CLASS NOTES

Overheads

 Water acidity

 Carbon dioxide and carbonic acid; natural water pH

 Water alkalinity

 Chemical equilibrium basics  (web-based tutorial from Chemistry 3600,

Quantitative Chemical Analysis)

 How to calculate and use the "a" fractional distributions (also from my
Chemistry 3600 course)

 pH dependent CO2 solubility

 pH dependent alkalinity

 Oxidation/Reduction and pE

 Biological Carbon Decomposition

 Hazardous Waste Transport in Ground Water

Water Acidity

http://www.chem.usu.edu/~sbialkow/Classes/3650/Acidity/Water%20Acidity.html

The simplest definition is to use the pH. In this case, "acidity" is related to proton
concentration.

pH = - log10[H+]

However, the acidic proton may be attached to the acid. The acid equilibrium is

HA ⇋ H+ + A-

The acid, HA, looses a proton, H+, to become the conjugate base, A-. Mathematically,
this equilibrium is given by the equilibrium equation:

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The "acid strength" is characterized by the pKA given by the equation:

pKA = - log10 KA

Acids with pKA less than 7 are said to be acidic (strong relative to water) while those
with pKA greater than 7 are said to be basic (weak relative to water).

Water acidity found by titration is used to determine the total concentration of protons.

If one titrates water with a strong base, the proton may react to form water:

OH- + HA ⇋ H2O + A-

The pH at the end-point of the titration is related to pKA by:

Titration to a methyl orange indicator end-point (pKIn = 4.3) is used to determine the
strong mineral acid content.

Titration to a phenolphthalein indicator end-point (pKIn = 8.2) determines total acids.

In summary, there are three ways to characterize water acidity.

1. through a measurement of pH.

2. with methyl orange end point titration with base to determine strong mineral
acidity.
3. with phenolphthalein indicator end point base titration to determine total acids.

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 Carbon Dioxide and Carbonic Acid. Natural water pH.

The most common source of acidity in water is dissolved carbon dioxide. Carbon
dioxide enters the water through equilibrium with the atmosphere

CO2 (aq) ⇋ CO2 (g)

and biological degradation/photosynthesis involving organic carbon, {CH2O}

{CH2O} + O2(aq)⇋ CO2 (aq) + H2O

Aqueous CO2 (aq) also undergoes a number of important inorganic equilibrium

reactions. First, it can dissolve limestone

CaCO3 + CO2 (aq) + H2O ⇋ Ca2+(aq) + 2 HCO3- (aq)

Second, it can react with the water to form carbonic acid

CO2 (aq) + H2O ⇋ H2CO3 (aq)

Only a small fraction exists as the acid

and the kinetics to form H2CO3 are relatively slow (on the time scale of seconds).

Carbon Dioxide and Carbonic Acid-Base Equilibria

Dissolved CO2 in the form of H2CO3 may loose up to two protons through the acid
equilibria:

H2CO3 (aq) ⇋ H+ (aq) + HCO3- (aq)

HCO3- (aq) ⇋ H+ (aq) + CO32- (aq)

The equilibrium equations for these are labeled as "1" and "2" hence:

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To account for the fact that CO2 (aq) is in equilibrium with H2CO3 (aq), the first acid
equilibrium is normally given by:

The acid equilibrium equations can be solved to give the fraction of carbonates in a
particular form.

Relative H2CO3 concentration is really CO2 (aq) in equilibrium with water.

In summary;

• CO2 enters water through interface with the atmosphere and the biological
processes of organic carbon digestion and photosynthesis.
• Aqueous carbon dioxide, CO2 (aq), reacts with water forming carbonic acid,
H2CO3 (aq).
• Carbonic acid may loose protons to form bicarbonate, HCO3- , and carbonate,
CO32-. In this case the proton is liberated to the water, decreasing pH.
• The complex chemical equilibria are described using two acid equilibrium
equations.
• The first acid equilibrium constant accounts for the CO2 (aq) - H2CO3 (aq)
equilibrium. It concequently seems to have a high pKa.
• The fraction of the inorganic carbon in a particular form is call the "alpha" and
there are simple equation to describe this alpha.

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 Graphical Results

Consequences of the fractional amount or "alpha" equations may be understood by

examination of the graphical results. Shown to the left is a plot of the various alpha as a
function of pH.

Some important points to observe are:

For pH well below pKa1 a (H2CO3) ~ 1

At pH = pKa1, a (H2CO3) = a (HCO3-)
For 7<pH<10, HCO3- is the predominant species

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 The pH of water (no lime)

We now have enough information to calculate the pH of water.

First, we calculate the amount of CO2 dissolved in water under an atmosphere of

pressure from Henry’s Law:

Since CO2 makes up 0.0355% of the atmosphere (on the average) and:

KCO2 =2 x 10-3

Since is in equilibrium with H2CO3 (aq), the first acid equilibrium is normally given by:

is predominant. Also since:

CO2 (aq) + H2O ⇋ H+ (aq) + HCO3- (aq)

The proton and bicarbonate concentrations are equal. Thus:

When we substitute the carbon dioxide concentration, and solve for pH, we get:

pH = 5.65

Since rain is in equilibrium with the atmosphere, this is the pH expected for natural rain.
It is also the pH expected if the body of water is in equilibrium with the atmosphere,
and does not contact limestone (e.g., CaCO3).

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 Water Alkalinity

Alkalinity is the defined as a body of water’s ability to react with the acidic proton. The
alkalinity is like buffer capacity in that higher alkalinity is associated with a body of
water’s ability to "soak up" proton without altering the pH. Alkalinity is an important
concept in understanding the effects of acid rain.

Alkalinity is different from basicity, which is directly related to the pH. The higher the
pH, the more basic the water.

Like acidity, there are different ways to measure and report alkalinity;

The first is to titrate the water with acid titrant to the phenolphthalein end point. This is
called the phenolphthalein alkalinity. Since phenolphthalein changes color at pH~8.3,
this corresponds to a pH where all the CO32- present would be protonated.

Second, acid titration to a methyl orange end point, pH~4.3, further converts the
bicarbonate to aqueous carbon dioxide. At this end point, some of the weaker conjugate
bases are protonated. The methyl orange end point titration indicates total alkalinity.

Alkalinity is typically defined in terms of the equivalent weight, in milligrams (mg), of

CaCO3 per liter of water. In other words, assuming that the alkalinity is due only to the
presence of CaCO3. The mg of CaCO3 per liter is determined assuming all HCO3- comes
from CaCO3.

The standard method used to determine alkalinity is to titrate 100 mL of water with 1.0
x 10-2 mole L-1 H2SO4 (sulfuric acid) titrant to a methyl orange end point. In this case,
the alkalinity, expressed in mg CaCO3 per liter, is simply 10 � mL titrant. The factor-
of-10 comes from the various volume fractions and the formula weight of 100 g mole -1
for CaCO3.

The alkalinity of a body of water is important in the context of the acid rain problem.
The more alkaline the water, the less susceptible it is to acidification. The EPA
classifies water susceptibility to acid rain based on the following:

Classification Alkalinity (mg CaCO3 /L)

critical below 2

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 endangered between 2 and 5

highly sensitive between 5 and 10

sensitive between 10 and 20

not sensitive above 20

In addition, a body of water is designated as acidified if the alkalinity classification is

"critical" and the pH is less than 5.

Using the model that all proton activity comes from the presence of CaCO3 results in a
neat expression for the alkalinity

[alk] = [HCO3-] + 2[CO32-] + [OH-] – [H+]

where [alk] is the effective alkali concentration (in equivalents or moles per liter). The
2[CO32-] factor takes into account that each CO32- reacts with 2 H+ to form CO2 (aq).

It might also be recognized that [OH-] and [H+] are always related through the water
equilibrium:

H2O ⇋ H+ + OH-

which has the equilibrium constant:

KW = [H+][OH-] = 10-14 @ 25oC

In addition, the relative amounts of total CO2 (aq) will be a function of pH. We examine
the pH-dependent solubility of CO2 before addressing the issue pH-dependent alkalinity.

How to calculate and use the "a" fractional distributions. Derivation of

the Distribution of Acid Species.

It is often necessary to determine the distribution of acids and conjugate bases as a

function of pH from first principles. This can most easily be accomplished by
determining the relative fractions, the α, in particular forms. To do this, we start with
the mass balance and equilibrium equations for the system, and then solve for the α
as functions of the equilibrium constants and [H3O+].

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As an example, consider a 'generic' tetra-protic acid (four protons) H4A. In solution, this
acid will be distributed in the form of five different species; the acid and the four
conjugate bases.

The mass balance equation for this acid is:

where FA is the formal concentration (formula weights per liter of solution) of the acid.
In addition to the chemical expressions, the acid equilibria are expressed by the four
equilibrium equations:

One can also find the formation constant, or β equations. These are found by taking
products of the equilibrium equations:

Notice that the Ka1 and β equations give concentrations of the conjugate bases in terms
of only the Ka's, [H4A], and [H3O+]. Using these equations, one then solves for the anion
concentrations, and substitutes the resulting equations into the mass balance equation.
The mass balance equation becomes:

One then multiplies both sides of the equation by [H3O+]4 to yield:

Rearrangement gives the first α, the fractional amount of acid in the form of H4A:

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Notice that this equation gives [H4A] in terms of known quantities, e.g., [H3O+], FA, and
the equilibrium constants. We have used a convention such that the α subscript signifies
the number of protons lost from the most protonated form of the acid. Thus α0 signifies
that no protons are lost. α1 would be the fraction of the first conjugate base, e.g., one
proton lost, α2 signifies two protons lost, etc.

To obtain the other α, one uses the K and β equilibrium equations to obtain the
conjugate base concentration in terms of [H4A], [H3O+], and the appropriate constants,
and then substitutes into the α0 equation. For example, α1 is found using the Ka1
equilibrium equation. Solving the Ka1 equilibrium equation for [H4A], one obtains:

Substitution into the α0 equation and rearranging, one gets:

Similarly, solving the βa2 equation for [H4A] yields:

which when substituted into the α0 equation yields:

Using the same procedure, i.e., solving the β equations for [H4A] followed by
substitution into the α0 equation, gives the remaining α equations:

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In general, for an n-proton acid, one finds that the " expression all have the same
denominator:

and the αk, where αk is the fractional amount of the k'th ion, will be of the form:

Use of Acid/Base Distributions in pH Problems

Once the fractional amounts of all species are known, we can put these expressions to
work in complex equilibria problems involving acids and bases at known pH's.

First, let's determine the relative amounts of all species in the phosphoric acid
equilibrium. If we were to control the pH, and to somehow measure the relative
amounts of H3PO4, H2PO4-, HPO42-, and PO43-, what would we expect to observe?
Phosphoric acid has three equilibria:

The corresponding α are:

where FA is the formal concentration of phosphoric acid in solution. One expects to find
more H3PO4 at lower pH since α0 is proportional to [H3O+]3 (low pH corresponds to high

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[H3O+]). Similarly, at very high pH (thus low [H3O+]) [H3PO4] will tend to zero while
[PO43-] would be maximum.

It is easy to calculate the fractional concentrations if we know the equilibrium constants.

The equilibrium constants for phosphoric acid are; Ka1=7.11x10-3; Ka2=6.32x10-8; and
Ka3=7.1x10-13. Using the α one could calculate the relative concentrations at any pH.

It is instructive to examine a plot of the α as a function of pH. Several interesting

'features' are apparent by examining trends illustrated in the plot with the equations
describing the concentrations. First, notice that the pH where two species concentrations
are the same is around the pKa for that equilibrium. In fact, for polyprotic acids with
pKa's that differ by over 3 to 4 units, the pH is equal to the pKa. Take for example the
point where [H3PO4] = [H2PO4-]. The equilibrium equation relating these two species is:

If we take the -log10, or "p", of this equation:

Since [H3PO4] = [H2PO4-], and log10(1) = 0, pH = pKa1.

Second, you might notice that the concentrations of the conjugate bases are maximum
half-way between the pKa points. For example, the point where [H2PO4-] is a maximum
lies half-way between pKa1 and pKa2. Since H2PO4- is the major species present in
solution, the major equilibrium is the disproportionation reaction:

This equilibrium cannot be used to solve for pH because [H3O+] doesn't occur in the
equilibrium equation. We solve the pH problem adding the first two equilibria
equations:

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Note that when we add chemical equilibria, we take the product of the equilibrium
equations. Taking the -log10 of the last equation:

Since the disproportionation reaction predicts [H3PO4] = [HPO42-]:

Use of Acid Distributions in Solubility Problems

For solutions with controlled pH, the counter ion solubility effects are easily accounted
for in determining the solubility of a salt producing a conjugate base. Say we have a
metal/conjugate base salt, MA, that ionizes (dissociates) in solution by

where An- is a conjugate base of an acid with equilibria

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etc.

Although the salt dissociates to form Mn+ and An-, the An- is basic and `grabs' protons
from water. Acidic forms of the An- anion do not form an insoluble salt complex.

The problem is not intractable. In fact, it is easy if the pH is known. To find the solution,
we note that for each mole of Mn+ dissolved, one mole of An- is initially formed. The An-,
in turn, is distributed among all acid forms.

From the αn definition we know that the fraction of acid as An- is

Substitution of this into the Ksp equation gives a simple result

As a concrete example, consider the molar solubility of calcium carbonate at pH 6.

Calcium carbonate dissociates by

The Ksp =6.0x10-9. Carbonate will be distributed as CO32-, HCO3-, and H2CO3

where Ka1 = 4.45x10-7 and Ka2 = 4.69x10-11. The α expressions are

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To find the molar solubility we use the table to find the amounts of solution phase
species.

CaCO3 (s) ⟶ Ca2+ (aq) CO32- (aq)

initial solid 0 0
change -x +x +x
final solid x x

For each x mole of CaCO3 that dissolves, x mole of Ca2+ and x mole of CO32- are
formed. The CO32- will be distributed in the different acid forms. But we know FA and
the concentrations of the various forms are still related to FA through the α

The Ksp equation is cast in the form

Using the values from the table

where x is equal to [Ca2+], FA, and is the molar solubility of CaCO3. To find the molar
solubility we first determine α2. At pH 6, [H3O+] =10-6 and α2=1.44x10-5. The molar
solubility is

Molar solubilities at other pH's are given in the Table below. Notice that CaCO3 is
soluble in acid solution but is insoluble in basic solution. This feature is used by
Geologists to test for carbonate rock (calcite). Calcite "fizzes" when HCl is dropped on
it but has no reaction with NaOH. Why does it "fizz?"

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 molar
pH pα2
solubility
2 12.68 170
4 8.68 1.70
6 4.84 0.020
8 2.34 0.0011
10 0.49 1.4x10-4
12 0.0092 7.8x10-5

solubility of CaCO3 as a function of pH

Use of equations in metal ion buffers. Distribution of Complexed Species.

Similar expressions can also be found for complexes formed from metal ions, Mn+, and
ligands, Lk-. The ligands are not always anions but the notation Lk- is used for generality.
For example, a particular metal may react with up to four ligands to form complexes in
a series of equilibrium steps

An example of a four ligand complex is the Pb 2+/I- system discussed in Harris's

Quantitative Chemical Analysis. The mass balance equation in this case is the sum of all
chemical species containing a metal

where FM is the formal concentration of the metal. The equilibria can be expressed in
the four formation constant equations

As with the acid, the β are formation constants equal to products of individual
equilibrium constants. One substitutes the formation constant equations into the mass
balance equation and obtains the formal metal concentration in terms of that of the
ligand and the equilibrium constants.

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Using the convention that the subscript on the a signifies the number of ligands around
the metal, α0 is

Solving the K1 equation for [Mn+] and substituting into a0 gives

The remaining a are found by solving the other equilibrium equations for [Mn+]
followed by substitution into the α0 expression. These are left up to the student as an
exercise.

pH dependent CO2 solubility. A river in New Hampshire.

These approximate calculations work for water buffered by acids/bases and when the
water is not in contact with limestone. Keep in mind that the water is probably not at
equilibrium.

The maximum total amount of CO2 that may dissolve in water is a function of pH.

This is because as pH changes, the fraction of the total dissolved CO2 as CO2 (aq) also
changes.

On the other hand, the concentration of CO2 as CO2 (aq) does not change because of
the Henry’s Law equilibrium between the large reservoir of gaseous CO2, i.e., the
atmosphere, and the relatively finite body of water.

It is relatively easy to calculate the fractional amount of CO2 (aq) as a function of pH

and the Henry’s Law concentration of CO2 (aq).

As shown in the overhead for the Carbon Dioxide and Carbonic Acid, the Henry’s Law
concentration (@ 25 oC) is

[CO2 (aq)]=1.2·10-5 mole/L

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Also, the fraction of carbonate species as CO2 (aq) is

One may solve this equation to obtain total CO2 (aq) as a function of [CO2 (aq)], [H+]
and the acid equilibrium constants

The total CO2 in moles per liter is plotted as a function of pH below.

Some points to keep in mind;

The pH is related to proton concentration by [H+]=10-pH

The acid constants for H2CO2 are Ka1=4.45x10-7 and Ka2=4.69x10-11
The first acid constant accounts for the relatively small fraction (~0.1%) of CO2 (aq)
as H2CO2
The CO2 (aq) concentration is a function of the Henry's Law solubility and the partial
pressure of CO2 (g) in the air above the water
CO2 (g) makes up ~0.0355% of the atmosphere (on the average) and has the Henry's
Law constant  KCO2 =2x10-3 @ 25oC.
While CO2 (aq) concentration is independent of pH, concentrations of the other
species, i.e., HCO3- and CO32-, vary with pH
Subsequently, total CO2 (aq) concentration increases with pH due to an increase in

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HCO3- and CO32-
The total CO2 (aq) concentration is stable at pH below 5.5 because the major species
is CO2 (aq)
The total CO2 (aq) concentration increases the pH range between 6 and 11 due to an
increase in HCO3-

Biological Reactions of Organic Carbon

1. Hydrocarbon Oxidation

Oxidation of organic carbon compounds may be classified into two main types
of reactions.

The first is the oxidation of hydrocarbons. This oxidation occurs in a multi-step

process. The first step is the oxidation of a terminal, or a carbon

Acid formation is more common than that forming the ketone. These reactions
probably involve intermediates (alcohols and aldehydes) and may involve H2O,
H+, and e-.

The next step removes the acid and the second, or b carbon, through a processes
call "b-oxidation"

β-oxidation may continue until the hydrocarbon is converted to CO2 and H2O.

β-oxidation requires labile bonds on the b carbon. Subsequently, branched

hydrocarbons are not oxidized as rapidly.

2. Aromatic Oxidation

The primary step of aromatic compound oxidation occurs by an epoxidation

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The epoxide may rearrange to the phenol in the hydroxylation reaction

or may be further oxidized to acids or ketones

Products in the oxidation of naphthalene by the fungus Cunninghamella elegans

are shown below. These products can be explained by initial epoxidation of the 1
and 2 carbons.

Notice that more than one oxidation is required to produce some of these
products.

Biological Reactions of Methane

Methane (CH4) production and oxidation by microorganisms is important to the

understanding of the global carbon cycle. Microorganisms are thought to
produce about 80% of the atmospheric methane.

Methane is produced in very low pE (reducing) environments under anaerobic

oxygen-free conditions by bacterial decomposition of organic materials.

The methane-forming (methanegenic) bacteria convert carbon dioxide to

methane

where the carbon dioxide comes from organic carbon

Overall, the combination of these two reactions is

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 The methanegenic bacteria are anaerobic. They die in oxygen. They significantly
reduce the BOD by the production of methane.

Since

and since CH4 is a gas which is vented from the water, each mole of CH4 gas
produced reduces the oxygen demand by 2 moles.

More Biological Reactions of Organic Carbon

3. Hydrolysis - Hydrolysis involves the addition of water to a relatively labile bond

accompanied by cleavage into two products.

One of the resulting compounds is protonated while the other is hydroxylated.

Hydrolysis is promoted by hydrolase enzymes. Esters (R-C=O-OR’), amides (R-

C=O-NHR’), and their analogs are labile to hydrolysis.

4. Organic Reduction - Biological reduction occurs via reductase enzymes. Table

6.2 gives some examples.
5. Dehalogenation – These reactions are nucleophilic substitutions of OH - for the
halides; I-, Br-, Cl-, and to a lesser extent, F-.

Microorganism dehalogenation does not always produce the alcohol, but rather
the alcohol, if it exists, is reduced to the hydrocarbon

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 Fluorocarbons are particularly difficult to defluorinate due to the high C-F bond
strength. This bond is generally stronger than the C-H bond.

6. Dealkylation – These reactions involve the removal and oxidation of an alkyl

group attached to a labile bond. It is similar to hydrolysis.

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