awarded an oxidation number of 2.
The electron is conserved, so the carbon atom
is deemed the loser (of electron density) and
awarded an oxidation number of +2.
It requires a large computer to accurately
calculate the distribution of electron charge in
a molecule. Oxidation numbers are an approx-
imation that provide remarkable insight into
how electrons move, how they delocalize, in a
chemical reaction. Because of the conservation
of electrons, the sum of the oxidation numbers
assigned to atoms in a molecular structure
must equal the net charge on the molecule or
ion. In lieu of a large computer calculation,
the assignment of oxidation numbers follows
a hierarchical pattern based on the competi-
2.39
 Chapter 2

Table CS2.1a
Rules of oxidation states
1. As noted, the oxidation state of an atom in a free
element is zero
2. The oxidation state of a monoatomic ion is equal to
its charge
3. B
 ecause electrons are neither produced nor destroyed
in a redox reaction, the sum of the oxidation states of
all atoms in:
A neutral molecule or molecular formula is 0
An ion is equal to the charge of the ion
4. M
 etals, when they form compounds, have positive
oxidation states
Group 1A metals always have an oxidation state
of +1
Group 2A metals always have and oxidation state
of +2
 hen non-metals form compounds, those non-
5. W
metals are assigned values according to the table
displayed here. Within this table, there is an ordering
of importance with the most important rule begin-
non-
ning at the top metals

elemental form
O0

oxidation state
in elemental form C0
O0 C0 O0 H0 H0 electron
electron
delocalization
delocalization O2
e e
Energy Energy
e
C 0
e
release e e release
O 2 e
C
+4 e
O 2
H +1
H+1

elemental form elemental form

H0 H0 H0 H0
C0 C0 C0
H0 H0 electron
delocalization H0 H0 electron
delocalization
H+1e e
H+1 H+1e e
H+1
Energy Energy
release e
C2 C2e release e
C4 e
H +1
H+1 H +1
H+1
Figure CS2.1b We can relate the change in oxidation state, the energy release and the delocalization of electron density for a selection of impor-
tant cases: CO2, H2CO, C2H4 and CH4.

2.40
 tive ability of individual atoms to draw electron density to
them in a chemical bond. This set of rules that establish the
hierarchy was presented in Table 2.4, and is reviewed here in
Table CS2.1a.
We can sketch some important examples by displaying
the transition from the elemental state with oxidation state
zero to the oxidation state of the molecule after bond forma-
tion, by designating of the direction of electron delocaliza-
tion and the resulting release of energy as shown in Figure
CS2.1b.
Note that the double bond between the carbon atoms
in C2H2, ethane, is not associated with any electron delocal-
ization. Thus, to summarize, oxidation states provide an ap-
proximate way, in the absence of a full computer calculation,
to describe the shift or delocalization of electron density in a
molecule or polyatomic ion. The process of assigning oxida-
tion states
Assumes that the more electronegative atoms takes (or
wins) the whole electron as if a shared electron bond
(a covalent bond) were really an ionic bond
Employs an arrow to mark the shift of electron density
relative to the atom in its elemental state
Each arrow designating this shift in electron density
is designated by an increase of 1 for the atom that is
oxidized (at the tail of the arrow) and a decrease of 1
for the atom that is reduced (at the arrow tip)
Bonds between like atoms, shown without arrows,
do not result in an electron shiftan electron
delocalizationand thus do not engender a change in
oxidation state.
The idea of an oxidation-reduction reaction, or redox
reaction, emerged in the developing understanding of chem-
ical reactions in the study of rapid, intense combustion of
hydrocarbon fuels in the presence of oxygen. A very familiar
example is the burning of natural gas in oxygen
CH4 + 2O2 2H2O + CO2
We can immediately assign oxidation states to each of
the atoms in the reactant molecules and in the product mol-
ecules using Table CS2.1a:
C4H4+1 + 2O20 2H2+1O2 + C+4O22
The reaction is a redox reaction because the carbon is oxi-
dized from C4 to C+4 and the oxygen is reduced from O0 to
O2.
But redox reactions are not always fast and intense. For
example the iron used for building bridges, or constructing
automobiles is invariably involved in a redox reaction where
Fe in its elemental state reacts with oxygen (mediated by the
presence of water) to produce Fe2O3. The process of corro-
sion.
2Fe + 3/2 O2 Fe2O3
In this case both reactants are in their elemental state with
an oxidation state of zero. The product (oxygen with a metal)
has the following oxidation state:
2Fe0 + 3/2 O20 Fe2+3O32
While the reaction releases considerable energy in the
form of heat, the reaction takes place over an extended pe-
riod of time (often years) such that the heat flows from the
reaction so slowly that it is imperceptible.
With this background on redox reactions, we proceed
to a discussion of how organisms, particularly bacteria, use
redox reactions to survive. If energy can be extracted, it can
be used to sustain vital processes that, when taken together,
constitutes a living organism. The key is to channel the ener-
gy captured from redox reactions and then use that energy to
instigate such objectives as muscular contraction, molecular
synthesis, response to light or sound, or keeping the organ-
ism at a fixed temperature. Organisms have evolved the abil-
ity to design membranes from protein building blocks to use
energy from redox reactions to sustain a remarkable range of
life forms. Before we can understand such systems, we must
advance our understanding of oxidation-reduction process
for they are the reactions that form the foundation, the mo-
tive energy, behind lifes most fundamental processes.
What is remarkable is that life forms that evolved to the
point where they could synthesize molecular structures from
H2O and CO2, photosynthesis,
H2O + CO2 + sunlight CH2O + O2
were evolved from life forms that had to operate using re-
dox reactions that did not involve oxygen. There are, today,
regions of the worlds oceans, lakes and estuaries where oxy-
gen, O2, is not available. These dead zones are usually the
result of introducing molecules that react with and remove
molecular oxygen from the water system, returning that sys-
tem to the conditions that were present prior to 3.5 billion
years ago when, as we will see, oxygen levels in the atmo-
sphere began to rise to levels comparable to O2 levels found
today. Our atmosphere began to approach current levels of
O2 approximately 1 billion years ago. So we use this transition
between aerobic (oxygen containing) and anaerobic (oxygen
depleted) condition to examine more fully how redox reac-
tions work and how we can harness an understanding of re-
dox chemistry to create new opportunities.
When oxygen is available (an aerobic environment), the
dominant biological redox process is respiration
CH2O + O2 CO2 + H2O + energy
Question:
Demonstrate explicitly why this reaction is a redox reac-
tion
2.41
 Chapter 2

Answer: vital to life (molecular synthesis, muscle contraction, etc.)

that constitutes this remarkable union between electron rear-
We know from the chapter that a redox reaction must
rangement and life. Both membrane architecture and redox
involve the movement of one or more electrons from one re-
reactions are required. We focus here on developing an un-
agent to or toward another. But more precisely, we must keep
derstanding of redox processes. We will examine the role of
track of the electrons assigned to each atom in both reactants
membranes in subsequent Case Studies.
and products in order to determine whether electrons have
What is universal is that redox reactions provide the en-
been transferred even though that transfer may simply be
ergy wherein reactants go to products and energy is released:
the delocalization or movement to or from the atoms cen-
ter. So lets do this accounting explicitly for the reactants and CH2O + O2
products in this reaction. To do this we use the Rules for Oxi-
dation States in Table CS2.2a.
Energy
All the atoms in our respiration reaction are non-metals,
release in
so we assign oxidation states, according to the order present-
redox reaction
ed in the Table: to hydrogen first, oxygen second and then CO2 + H2O
apply the requirement that the oxidation states sum to zero
for each of our (neutral) molecules (Rule 3). However, for more than 1 billion years, life forms were pri-
Step 6 Step 5 marily the domain of bacteria, principally because bacteria
oxidation oxidation evolved to employ redox reactions in the absence of oxygen.
state of state of
C is +4 O atom is 2 In fact bacteria evolved to become the masters of the game
of extracting energy from an array of redox reactions in the
C H2 O + O2 C O2 + H2 O absence of oxygen.

Step 3 Step 1 Step 2 Step 4 Step 7 Step 8

oxidation oxidation oxidation oxidation Oxidation Oxidation Question:
state 0 state +1 state 2 state in state of state of
a free each H O atom Why is the chemistry of oxygen and of water so central
must be sum +2 sum 2 element is +1 is 2
zero, because is zero
to redox reactions and to the development of life forms?
molecule is
neutral
Answer:
Thus, when we examine the movement of electrons on
an atom-by-atom basis in the transition from reactant to We will repeatedly examine the implications of electron
product movement in chemical transformations that result from the
Reactant Product differing ability of atoms to draw electrons to them resulting
in a lower energy configuration. Water is the medium within
oxidation oxidation
H state +1 H state +1 which life takes placewhether at the ocean bottom in vents
oxidation oxidation that spawned primitive life forms 3.5 billion years ago or
O state 2, 0 O state 2, 2 within complex cells of advanced life forms. Waters central
oxidation oxidation
C state 0 C state +4
role in all this emerges from two primary traits: (1) the ability
of the oxygen to extract electron density from hydrogen in a
By virtue of the carbon atom from a molecular structure chemical bond and (2) the shape of the water molecule. It is
involving two hydrogen atoms and an oxygen atom (CH2O) bent with electron density localized on the (electron rich)
with resulting oxidation state of zero, to a molecular struc- oxygen and with the electron poor hydrogens extending
ture involving two oxygen atoms (CO2), the carbon atom outward as shown in Figure CS2.1c.
donated 4 electrons and was thus oxidized. In the process, O
was reduced because it transitioned from an oxidation state Figure CS2.1c
The remarkable
of zero in O2, to an oxidation state of 2 in CO2. All higher influence that water
life forms obtain their energy by respiration. The abundance molecules have on
of free oxygen makes life easy because an immense amount chemical reactivity
stems from both the
of energy can be harvested with this strong oxidizing agent
ubiquitous presence
available. of the molecule and
Notice that it is the combination of the organisms abil- the fact that H2O has
ity to channel the energy released from the rearrangement an electron rich end
(the oxygen) and an
of electron density in the redox reaction that constitutes
electron deficient end (the hydrogens) that are spatially separated.
the key transformation. This is done by using sophisticated
membranes that use the energy release to carry out processes
While we will fully develop the principles that deter-

2.42
 mine this structure in subsequent chapters, we will concen-
trate here on the consequences of this combination of shape
and charge distribution intrinsic to the water molecule.
When an ionic solida solid comprised of atoms held
together by ionic bonds as described on page 2.17, is im-
mersed in water, the negative (oxygen) end of H2O attracts
the positive (cation) of the ionic solid while the positive (hy-
drogen) end of H2O attracts the negative (anion) of the ionic
solid. This becomes a battle between the ionic bonding be-
tween the cation and anion in the solid and the Coulomb at-
traction between the polar water molecules and the separated
cations and anions in the water. We can depict this graphical-
ly in Figure CS2.1d that displays the release of the cation that
is then surrounded by numerous water molecules with their
negative (oxygen) ends turned toward the central cation.
Figure CS2.1d When an ionic solid is placed in water, the polar
nature of water is such that the anions are extracted from the solid by
the positive (hydrogen) end of water and the cations are attracted to
the negative (oxygen) end of the water molecule.
Also shown is the corresponding anion that, when re-
leased from the ionic solid, is surrounded by the accessible
positive (hydrogen) ends of multiple H2O solvent molecules.
Why does the ionic solid decide to break up into cations
and anions? Because, in so doing, energy is released. We can
sketch this on an energy diagram shown in Figure CS2.1e.
NaCl + nH2O
Energy
release from
conversion of
ionic solid to cations/anions
in solution
Figure CS2.1e When NaCl is placed in water, the ionic bond
between Na+ and Cl in the solid is broken. It is broken because that
bond is not strong enough to compete with the multiple bonds
formed in the attraction between individual Na+ cations and the
negative end of the water molecules, in combination with the attrac-
tion between the Cl and the positive end of other water molecules
that cluster about the Na+ and Cl. The result is a release of energy
and the dissociation of NaCl in water.
This begins to connect the chemistry of water and ox-
ygen with the concept of redox reactions and then to the
mechanisms by which redox reactions power life.
Elements can exist in different oxidation states depend-
ing upon how many electrons are added to or removed from
their valence shells. In an aqueous medium, the amount of
energy releasedthe stability of a given oxidation state
depends on the properties of water as described above. For
group 1 and Group 2 metals, for example sodium and mag-
nesium, there are 1 and 2 weakly bound electrons respective-
ly in the valence shell so invariably if energy is released in the
solution (the addition of the ionic solid to water), Na+ and
Mg2+ are formed from ionic solids that dissociate in water.
All metals form cations (positive ions) in water. As we move
to the right in the periodic table, electrons are bound more
tightly and we can have multiple possibilities for oxidation
states. An important example is iron, for which either Fe2+ or
Fe3+ can exist in water.
Thus we have a general picture of metals, M, donating
electrons to the surrounding aqueous medium as shown in
Figure CS2.1f.
metal
H2O
e
Energy metal
release
H2O
Figure CS2.1f When a metal is placed in water, the
metal typically gives up an electron to the surrounding
water molecules.
As we will see in greater detail in the development of
atomic structure and molecular bonding, as we move to the
non-metals that occupy the upper right hand side of the pe-
riodic table, the elements develop an increasing ability to ex-
tract electron density from other atoms in a chemical bond.
This means that these non-metals can acquire negative oxi-
dation states, such as O2 with an oxidation state 2 in water.
It is standard procedure to use Roman numerals to designate
the oxidation number that systematically distinguishes the
oxidation number from the actual charge. The lowest oxida-
tion state attainable by fluorine, oxygen, nitrogen and carbon
are I, II, III and IV respectively.
2.43
 Chapter 2

As we will see, this is why nitrogen is so important for

plant growth. Eight electrons must be removed from N in the
conversion of NH3 to NO3 and this provides an energy lad-
der by which organisms use the oxidation states of nitrogen
to sustain themselves. We summarize the terminology for re-
dox reactions in Figure CS2.1g.

Figure CS2.1g There are a series

of terms applied when an electron is
either transferred completely or shifts
partially from a donating species X to
a receiving species Y. The four major
examples are presented here.

But positive oxidation levels are also accessible to non-

metals because of the very large propensity for oxygen to ex- Question:
tract electron density from other elements. This is the reason
What is the oxidation state of N in the nitrite ion NO2?
carbon, nitrogen, sulfur and chlorine are in their maximum
oxidation states +IV, +V. +VI and +VII when surrounded by
an oxide: CO2 (or CO32), NO32, SO42 and ClO4. Answer:
We can sketch this by noting the transfer of electron All atoms involved are non-metals. There is no fluorine
density from the non-metal to oxygen in a chemical bond: or hydrogen, so oxygen has an oxidation state of II, and the
e net charge is 1 so N has an effective charge of +3 so it has an
oxidation state of +III.
non-
oxygen
metal

What is important to recognize is that in the assignment

of oxidation states, the designation represents a movement, a
shift, a delocalization away from the non-metal to oxygen,
not a complete transfer of an electron or electrons. As a re-
sult, the actual charges on the non-metal in a non-metal to
oxygen bond are much less than the +4, +5, +6, +7 in CO2,
NO32, SO42, ClO4 respectively. However, the reason we keep
careful track of the oxidation state of an atom in a molecular
structure and why we keep track of how that oxidation state
changes in a chemical reaction is that energy is at stake. A
change in oxidation state virtually without exception implies
a change in energy. This is why living organisms evolved to
become masters of manipulation when it comes to oxidation
states and thus of redox reactions.

2.44
 When reactions (1), (2), and (3) are added together, the net
reaction is
FeS2 + 15/4 O2 + 7/2 H2O Fe(OH)3 + 2H+ + 2 HSO4

Thus for each molecule (or mole) of Fe S2, two molecules (or
moles) of sulfuric acid are formed. One molecule (or mole)
of Fe(OH)3 is the other product.
The ferric hydroxide, Fe(OH)3 , precipitates out, form-
ing a brown film on the stream or river bed that emerges
from or passes through the mine. The acidity of the stream
can increase dramatically as a result, and the impact of an
abandoned mine can be very serious for years after a mine
is abandoned.

We move now to develop this relationship between re-

dox reactions and how life forms utilize the release of energy
from (sometimes subtle) shifts in the electron density in mo-
lecular structures, i.e. redox reactions. Examples extend from
bacterial mediated of sulfur compounds in mine drainage, to
reactions at the sea floor in geothermal vents, to denitrify-
ing bacteria that consume nitrate and release N2 and N2O,
laughing gas.
We begin with the bacterium thiobacillus ferrooxidans
which mediates the oxidation of FeS2 as an energy source to
sustain the existence of this strain of bacteria. Thus there is a prevailing link between bacterial media-
Because sulfur is bound into the structure of coal, when tion, redox reactions, metals and non-metals in both the evo-
the coal is mined the sulfur is released as iron pyrite (FeS2) lution of life and the interaction
that has the appearance of gold, and is commonly termed of biology and chemistry in to-
fools gold because of its appearance. The initial reaction days environment. While theo-
that is employed by thiobacillus ferrooxidans is the redox re- ries for the origin of life focused
action for most of human history on
(1) FeS2 + 7/2O2 + H2O Fe2+ + 2HSO4- how life forms could have ar-
rived on Earth from outside the
NOTE: Determine the oxidation state of each atom in the solar system or through the
reaction and identify the oxidizing agent and the reducing synthesis of molecules in elec-
agent. trical discharges, the discovery Figure CS2.1h Deep
Following the initial oxidation of FeS2, the ferrous cation of deep sea vents in 1977 dra- sea vents were discovered
reacts with oxygen and water at the ocean bottom along
matically altered the debate. the tectonic plate boundar-
(2) Fe2+ + O2 + H2O Fe 3+ + OH These vents, shown in Figure ies. It is now believed that
(3) Fe3+ + 3H2O Fe(OH)3+ 3H+ CS2.1h, form over tectonic plate this is where life forms first
boundaries at the sea floor. emerged on Earth.

2.45

The molten magma at temperatures of 1200C create
convective zones that entrain metals, non-metals such as
sulfur, and water that are ejected from fissures in the ocean
floor as displayed in Figure CS2.1i providing a rich environ-
ment of redox reactions. Bacteria evolved to take advantage
of this rich mix of reactants. This discovery changed the en-
tire framework of the debate and brought chemosynthetic
bacteria to the forefront. A key discovery was that hydrother-
mal vent zones have a density of organisms 104 to 105 times
greater than ocean floor zones that are not in the vicinity of
these hydrothermal vents. It is literally the organic material
produced by chemosynthetic bacteria that sustain these or-
ganic colonies on the ocean floor.
Figure CS2.1i The transect through a deep sea vent reveals the
chemical and physical complexity of these systems.
These ecosystems offer a wide range of temperatures,
nutrients and structures conducive to the evolution of or-
ganisms, and they almost certainly constitute the site for the
initiation of life forms on Earth. They also underline the re-
markable role that bacteria have and continue to play in the
evolution of life.
Two examples of bacteria that evolved within the do-
main of these hydrothermal vents include
1. Thiobacillus Beggiatoa that is sustained by the redox re-
action
2H2S + O2 2S + 2H2O + energy
and
2. Ferrobacillus Gallionella that mediates the oxidation of
ferrus carbonate
4Fe CO3 + 6H2O + O2 4Fe(OH)3 + 4CO2 + energy
Question:
Indicate the oxidation state for each atom in these two
reactions and indicate the oxidizing and reducing agent for
each reaction.
This brings us to redox reactions and their link to bio-
logical systems today. What is remarkable is that the wide
variety of bacteria that struggled for existence and evolved
therein under conditions devoid of oxygen in the early stages
of the evolution of life on the planet, now play an increas-
2.46
Chapter 2
ingly important part in biological systems or ecosystems,
that are today increasingly subject to the anaerobic condi-
tion. Oxygen deficient conditions created by the dumping of
nitrates, sulfates and organic waste into ground water, lakes,
estuaries and wet lands worldwide.
When water is stripped of oxygen, organisms that de-
pend upon respiration cannot survivethat includes all
higher forms of life. Under those anaerobic conditions, bac-
teria take over. The bacteria utilize oxidants other than O2.
This is important. Notice that reduced molecular structures,
fuels, are plentiful but oxidants are in general in short sup-
ply. Those alternative oxidants that bacteria can use in che-
mosynthesis (rather than photosynthesis) are all less able
than oxygen to produce energy in redox reactions, but bac-
teria can successfully mediate these non-oxygen redox reac-
tions to extract enough energy to survive. While there are
many molecules that can serve as oxidants in bacterial me-
diated chemosynthesis, four molecules in particular control
the oxidizing power of anaerobic regions of the biosphere:
nitrate (NO3), manganese dioxide (MnO2), ferric hydroxide
(Fe(OH)3), and sulfate (SO42).
As a result, a series of bacterially mediated oxidation
steps of organic matter forms a coherent sequence of reac-
tions that cascade to lower and lower energy as each of the
oxidizing reagents is used up.
So here is how it works. Whenever oxygen is mixed with
water or whenever oxygen can diffuses into water, that water
contains approximately 9 mg of O2 in each liter of water. We
will develop a quantitative treatment of oxygen dissolving in
water in subsequent Case Studies. So microbial metabolism
will use this oxygen in the familiar respiration step
CH2O + O2 CO2 + H2O
until the O2 is depleted. Examples of this include the oxida-
tive aerobic digestion of sewage waste and the decomposi-
tion of organic matter near the surface of soils exposed to the
atmosphere.
When this available oxygen is used up, bacteria that can
use the next most powerful oxidizing species, nitrate (NO32)
take over. The key reaction is the bacterial mediated oxida-
tion of organic matter
CH2O + 4/5 NO32 + 4/5 H+ CO2 + 7/5 H2O + 2/5 N2
that releases CO2 and N2 into the atmosphere. This reaction
is dominant in heavily polluted rivers, lakes and estuaries
because typically both organic waste and nitrate from agri-
cultural over-fertilization are dumped in the river systems
together.
Question:
Identify the oxidation state of each atom in the reaction
and indicate the oxidizing agent and the reducing agent.
 When the nitrate is consumed, or when more is added
as an agricultural by-product, the next most powerful oxidiz-
ing agent that the bacteria use is manganese oxide (MnO2)
followed by ferric hydroxide Fe(OH)3. The significance of
those metal oxides is that they serve not only as the oxidizing
agent employed by the bacteria but also they bind to more
toxic heavy metals such as mercury and chromium as well
as to phosphates and carcinogenic organic compounds. The
initiating redox reaction for manganese dioxide is

2 MnO2 + CH2O + H+ 2 Mn2+ + 3 H2O + CO2

For ferric hydroxide the redox reactions is

Figure CS2.1j When an organic substance is introduced into
4 Fe(OH)3 + CH2O + 8 H+ 4 Fe2+ + 11 H2O + CO2 an ecosystem, a series of oxidation steps occurs, depending upon
the amount of organic material beginning with respiration wherein
oxygen is the primary oxidizing agent, and then moving downward
Question: through a series of bacterially mediated steps employing NO3, MnO2,
What are the oxidation states of each atom in the reac- Fe(OH)3, SO42 as oxidizing agents.
tions and which is the oxidizing agent and what is the reduc-
ing agent?
Following the consumption of the available metal ox-
ides, the bacteria turn to sulfur compounds as the available
oxidizing agent. Sulfate reduction by the reaction

SO42 + CH2O + H+ H2S + H2O + CO2

is common in marine sediments because there is ample or-

ganic material that has rained down from the biological
activity near the surface where sunlight penetrates to drive
photosynthesis and sulfate compounds dissolve readily in
seawater. In freshwater systems the sulfate is provided by sul-
furic acid addition as was the case with acid run off from coal
mining. In all cases it is the union of bacterial action with
redox reactions that facilitate the oxidation of organic com-
pounds and sustains the mediating bacterial colony.
We can capture this sequence by graphing, in Figure
CS2.1j, the energy available in each of the redox reactions
as a function of the total amount of organic matter available
for the bacteria to moderate the redox reaction that produces
the energy to sustain those same bacteria.

2.47