Lecture #5: Water Chemistry

(Chapter 9 in Faure, 1998)

Activity vs. Concentration with Minimal Mathematics
Most textbooks define the concentration and activity ("effective concentration") of a
chemical species in a water sample with the following equation:
a = m
where:
a = "activity" or "effective concentration" of the dissolved species
m = molar or molal concentration of the dissolved species
= "activity coefficient"
But, what does this equation really mean on an atomic level? Lets look at the
significance of concentration and activity by using KCl (sylvite) dissolved in water as an
example.
Potassium chloride (KCl) is very soluble in water. In very dilute solutions, abundant
water molecules almost completely separate KCl into distinctive K+ and Cl- ions (see
Figure 1 on the next sheet, Nebergall et al., 1976, p. 316). The positive partial charges
(+) on the hydrogens of the water molecules surround the Cl- and the partial negative
charges (-) on the oxygens of other water molecules are attracted towards the K+. The
presence of abundant water molecules around the K+ and Cl- essentially makes the ions
independent of each other.
The potassium concentration of the solution refers to the total number of potassium
atoms in the solution or the mass of the potassium in the solution. Typically, the
concentration is given in milligrams of potassium per liter of water (mg/L). Because a
liter of water has an approximate mass of l kilogram (compare Table 9.1, p. 114), we can
also express mg/L mg/kg, where: 1 mg/kg = 1 part per million (ppm). If we're more
interested in the number of potassium atoms in the solution rather than the mass of the
potassium in the solution, we can express the concentration as moles of solute/liter of
solvent = molar = M.
Solute = dissolved material. Solvent = the dissolving medium, often water.
A mole of a substance is the atomic weight of the element or the formula weight of the
compound expressed in grams. For example, the atomic weight of mercury is 200.59.
Therefore, 1 mole of pure liquid mercury is 200.59 grams. One mole contains
Avogadro's number of molecules or atoms, or 6.022 x 1023. Therefore, one mole of

mercury contains 6.022 x 1023 atoms of mercury. The formula weight of KCl is 39.0983
(K) + 35.453 (Cl) = 74.5513 g/mole. One mole of solid KCl is 74.5513 grams and
contains 6.022 x 1023 molecules of KCl and 6.022 x 1023 atoms of potassium and 6.022 x
1023 atoms of chloride. If the concentration of KCl in an aqueous solution is very low, it
is easier to use millimoles of KCl/liter of water (mM/L). Recall that m = milli = 1/1000,
micro = = 1/millionth.
The activity of potassium in a solution refers to the total number of independent K+ in the
solution. Because the potassiums are well dissolved and dissociated from the chlorides
in dilute KCl solutions, the K+ activity and potassium concentration of a dilute (let's say
0.0001 M) KCl solution are essentially equal. That is, essentially 100% of the
potassiums are K+ that are unbonded to Cl-.
In more concentrated KCl solutions, there are less water molecules to shield all of the K+
and Cl- from each other. In concentrated solutions, the unshielded ions begin to attract
each other and form K+Cl- pairs or complexes (Figure 2, Nebergall et al., 1976, p. 316).
That is, some of the K+ are no longer "active" or independent of the Cl-. Therefore, in a
concentrated solution (such as 1 M KCl), the concentration of the potassium is 1 M, but
the activity, the number of independent K+, may be much less.
The K+Cl- pairs and groups of associated K+Cl- won't affect the boiling or freezing points
of the solutions as much as if they were well dissociated and active K+ and Cl-.
Specifically, independent or active K+ and Cl- attract the partial charges of water
molecules and hinder the water molecules from boiling off or arranging themselves into
ice. Therefore, K+ and Cl- lower the freezing point of water and raise the boiling point.
However, when K+ and Cl- combine into K+Cl- pairs and groups in more concentrated
KCl solutions, the K+Cl- partially neutralize each others charges, less water molecules
are then attracted to the potassiums and chlorides, and the water molecules are not as
hindered from boiling off or freezing into ice as they are in the presence of strongly
charged and independent K+ and Cl-. Although concentrated KCl solutions with their
K+Cl- pairs and groups still suppress freezing points and enhance boiling points, the
freezing and boiling points are not as affected as they would be if the potassium and
chloride ions were entirely independent and active.
Once an evaporating KCl solution reaches 4.65 M or 347 g/L at 20oC, the solution
becomes saturated. That is, the water molecules can no longer separate the high
concentrations of potassiums and chlorides. The K+, Cl-, and K+Cl- readily attract each
other and begin to grow into KCl crystals, which precipitate (Figure 3 on the attached
sheet).
Concentration = what's there. Activity = how much of what's there really affects the
chemical and physical properties of the solution. Activities are used with liquids and
solids. Fugacities describe the activities of gases.

We use activity coefficients, , to mathematically relate the concentration and activity of

a species in a solution.
a = m
again where:
a = activity
m = molar or molal concentration
= activity coefficient
In very dilute solutions, = 1 and a = m.
Example:
Let's say that we have 0.100 moles of NaCl in 1.000 kilogram of pure water (0.100 molal
NaCl).
molal = number of moles of a substance dissolved in 1.000 kilogram of solvent
(often water).
For simplicity, let's convert moles to grams:
NaCl = 22.98977 g Na /mole + 35.453 g Cl / mole = 58.443 g NaCl / mole.
Therefore, 5.8443 g of NaCl are dissolved in 1 kg of water to form a 0.100 NaCl molal
solution.
From the literature, = 0.778 for a 0.100 molal NaCl solution at 25oC. (Later, in Chapter
10, well discuss the equations that are used to calculate [activity coefficients]).
Therefore:
a = 0.100 x 0.778 = 0.0778 molal of Na+ independent of Cl- and 0.0778 molal of
Cl- independent of Na+. This means that 0.1000 - 0.0778 = 0.0222 molal of Na+ and Clhave formed ion groups with each other and are "inactive" or not part of the Na+ and Clactivity.

pH
pH = "the negative log of the H+ activity in a water sample."
The pH values do not include hydrogens covalently bonded with oxygen as H 2 O, but
only include "H+." In reality, however, H+ does not exist in water. Instead, the H+
attaches onto the - of individual water molecules as H 3 O+ or, less commonly, groups of

hydrogen bonded water molecules to form H 5 O 2 +, H 7 O 3 +, and larger complexes.

Scientists, being lazy and practical, prefer to write H+ as an abbreviation for H 3 O+,
H 5 O 2 +, H 7 O 3 +, etc.
Sketches of H 3 O+ and hydrogen-bonded H 5 O 2 + and H 7 O 3 +:

Almost all water exists as undissociated H 2 O. Only about 1 out of 1014 H 2 O molecules
dissociates as follows:
H 2 O + H 2 O H 3 O+ + OHOr using simplified abbreviations:
H 2 O H+ + OHWe can write the following mathematical equation to represent the dissociation of 1 out
of 1014 H 2 O molecules into H+ + OH- at 25oC:
[H+] [OH-]
------------[H 2 O]

1
= -----------1014

Where:
[H+], [OH-] = activities of H+ and OH-, respectively, in water.
(H+), (OH-) = concentrations of H+ and OH-, respectively, in water. In water at 25oC, the
H+ and OH- activities and concentrations are approximately equal.

The preferred format for the equation is:

Activities of the Products
-------------------------------

= constant

Activities of the Reactants

Or:
[H+] [OH-]
------------- = K W = 10-14
[H 2 O]
Because only 1 out of 1014 H 2 O molecules breaks up (dissociates) into H+ + OH-,
mathematically [H+] x [OH-] = 10-14 and [H 2 O] becomes 1.
K W = a constant, an equilibrium constant for the reaction: H 2 O H+ + OH-, K W is also
called the ion-product constant of water. Because only 1 out of 1014 H 2 O molecules
breaks up into H+ + OH-, then from the above equation, K W = 10-14.
Example Problem: What is the concentration of H+ and OH- in pure water?

We know:
[H+] [OH-]
------------- = K W = 10-14
[H 2 O]
Since [H 2 O] = 1:
[H+] [OH-] = K W = 10-14
In pure water, the following reaction is balanced:
H 2 O = H+ + OHThe reaction produces equal amounts (moles) of H+ and OH-, and therefore the activities
of the two species are equal:
[H+] = [OH-]
Because [H+] = [OH-], we can use algebra and substitute [H+] for [OH-]:
[H+] [OH-] = [H+] [H+] = [H+]2 = 10-14
_____
____
+ 2
[H ]
= 10-14
[H+] = 10-7 = [OH-]
The activities are expressed in moles/liter (molar, M). Therefore: [H+] = [OH-] = 10-7 M.

Because we're dealing with dilute solutions, activities approximately equal

concentrations. Therefore: (H+) = (OH-) 10-7 M at 25oC.
pH = -log of [H+] = -log of 10-7 = 7. Theoretically, pure water has activities
(concentrations) of [H+] = [OH-] = 10-7 M and a pH of 7.
pOH is the -log of [OH-].
pOH = 14 - pH.
Therefore, a solution with a pH of 7 has a pOH of 7, and a solution with a pH of 4 has a
pOH of 10.
We can design the following table:
[H+],
moles/liter
100 = 1
10-1 = 0.1
10-2 = 0.01
10-6
10-7
10-8
10-12
10-13
10-14

[OH-],
moles/liter
10-14
10-13
10-12
10-8
10-7
10-6
10-2 = 0.01
10-1 = 0.1
100 = 1

pH

pOH

K W at 25oC

Comment

0
1
2
6
7
8
12
13
14

14
13
12
8
7
6
2
1
0

1 x 10-14
1 x 10-14
1 x 10-14
1 x 10-14
1 x 10-14
1 x 10-14
1 x 10-14
1 x 10-14
1 x 10-14

Strong acid

Weak acid
Neutral
Weak base

Strong base

The pH values of some common materials:

Lemon juice = 2
White vinegar = 3
Beer, coffee = 4
"Clean" rainwater (contains carbonic acid from contact with CO 2 in air) = 5.7
Milk = 6.8
1 gram of baking soda (NaHCO 3 ) in 100 ml H 2 O = 8
Seawater = 8.1 to 8.3
Milk of magnesia = 10.5

Household ammonia = 11
Clam shells are made of calcite or aragonite (both are calcium carbonate, CaCO 3 ).
CaCO 3 is fairly soluble in acidic freshwater. Therefore, freshwater clams are covered
with organic layers, which protect their CaCO 3 shells from being dissolved in acidic
freshwater. Seawater has pH values of 8.1 to 8.3. CaCO 3 does not appreciably dissolve
in alkaline (basic) seawater. Therefore, marine clams do not require protective organic
coverings on the outside of their shells.
Shell Chemistry of Freshwater and Marine Clams:

Rainwater Chemistry
Uncontaminated rainwater and purified (distilled) laboratory water does not have a pH of
7. Carbon dioxide from the air readily reacts with the water to produce carbonic acid
(H 2 CO 3 ), which gives distilled water and "clean" rainwater a slightly acidic pH of about
5.7:
H 2 O + CO 2 = H 2 CO 3
Carbonic acid readily decomposes into bicarbonate (HCO 3 -) and carbonate (CO 3 2-):
H 2 CO 3 + H 2 O = HCO 3 - + H 3 O+
H 2 CO 3 + 2H 2 O = CO 3 2- + 2 H 3 O+
Carbonic acid also reacts with calcite (CaCO 3 ) in limestones and produces caves! That
is:
H 2 CO 3 + H 2 O = H 3 O+ + HCO 3 H 3 O+ + CaCO 3 = Ca2+ + H 2 O + HCO 3 Later, we'll demonstrate that the pH of "pure" rain water is about 5.7.

Rainwater chemistry is also affected by other sources:

Coal-fired power plants release SO 2 gases into the atmosphere. The SO 2 reacts
with water and oxygen in the atmosphere to produce sulfuric acid rain:
2SO 2 + 2H 2 O + O 2 = 2H 2 SO 4
Cars, lightning, and coal-fired power plants release NO, NO 2 and other nitrogen
oxides into the atmosphere, which produce nitric acid rain:
4NO + 2H 2 O + 3O 2 4HNO 3
4NO 2 + O 2 + 2H 2 O 4HNO 3
Organisms and fertilizers also release ammonia into the air and winds may blow
nitrates into the atmosphere, all of which may be converted into nitric acid.
Ocean waves break on beaches, especially during storms, and send NaCl and
other salts as dusts into the atmosphere.
Mercury is released into the atmosphere as Hg0 vapor by coal-fired power plants,
volcanoes, crematoria, forest fires, municipal waste incinerators, ocean water,
paper mills, and chloralkali plants.

pH Buffers
Buffering is the ability of a solution to resist a change in pH when an acid or base is
added. "Pure" distilled water is poorly buffered. Just a little acid or base will greatly
change the pH of distilled water. For example, a small drop of nitric acid may cause the
pH of a distilled water sample to drop from 5.7 to below 2.0. In contrast, seawater is well
buffered. A small addition of acid or base only leads to a small change in pH. For
example, a small drop of nitric acid to a sample of seawater may cause no noticeable
change in the pH. The seawater contains H 2 CO 3 and HCO 3 -, which are capable of
neutralizing (buffering) the acid or base:
To neutralize an acid (H+) that has been added to seawater:
H+ + HCO 3 - H 2 CO 3
To neutralize a base (OH-) that has been added to seawater:
OH- + H 2 CO 3 HCO 3 - + H 2 O

Another example of a buffer (a weak acid and a salt of the acid):

acetic acid (vinegar) + sodium acetate
The solution contains both CH 3 CO 2 - and CH 3 CO 2 Ho. If we add an acid, such as HCl,
the H+ is removed or neutralized by the following buffering reaction:
CH 3 CO 2 - + H+ CH 3 CO 2 Ho
If we add a base, such as NaOH, the OH- is removed or neutralized by the following
buffering reaction:
CH 3 CO 2 Ho + OH- CH 3 CO 2 - + H 2 O
Human blood is another good buffer and typically attempts to maintain a pH near 7.35.
Like seawater, blood neutralizes acids and bases with HCO 3 - and H 2 CO 3 .
The buffering reactions in human blood are:
To neutralize an acid in human blood:
H+ + HCO 3 - H 2 CO 3
To neutralize a base in human blood:
OH- + H 2 CO 3 HCO 3 - + H 2 O
Buffers may also be produced by mixing a weak base and a salt of the weak base (such as
NH 3 and NH 4 +).
Obviously, the ability of buffers to maintain nearly constant pH values may be destroyed
if too much acid or base is added to them.
Buffering has profound effects on water pollution. For example, acid rain may easily
acidify a poorly buffered lake and kill its fish, since the lake contains no large
concentrations of dissolved anions to neutralize the acid. Acid-sensitive lakes are
located in Minnesota and New England, where granites, sandstones and other waterinsoluble silicate-rich rocks are present. In contrast, lakes that contain limestones tend to
be better buffered because the calcite in the limestones can dissolve to neutralize the acid.
Again, seawater also contains abundant HCO 3 - that neutralizes acids.

References

Nebergall, W.H.; F.C. Schmidt and H.F. Holtzclaw, Jr., 1976, College Chemistry, 5th ed.,
D.C. Heath & Co., Lexington, Massachusetts.

Lecture #6: More Water Chemistry

(Chapter 20 in Faure, 1998)
Total Dissolved Solids (TDS)
Total dissolved solids (TDS) refer to the total amount of solids dissolved in an aqueous
solution, usually given in mg/L. Solids are ASSUMED to be "dissolved" if they can pass
through a 0.45 micron (m) filter. Filtering removes any suspended materials from a
water sample. TDS is usually determined through one of the three following methods:

Evaporate a known volume of a filtered water sample to dryness and weigh the
residue.
(+): easy and cheap to do.
(-): Some residues are hydrated, such as gypsum (CaSO 4 2H 2 O). The
water in the residues throws off the results. Heating the residue to drive
off the water may also evaporate some of the desired solids.

Measure the major components (Na, Ca, K, Si, Al, sulfate, carbonate species, Mg,
chloride, Fe, etc.) in the filtered water and add up their concentrations.
(+): Usually fairly accurate.
(-): Costly and locally important ions may be overlooked in the analyses,
such as boron or fluoride.

Measure the conductivity of the solution and use an equation:

The conductivity of the solution is easily measured with a portable meter.
TDS AC
C = conductivity in microsiemens or micromhos.
A = a constant taken from the literature, usually 0.55 to 0.75, depending
on SO 4 2-/Cl- of the water sample.

(+): Simple method. The meter is easy to use.

(-): Errors associated with the value of A.
(-): The equation doesn't work with seawater and other high TDS
solutions.
Waters are typically classified into several "quality classes" by their TDS values (p. 372):
Fresh: 0 to 1000 mg/L TDS. Usually suitable for drinking by humans.
Brackish: 1000 to 10,000 mg/L TDS. Unfit for human consumption, but lower TDS
brackish waters may be used for industrial purposes, crop irrigation or watering livestock.
Saline: 10,000 to 100,000 mg/L TDS. Seawater is about 35,000 mg/L. These waters are
generally unfit for industrial or agricultural uses.
Brine: >100,000 mg/L TDS. Great Salt Lake, Utah and some deep groundwaters. Used
for underground disposal of liquid wastes.
Underground Injection of Liquid Wastes into the Brines:

Water Hardness
Water hardness is determined by the amount of Mg2+ and Ca2+ in the water:
Hardness = 2.5(Ca2+) + 4.1(Mg2+)
The concentrations of Mg2+ and Ca2+ are in mg/L.

"Hard water": Hardness > 150 mg/L

"Intermediate water": Hardness of 60 - 150 mg/L
"Soft water": Hardness < 60 mg/L
Hard water leaves calcium and magnesium carbonate deposits in water heaters, boilers,
shower heads, pipes and drains. In boilers and water heaters, the scale acts as an
insulator, which requires more fuel to heat the water. Hard water keeps soaps from
lathering and produces bathtub rings. Hard water leaves scum on clothes rather than
cleaning them in washing machines. Therefore, more soap is needed to clean yourself
and your clothes with hard water.
If thick hard water deposits are present on the inner walls of a water heater tank, the tanks
must become very hot to boil the insulated water. If the scale cracks, hot water may flow
into the cracks and become exposed to hot elemental iron in the boiler wall. Explosive
hydrogen gas may then be produced:
4 H 2 O + 3 Fe0 (hot) Fe 3 O 4 + 4 H 2 (BOOM!!)
Note: Fe 3 O 4 = (Fe3+) 2 Fe2+O 4

Water Softening
Water "softening" refers to the removal of calcium from water with sodium zeolites. In
the softening process, sodium is released into the water.
Removal of calcium from water with sodium zeolites:
2 NaAlSi 2 O 6 nH 2 O + Ca2+ Ca(AlSi 2 O 6 ) 2 nH 2 O + 2 Na+
The reaction is then reversed with concentrated NaCl solutions and the zeolite is
regenerated for reuse:
Ca(AlSi 2 O 6 ) 2 nH 2 O + 2 Na+ 2 NaAlSi 2 O 6 nH 2 O + Ca2+
Dissolved Oxygen (DO)
Oceans, lakes, ponds and streams must contain enough dissolved oxygen (DO) to
support aquatic life. DO is usually measured with a meter and may be done in the field.
The DO concentration of a water sample is affected by the life forms in the water,
temperature, pressure, and water chemistry, including the presence of pollutants. Organic
matter, FeS 2 , other sulfides, and many life forms consume DO. Typically, fresh water at

5oC has a maximum DO concentration of about 12 mg/L (see the attached sheet with
Table 8-1 from Drever, 1997, p. 167). At 30oC, the DO concentration drops to 7.5 mg/L.
Biological Oxygen Demand (BOD) and Chemical Oxygen Demand (COD)
Some organic pollutants are nutrients for organisms. Therefore, the release of sewage
and other organic pollutants into surface waters may cause dramatic increases in the
growth of bacteria, algae, and other organisms. The organisms obtain energy from
organic compounds by breaking down the organics into simpler compounds and CO 2 .
Overpopulating bacteria and algae may lower DO concentrations and cause fish kills and
other ecological damage in lakes, ponds, and streams.
Not every organic compound is biodegradable and readily available as food for
organisms. As examples, tars, most plastics, and other organics consisting of large and
complex molecules tend to be non-biodegradable. Organisms prefer to eat small organic
molecules and small molecules are also more susceptible to destruction from oxygen or
other chemical reactions. Biological (or biochemical) oxygen demand (BOD) estimates
the amount of biodegradable carbon in a water sample, which is a potential food supply
for bacteria and other organisms. High BOD surface waters may cause organisms to
overpopulate and kill fish. Chemical oxygen demand (COD) measures the amount of
organic matter in a water sample that may decompose through chemical oxidation. Both
BOD and COD concentrations in mg/L provide some indication of the health or level
of pollution in a ground or surface water.
Biological (or Biochemical) Oxygen Demand (BOD)
While pH and dissolved oxygen may be measured in the field with meters, BOD must be
measured in an analytical laboratory. The sample is diluted with oxygenated water. The
sample is then stored in the dark at 20oC and the dissolved oxygen concentration is
measured 5 days later. The amount of dissolved oxygen that is consumed over the five
days gives some idea of the amount of readily biodegradable (reactive) organic
contaminants that are present in the water sample. That is, the bacteria and other
organisms in the water consume the organic matter and oxygen in the water during the 5day analysis.
Example: A sewage treatment plant is being constructed along a river. How does the
amount of biodegradable organic matter vary in the river before the construction of the
plant, during plant construction, and once the plant is operating? Take BOD
measurements downstream from the plant construction site before, during and after the
plant is built.

Chemical Oxygen Demand (COD)

Chemical oxygen demand (COD) analyses are generally more rigorous and faster than
BODs. COD is a measure of the amount of chemically destructible organic matter in a
water sample, which includes the biodegradable organic materials detected by BOD
analyses and organics that are more resistant to biodegradation and not detected by
BODs. Specifically, COD is a measure of the amount of organic materials that will react
with strong oxidizing agents, either potassium permanganate (KMnO 4 ) or potassium
dichromate (K 2 Cr 2 O 7 ). (We'll discuss the oxidation of organic matter later.) BOD is
probably a better estimate of the amount of carbon that is likely to react in nature, but
COD analyses don't require 5 days to analyze. You also have to subtract out the
carbonate (inorganic carbon) concentrations (CO 3 2-, HCO 3 -, H 2 CO 3 0) from the COD
results. The amounts of CO 3 2-, HCO 3 -, H 2 CO 3 0 in a water sample will vary with pH and
other conditions. Professional analytical chemists can usually determine the
concentrations of various carbonate species in water samples.
Total Organic Carbon (TOC)

Total Organic Carbon (TOC) refers to the entire concentration of all organic materials
in an unfiltered water sample, including: microorganisms, plant and animal debris,
suspended materials and dissolved materials. If the sample is filtered at 0.45 microns
(m) before the carbon analysis, the results are called "dissolved" organic carbon
(DOC). Filtering at 0.45 m is arbitrary and was once considered the size boundary
between "dissolved" and "suspended" particles. That is, particles smaller than 0.45 m
were once considered "dissolved" and potentially able to readily move through ground
and surface waters. Particles larger than 0.45 m were considered "suspended" and were
expected to settle out of surface waters in short periods of time or be filtered out of
ground water as the ground water passed through the subsurface. As we will see later
when we discuss colloids, these assumptions are now known to be often incorrect and
may lead to profound errors in predicting the movement of contaminants through natural
waters.
TOC and DOC analyses are performed in analytical laboratories. The carbon in the dried
residue of a water sample is burned, the resulting CO 2 is measured, and the TOC or DOC
is then calculated from the CO 2 analysis after subtracting out the inorganic carbon
(carbonate). Rainwater, seawater and most groundwater typically have about 0.5 mg/L of
DOC. DOC values of rivers and lakes usually are 2-10 mg/L (Drever, 1997, p. 107).
Waters from soils, marshes and bogs may contain more than 50 mg/L DOC. "Black
waters" are brownish, high DOC waters that are common in tropical wetlands.

How Good are Your Water Analyses? Did You Analyze All of the Important
Constituents? Possible Answers Using Water Ion Balances
If the chemical analyses of a water sample are reliable and complete, the number of anion
charges should equal the number of cation charges. If the measured cation and anion
charges are not similar, then:

significant errors may be present in the analyses. For example, if the sulfate
(SO 4 2-) analysis is too low, then the total measured amount of cations may exceed
the total measured amount of anions.

some ions that are usually not in significant concentrations in water samples may
be present in significant concentrations in the sample and are being overlooked
(such as: iron, aluminum, boron or fluoride).

The following equation is used in the ion balance analysis:

E = [( /z/m c - /z/m a ) / ( /z/m c + /z/m a )] x 100
where:
E = charge balance error in %. For acceptable results, E < 5%.
m c = moles of each cation
m a = moles of each anion
/z/ = absolute value of the charge of the ion
Of course, it's possible that errors in the cation analyses may cancel out errors in the
anion analyses. Therefore, a low E value does not guarantee the accuracy of the
chemical analyses of a water analysis. Furthermore, the sum of the concentrations in
mg/L of the anions, cations and dissolved neutral species (such as H 2 CO 3 o and SiO 2 o)
should equal the total dissolved solids (TDS) of the sample in mg/L.
For the charge balance equation to work, we need to balance the charges on all of the ions
in the water sample. This means that we need to work with moles and not mg/L (weight
per volume) in the equation. We also need to account for charge differences (z) among
the different ions.

For example, a charge balance between Ca2+ and HCO 3 - in water:

Ca2+

HCO 3 -

atomic mass units = 40.08

atomic mass units = 61.02

1 cation +2 charge

1 anion -1 charge

We need two HCO 3 - to charge balance every Ca2+. We're interested in the
charges of each ion and their numbers (moles), and not their weights. Therefore,
we'll work with moles (m) and charges (z), and not milligrams.

Example: A water sample has the following concentrations:

Species
Na+
K+
Ca2+
Mg2+
Sr2+
SO 4 2ClHCO 3 SiO 2 0
pH

Except pH, concentrations in ppm

120
15
380
22
0.8
1115
15
150
21
7.4

Perform a charge balance. (Watch significant digits!!):

SiO 2 o and any other neutral species have z = 0, and are not involved in the charge
balance. They are ignored. The pH of the water = 7.4 or H+ = 1 x 10-7.4 M is insignificant
and will be ignored in the charge balance analysis. At pH 7, the OH- concentration is
also insignificant.
parts per million = ppm = mg/kg

Cations
Cation

ppm =
mg/kg

mg/kg
1000 mg/g
= g/kg

Na+
K+
Ca2+
Mg2+
Sr2+
Cation
Sum

120
15
380
22
0.8

0.120
0.015
0.380
0.022
0.0008

atomic
mass
(g/mole)
22.99
39.10
40.08
24.31
87.62

= moles/kg
(molal, m)

Absolute
value of
charge on
ion, /z/

mcz

0.00522
0.00038
0.00948
0.000905
0.000009

1
1
2
2
2

0.00522
0.00038
0.01896
0.00181
0.000018
0.0264

Anions
Anion

ppm =
mg/kg

mg/kg
1000 mg/g
= g/kg

mass
(g/mole)

= moles/kg
(molal, m)

maz

SO 4 2ClHCO 3 Anion
Sum

Absolute
value of
charge on
ion, /z/

1115
15
150

1.115
0.015
0.150

96.06
35.45
61.02

0.01161
0.00042
0.00246

2
1
1

0.02322
0.00042
0.00246
0.0261

Significant digits: DO NOT round off the results until you get the final answer!!
E = [0.0264 - 0.0261)/(0.0264 + 0.0261)] x 100
E = 0.0003/0.0525 x 100
E = 0.6%, which is very good. E < 5% is acceptable.
Chemical Compatibility in a Water Sample: A Few Examples
Some chemical species are incompatible with each other in water. For example, if the
sulfate concentration of a water sample is much greater than about 1000 mg/L, the
barium concentration should be less than 1 mg/L. In the presence of sulfate, barium
precipitates as water-insoluble barium sulfate. Unless the pH is low, barium
concentrations should also be low in the presence of more than 1000 mg/L of carbonate.
Barium carbonate is also sparsely soluble in unacidified water. Silver is insoluble in the
presence of chloride in water. These relationships may be used to detect questionable
analytical results. More examples will be given later.

Brief Comments on Field and Laboratory Blanks and Standards

Field and laboratory blanks and standards are important for verifying the quality of
analytical data from laboratories. For example, if you believe that your surface or ground
water samples contain about 100 mg/L of chloride and 100 mg/L of sodium, dissolve
ultrapure sodium hydroxide (NaOH) and hydrochloric acid (HCl) into clean (distilled and
deionized) laboratory water to produce a standard that contains only 100 mg/L of
chloride, 100 mg/L of sodium and nothing else. Anomalously submit the standard to the
analytical laboratory along with your water samples. Also submit, as "blanks," samples of
distilled and deionized water and any acids that are used to preserve the ground or surface
water samples. For the blanks and standards, use the same types of containers that were
used for your water samples. If the water and acids blanks and their containers are
properly clean and if the laboratory is using appropriate procedures, nothing significant
should be detected in the blanks. The analytical laboratory should only detect sodium
and chloride in the standard and they should obtain values that are within 5-10% of the
known concentrations of sodium and chloride (that is, in the case of a 100 mg/L chloride
and sodium standard, the lab should report between 90 to 110 mg/L of sodium and
chloride). If the values are off, find another laboratory. It is always a good idea, if you
can afford it, to submit a few samples to a second laboratory to confirm the analytical
results of the primary laboratory.
Furthermore, if your water samples contain more than 5,000 mg/L TDS, it is important to
find a laboratory that routinely analyzes seawater and other high TDS samples. You may
have to ship your water samples off to New Orleans, New York or other coastal cities to
find an analytical laboratory that routinely analyzes high TDS samples. There have been
cases of laboratories in the Lexington area finding toxic concentrations of silver and
other contaminants in water samples. In reality, the metals were not in significant
concentrations. High concentrations of sodium, chloride, sulfate and other ions in water
samples often produce interferences in analytical equipment that appear as falsely high
concentrations of silver, cadmium, arsenic and other toxic metals. For example, I've seen
an arsenic-free 1000 mg/L aluminum standard produce a false measurement of about "3
mg/L" of arsenic. Many analytical chemists are not trained to spot and correct for these
interferences and simply report the imaginary results as being real. Obviously, bad data
can lead to erroneous interpretations and, without proper confirmation, could lead to
unnecessary remediation (site clean up) efforts that waste a lot of valuable time and
money. In other words, DONT ALWAYS BELIEVE YOUR DATA! More later...
Piper and Stiff Diagrams
"Pictures and Graphs are Worth a Thousand Numbers."
Water chemical data are better seen and understood in Piper and Stiff diagrams rather
than in long tables and lists of numbers. Piper diagrams are discussed on p. 372, 374 in
Faure (1998). Stiff diagrams are explained in Appendix I of Drever, p. 409-412, which
are attached to this handout.

Piper Diagrams
Piper diagrams show the major anion and cation chemistry of a water sample as a point
on a trilinear diagram, as shown in Figure 20.2 on p. 374. Before the concentrations of
the major cations and anions can be plotted on the Piper diagram, the concentrations must
be in the form of "equivalents of ion per kilogram of water." Here are the conversion
steps from ppm to equivalents/kg, which closely resemble the steps used with the charge
balance equation:
ppm = mg/kg
mg/kg 1000 mg/g = g/kg
g/kg atomic mass units in g/mole = mole/kg x /z/ = equivalents/kg
Example:
Convert 40.00 ppm Ca2+ to equivalents/kg:
40.00 ppm = 40.00 mg/kg
40.00 mg/kg 1000 mg/g = 0.0400 g/kg
0.0400 g/kg 40.08 g/mole = 9.980 x 10-4 moles/kg
9.980 x 10-4 moles/kg /+2/ = 1.996 x 10-3 equivalents/kg
Let's say that we have a water sample with the following concentrations:
Ca2+ = 40.00 ppm, 1.996 x 10-3 equivalents/kg
Mg2+ = 15.00 ppm, 1.234 x 10-3 equivalents/kg
Na+ = 120 ppm, 5.22 x 10-3 equivalents/kg
K+ = 20.0 ppm, 0.51 x 10-3 equivalents/kg
Sum cations = 8.96 x 10-3 equivalents/kg
Next convert the concentrations of the cations to percentages of the total equivalents/kg.
The percentages of potassium and sodium are combined:
Ca2+ 22.3 %
Mg2+ 13.7 %
Na+ + K+ 64.0%
______________
Sum: 100.0 %

They should sum to 100.0% and they do.

For the anions:

The alkalinity of the water sample (essentially CO 3 2- + HCO 3 - in most waters)
was measured as 2.8 meq/kg.
2.8 meq/kg = milliequivalents/kg = 2.8 x 10-3 equivalents/kg
Sulfate = 234 ppm = 4.88 x 10-3 equivalents/kg
Chloride = 45.0 ppm = 1.27 x 10-3 equivalents/kg
The anions' equivalents/kg are also summed and converted to percentages:
Alkalinity (CO 3 2- + HCO 3 -) 31.3 %
54.5 %
SO 4 2Cl
14.2 %
___________
Sum anions:

100.0%

The percentages are then plotted on the Piper plot, as shown in Figure 1, Drever (1997, p.
410) on the attached sheets. On the lower left side of the Piper plot is a triangle with Mg
on the top, Ca on the lower left and Na + K on the lower right. Each corner of the
triangle represents 100% of the element on the corner. In other words, a water sample
with 100% Mg and no Ca, Na, or K would plot as a point on the very top of the triangle.
Figure 1 on p. 410 shows the location of a point with 64.0% Na + K, 13.7 % Mg and 22.3
% Ca. As expected, the point is located nearest to the Na + K corner.
The anions are plotted on a triangle on the lower right corner of the Piper plot (Figure 1,
p. 410 on the attached sheet). 100% Alkalinity is located on the lower left corner of the
triangle, 100% sulfate on the top corner of the triangle and 100% chloride on the lower
right corner. Finally, a line is drawn from the point in the cation triangle parallel to the
triangular graph lines and into the diamond in the center of the diagram (Figure 1, p.
410). Another line is drawn from the anion point parallel to the graph lines in the anion
triangle and into the diamond. The point in the diamond of the Piper plot, where the two
lines cross, represents the major anion and cation chemistry of the water sample. Notice
that the points represent relative concentrations between the major ions rather than
absolute concentrations. Therefore, the chemistries of a 100,000 mg/L TDS brine and a
500 mg/L TDS fresh water sample could plot in the same location on the diagram.
Piper diagrams are very useful for plotting the chemistries of groundwaters or natural
waters from a given area and comparing them. Also, the chemistry of a particular river,
lake or groundwater may be plotted on a Piper diagram over time to track chemical

changes in the water because of increased pollution, droughts, increased crop irrigation,
urban development, etc. The data are easier to interpret on Piper diagrams than in long
lists of tables.
Stiff Diagrams
A Stiff diagram is another convenient way of plotting the major ion chemistry of a water
sample (Drever, 1997, p. 411-412 on the attached sheets). Stiff diagrams are polygons.
Stiff diagrams for particular rivers, lakes or well waters may be easily and conveniently
plotted on a map of an area. Typically, only the Na + K, Mg, Ca, carbonate, sulfate, and
chloride concentrations are plotted on Stiff diagrams. The ions are usually plotted in
milliequivalents/liter. The larger the polygon is, the higher the TDS of the water.
Furthermore, if the major cations and anions are balanced, the right side of the polygon
should have roughly the same area as the left side. If not, as with the ion balance
equation, the following problems may be present:

significant errors may be present in the analyses. For example, if the sulfate
analysis is too low, then the total area represented by the cations may exceed the
area of the polygon represented by the anions.

some ions that are usually not in significant concentrations in water samples may
be present in this sample and are being overlooked (such as: iron, aluminum,
boron or fluoride).

Figure 3 in Drever, 1997 (p. 412 on the attached sheets) shows how Stiff diagrams are
plotted. Notice the shape and size differences of the high TDS (Figure 3b) and low TDS
(Figure 3c) calcium carbonate-rich waters.
The cation and anion concentrations in milliequivalents/liter of the water analysis on page
409 in Drever (1997, see attachments) are:
Ca2+
Mg2+
Na+ + K+

1.996 x 10-3 equivalents/kg 2.0 milliequivalents/liter

1.234 x 10-3 equivalents/kg 1.2 milliequivalents/liter
5.73 x 10-3 equivalents/kg 5.7 milliequivalents/liter

Alkalinity (CO 3 2- + HCO 3 -) 2.8 x 10-3 equivalents/kg 2.8 milliequivalents/liter

SO 4 24.88 x 10-3 equivalents/kg 4.9 milliequivalents/liter
Cl1.27 x 10-3 equivalents/kg 1.3 milliequivalents/liter
Because it's difficult to plot Stiff diagrams to an accuracy of greater than 0.1
milliequivalents/liter, only two significant digits are listed above.

Using a ruler and the guidelines in Figure 3, the Stiff diagram may be easily plotted. A
Stiff diagram for the water analysis plotted on the Piper diagram in Figure 1, p. 410 is
shown in Figure 3a, p. 412 (see attached sheets).
Estimating Relative TDS values and Charge Balances for Water Samples Using Stiff
Diagrams on Maps. Which water sample has the lowest TDS? Which water sample
shows a charge imbalance?

References:
Drever, J.I., 1997, The Geochemistry of Natural Waters, 3rd ed., Prentice Hall,
Upper Saddle River, NJ 07458.

Lecture #9: Systems and Chemical Equilibrium

(Chapters 9 - 11 in Faure, 1998)
Systems
A system is a part of the Universe that is under consideration or study. A garbage
landfill is an example of a system. Lake Superior or the Atlantic Ocean also may be
identified as systems. Our home galaxy, the Milky Way, may be considered as another
system. The surroundings are the rest of the Universe outside of the system.
Systems may be classified as open, closed, or isolated. An open system allows for the
exchange of matter and energy with its surroundings. For example, the biosphere is an
open system. A tree is another open system. It takes energy from the sun, absorbs water
with its roots, and releases oxygen and water to soils and the atmosphere. Closed
systems exchange energy with their surroundings, but not matter. Isolated systems do
not exchange energy or matter with their surroundings. Closed systems are rare in nature,
but may exist under laboratory conditions. Isolated systems are essentially absent from
nature and can only be approximated in the laboratory.
A garbage landfill is an attempt to develop a closed system. Supposedly, the waste is
indefinitely locked up in the landfill. The landfill is designed to keep the wastes from
contaminating soils, sediments and water outside of the landfill (the immediate
surroundings). At the same time, landfill engineers usually dont care if seasonal
temperatures within the landfill vary somewhat because of the exchange of heat energy
between the landfill and its surroundings. That is, the engineers have no interest or
budget in making the landfill an isolated system.
Open, Closed and Isolated Systems:
matter, energy

Open System Surroundings

energy only

Closed System Surroundings

[ Isolated System ]

Surroundings

A Landfill as a Closed System (the Ideal) and as an Open System (Reality):

Systems may also be described as dynamic (changing) or static (not changing) over
time. Most systems on Earth are dynamic. Trees grow and die. Continental elevations
build up through tectonic uplift and volcanism, and wear down through erosion. The
Moon, in contrast, is essentially static and only changes slightly from the impacts of
cosmic dust and occasional meteorites.
Chemical Equilibrium
If we mix an aqueous solution of 1 M barium chloride with another aqueous solution of 1
M sodium sulfate, the mixture will immediately turn cloudy white. The cloudy
precipitate is barium sulfate. We can write an equation for the reaction. Initially, the
reaction will move to the right to produce the barium sulfate precipitate:
Ba2+ + 2 Cl- + 2 Na+ + SO 4 2- + H 2 O BaSO 4 + H 2 O + 2 Cl- + 2 Na+
Since many of the chemical species in the mixture don't readily react, we can rewrite the
reaction to only show the relevant reactants and products:
Ba2+ + SO 4 2- BaSO 4
We can graph the progress of the reaction between 1 M Ba2+ and 1 M SO 4 2- (compare
Figure 9.1, p. 111):
1|
|
|
|
Molar |
Conc. |
|
|
0 |________________________________
Time
------ SO 4 2- concentration ***** Ba2+ concentration

+++++ BaSO 4 concentration

Sometime later, the reaction will reach equilibrium:

Ba2+ + SO 4 2- = BaSO 4
At chemical equilibrium, the concentrations appear constant or parallel to each other on
the above graph. At equilibrium, both sides of the reaction occur at the same rate (that is,
the rate of Ba2+ + SO 4 2- BaSO 4 is the same as Ba2+ + SO 4 2- BaSO 4 ). However,
this DOES NOT mean that the species on each side of the reaction are in equal
concentrations. At equilibrium, chemical analyses indicate that almost all of the barium
and sulfate are located in the BaSO 4 . However, a small amount of the barium and the
sulfate, only about 1.37 mg/L of barium and about 0.96 mg/L of sulfate (1 x 10-5 M of
each), will exist as Ba2+ and SO 4 2-. At equilibrium, these trace amounts of Ba2+ and
SO 4 2- are constantly reacting to form small amounts of BaSO 4 and small amounts of
BaSO 4 are constantly dissolving to replenish the trace amounts of Ba2+ and SO 4 2-. That
is, at equilibrium, the formation of barium sulfate from the remaining trace amounts of
Ba2+ and SO 4 2- (the forward reaction) is balanced by the dissolution of small amounts of
barium sulfate to produce Ba2+ and SO 4 2- (the reverse reaction).
Equilibrium Constants
In Lecture #5, when we defined pH, we derived an ion-product constant (K W ) for water,
which is a type of equilibrium constant:
H 2 O = H+ + OHActivities of the Products
------------------------------- = equilibrium constant
Activities of the Reactants
[H+] [OH-]
------------- = K W = 10-14
[H 2 O]
[H 2 O] = 1
Therefore:

[H+] [OH-] = 10-14

Similarly, we can derive equilibrium constants for other chemical reactions. That is,
when a reaction, such as Ba2+ + SO 4 2- = BaSO 4 , reaches equilibrium, the ratio of the
activities of the products to the reactants yields a constant, an equilibrium constant, K eq .
[BaSO 4 ]
----------------- = K eq
[Ba2+] [SO 4 2-]

The general format for the K eq of a reaction at equilibrium is:

aA + bB = cC + dD
where:
A and B = the reactants
C and D = the products
a, b, c, and d = the number of moles of A, B, C and D, respectively.
[C]c [D]d
----------- = K eq
[A]a [B]b
where:
[C] and [D] = activities of the products
[A] and [B] = activities of the reactants
K eq = equilibrium constant. Each chemical reaction has its own K eq .
If [A], [B], [C], or [D] are undissolved solids or liquids in solutions, their
activities are considered to be 1 and they are ignored in the equilibrium constant
calculations. However if the solids or liquids are dissolved neutral molecules
(such as SiO 2 0 or H 2 CO 3 0), then they are considered part of the calculations.
Similarly, undissolved gases are not considered in the K eq calculations. However,
dissolved gases (such as O 2 0, Hg0, and CO 2 0), along with ions and other dissolved
neutral molecules, are considered in the K eq calculations. As examples:
Ba2+ + SO 4 2- + H 2 O = BaSO 4
H 2 O and BaSO 4 are distinctively separate, undissolved and electrically neutral
compounds, therefore for this reaction:
1
------------= K eq
[Ba2+] [SO 4 2-]
With the following reaction, notice the zero charge on the carbonic acid:
H 2 CO 3 0 = H 2 O + CO 2

The zero charge symbol indicates that the carbonic acid exists as dissolved
molecules rather than as a distinct liquid. Therefore, the carbonic acid molecules
are part of the equilibrium constant calculations. Also, CO 2 gas may dissolve in
the water along with the carbonic acid molecules, H 2 CO 3 0. Therefore, the
dissolved portion of the CO 2 is also considered in the K eq calculations:
K eq = [CO 2 0] / [H 2 CO 3 0]
Later, we'll show how to distinguish dissolved from non-dissolved CO 2 for the
K eq calculations.
So, if you see a zero superscript on a neutral species (including if the species is a
dissolved gas), they are relevant to the equilibrium constant calculations.
However, water, undissolved gases and solid precipitates are ignored in the
calculations.
As mentioned earlier, concentrations are usually easier to measure than activities. As
long as the concentrations are low and the temperatures of the solutions are around 25oC,
we can use concentrations instead of activities to calculate the equilibrium constants.
Like Faure (1998, p. 113), we'll use brackets [ ] to denote activities and parentheses ( ) to
denote concentrations in equilibrium constant calculations. Note: some textbooks use
the opposite convention, that is, [ ] denote concentrations and ( ) to denote activities.

LeChateliers Principle
The addition or removal of reactants or products from a reaction readily disrupts the
equilibrium of the reaction. LeChatelier's Principle says that if the concentrations of
reactants or products, temperature, or pressure are changed for a reaction in
equilibrium, the equilibrium will shift in a way to undo the effect of the change. Let's
look at the barium sulfate reaction again:
Ba2+ + SO 4 2- = BaSO 4
What would happen if we add more Ba2+ to the mixture? The excess barium would react
with much of the 0.96 mg/L of SO 4 2- to produce more barium sulfate. In other words,
LeChatelier's Principle states that the reaction would move to the right and the 0.96 mg/L
of SO 4 2- would decrease to even lower concentrations.
What would happen if we were to filter out (remove) the barium sulfate from the
mixture? The small amounts of Ba2+ and SO 4 2- would tend to react and precipitate new
barium sulfate. However, with the solid barium sulfate essentially removed, there is no
abundant barium sulfate to dissolve and replace the small amounts of Ba2+ and SO 4 2-.
Therefore, according to LeChatelier's Principle, the removal of barium sulfate from the
mixture through filtering would cause the reaction to move towards the right.

The effects of LeChatelier's Principle may be seen when sulfate-rich groundwater reacts
with spilled water-soluble barium nitrate from a fireworks factory. The presence of SO 4 2>> Ba2+ in the mixing of barium nitrate and sulfate-rich groundwater will cause the
reaction to move to the right according to LeChatelier's Principle:
Ba2+ + excess SO 4 2- BaSO 4
Because of the excess sulfate from the groundwater, the concentration of the remaining
Ba2+may be much lower than 1.37 mg/L and not a serious environmental problem.
On the other hand, in rare circumstances, if Ba2+ >> SO 4 2- + CO 3 2- + HCO 3 -, not all of
the Ba2+ will precipitate as BaCO 3 or BaSO 4 , and the Ba2+ may be a groundwater
contamination problem.
LeChateliers Principle: Barium Nitrate Pollution from Fireworks Factories into Low
and High Sulfate Groundwaters:

LeChatelier's Principle is also affected by the addition or removal of heat. Let's look at
the following reaction:
CaO + H 2 O = Ca(OH) 2 + Heat!!
When lime (CaO) is placed in water, it violently reacts with the water to produce
Ca(OH) 2 and a lot of heat! Sometimes the reaction is so exothermic (heat-releasing) that
the water boils! Now, imagine what would happen if you were to add considerably more
heat to a container with reacting lime and water. LeChatelier's Principle says that the
reaction would move to the left. The excess heat would cause Ca(OH) 2 to dehydrate to
CaO and steam:
CaO + H 2 O (as steam) Ca(OH) 2 + More heat
It will take a lot of heat to get the reaction to noticeably move to the left because
substantial amounts of Ca(OH) 2 are not dehydrated until temperatures reach about 580oC.
On the other hand, the addition of ice to the reaction would remove the produced heat and
force the reaction to the right.

The effect of temperature on LeChatelier's Principle may also be seen with the following
reaction between H 2 and Cl 2 gases to produce HCl gas:
H 2 + Cl 2 = 2 HCl + Heat
At higher temperatures, the reaction goes to the left and HCl decomposes to H 2 and Cl 2 .
If the heat is removed by lowering the temperature, the reaction moves to the right and
more of the H 2 and Cl 2 gases react to produce HCl.
Solubility Product Constant
A solubility product constant (K sp ) is a special type of equilibrium constant that is used
to describe the dissolution of a slightly soluble compound in water and calculate the
activities or concentrations of the dissolution products in a saturated solution. When
studying the dissolution of a solid in water with K sp values, the dissolving solids are
considered reactants. As an example:
BaSO 4 = Ba2+ + SO 4 2[Ba2+] [SO 4 2-] = K sp
From Faure (1998, p. 132): K sp = 10-10. Often K sp is written as pK sp = 10.0 or the
negative log of K sp .
By knowing the K sp , we can calculate the solubility of Ba2+ and SO 4 2- in a saturated
solution of BaSO 4 :
[Ba2+] [SO 4 2-] = 10-10
Because BaSO 4 dissolves into an equal number of moles of Ba2+ and SO 4 2-:
[Ba2+] = [SO 4 2-]
Therefore, to find [Ba2+], we can substitute [Ba2+] for [SO 4 2-]:
[Ba2+] [Ba2+] = 10-10
[Ba2+]2 = 10-10
_____
2+
[Ba ] = 10-10 = 10-5 M = [SO 4 2-]
10-5 moles/L SO 4 2- x 96.06 g/mole SO 4 2- = 0.0009606 g/L SO 4 20.0009606 g/L SO 4 2- = 0.96 mg/L SO 4 2-

10-5 moles/L Ba2+ x 137.34 g/mole Ba2+ = 0.00137 g/L Ba2+

0.00137 g/L Ba2+ = 1.37 mg/L Ba2+
How many moles of BaSO 4 dissolved to produce the 10-5 M SO 4 2- and 10-5 M Ba2+?
BaSO 4 = Ba2+ + SO 4 22+

Therefore 10-5 M of BaSO 4 dissolves to produce 10-5 M SO 4 2- and the 10-5 M

Ba .
10-5 M of BaSO 4 x 233.4 g/mole BaSO 4 = 0.002334 g/L = 2.33 mg/L BaSO 4
As a check, we note that:
1.37 mg/L Ba2+ + 0.96 mg/L SO 4 2- = 2.33 mg/L dissolving BaSO 4
A more complex example: Is it illegal to dump a saturated solution of Ag 2 SO 4 down the
drain? Note: Federal regulations state that it is illegal to dump silver solutions down the
drain if they contain more than 5 mg/L of silver. Solutions with more than 5 mg/L of
silver are considered hazardous and must undergo proper treatment and disposal. Using
the pK sp of Ag 2 SO 4 from Faure (1998, p. 132):
Ag 2 SO 4 = 2 Ag+ + SO 4 2[Ag+]2 [SO 4 2-] = K sp = 10-4.81 = 1.55 x 10-5
Notice that the dissolution of Ag 2 SO 4 produces twice as many moles of silver as sulfate.
We have two unknowns: [Ag+] and [SO 4 2-]. The sulfate activity has to be doubled to
equal the silver activity. Note: this is hard to visualize!! Therefore:
[Ag+] = 2 x [SO 4 2-]
We now have two equations for the two unknowns. We can now solve for the unknowns,
the activities of the silver and sulfate in the saturated silver sulfate solution.
[Ag+]2 [SO 4 2-] = 1.55 x 10-5
[Ag+] = 2 x [SO 4 2-]
Using algebra, let's substitute the second equation into the first to solve for the sulfate
activity:
[2 x SO 4 2-]2 [SO 4 2-] = 1.55 x 10-5

4 [SO 4 2-]2 [SO 4 2-] = 1.55 x 10-5

4 [SO 4 2-]3 = 1.55 x 10-5
[SO 4 2-]3 = 3.88 x 10-6
Take the cube root of both sides.
[SO 4 2-] = 0.0157 M
Since:
[Ag+] = 2 x [SO 4 2-]
[Ag+] = 2 x 0.0157 M = 0.0314 M = 0.0314 moles/L
Ag+ = 107.8682 g/mole
[Ag+] = 3.39 g/L = 3390 mg/L, It's illegal.

Disequilibrium
Some reactions are so slow that they may take years to reach equilibrium. If a reaction in
a solution is not at equilibrium, the solution may become supersaturated with some
species. A reaction that is NOT at equilibrium has:
[C]c [D]d
----------- K eq
[A]a [B]b
But we can still calculate an activity product (AP) from the activities of the reactants
and products:
[C]c [D]d
----------- = AP K eq
[A]a [B]b
If the reaction involves ions, the activity product is an ion activity product (IAP).
If AP/K eq > 1, the activities or concentrations of the products (C and D) are higher than
expected and LeChatelier's Principle dictates that the reaction should proceed to the left
to regenerate more A and B (reactants) so that equilibrium may be eventually achieved
(Faure, 1998, p. 131):
aA + bB cC + dD

If AP/K eq < 1, A and B (the reactants) are more abundant than expected at equilibrium
and LeChatelier's Principle dictates that the reaction should proceed to the right to
produce more products and eventually achieve equilibrium:
aA + bB cC + dD
At equilibrium:
aA + bB = cC + dD
AP/K eq = 1 or AP = K eq

10

Lecture #12: Ionic Strength of Aqueous Solutions

(Chapter 10 in Faure, 1998)
In previous lectures, we examined the solubilities of substances in pure water at various
temperatures. However, pure water doesn't exist in nature and, for environmental
geochemistry, we need to examine the solubilities of toxic substances in natural waters,
which may have substantial TDS values. Earlier, we described how excess SO 4 2-, CO 3 2-,
or Ba2+ may influence the solubility of BaSO 4 in water via LeChateliers Principle or
through the precipitation of BaCO 3 . Na+, Cl-, Mg2+, and other ions that normally don't
react with Ba2+ or SO 4 2- in water may actually increase the solubility of BaSO 4 , if they
are in great abundance. As mentioned earlier, in dilute solutions, water molecules may
surround the Ba2+ or SO 4 2- and hinder them from reacting. As Ba2+ and SO 4 2concentrations substantially increase in pure water, the Ba2+ and SO 4 2- begin to find each
other and precipitate as BaSO 4 . However, the presence of abundant Na+ and Cl- may
increase the solubility of BaSO 4 by more effectively shielding the Ba2+ and SO 4 2- from
each other than water molecules. Furthermore, +2 and -2 ions have greater abilities to
shield Ba2+ and SO 4 2- from each other than -1 or +1 ions.
Ionic strength describes the concentrations of ions in water. The attached figure from
Bird and Krauskopf (1995, p. 51) shows the solubility of BaSO 4 in moles/liter (molarity,
M) with increasing ionic strength.
The following equation is often used to calculate ionic strength from the concentrations
of the major cations and anions in a water sample:
I = 1/2 (m i (z2))
where:
I = ionic strength
m i = molal concentrations of each ion (not mg/L)
z = the charge of the ion
Unlike ionic strength, TDS (total dissolved solids) ignores the charges on the ions and
includes the concentrations of neutral species, such as SiO 2 0 and H 2 CO 3 0. Ions in
aqueous solutions are electrolytes because the conduct electricity. The more ions in a
water sample, the greater the ability of the sample to conduct electricity and the higher
the ionic strength. Because the number of ions in a water sample affects both its
conductivity and ionic strength, it's not surprising that equations may be derived to relate
ionic strength (in molality) and electrical conductivity (Langmuir, 1997, p. 124):

Used with NaCl waters: I 0.8 x 10-5 Conductivity in mhos/cm

Used with Ca-Mg sulfate waters: I 1.7 x 10-5 Conductivity in mhos/cm
Used with calcium carbonate waters: I 1.9 x 10-5 Conductivity in mhos/cm
These equations are cheaper alternatives for estimating ionic strength than measuring the
major ions for $$$ and using I = 1/2 m i (z2).
TDS and ionic strength are also closely related. Langmuir (1997, p. 124) provides
several equations that relate the two parameters (TDS is in mg/L and I in molality):
I 2.5 x 10-5 TDS for an average water
I 2 x 10-5 TDS for NaCl waters.
I 2.8 x 10-5 TDS for calcium carbonate waters.

Some typical ionic strengths (in molal) for natural waters:

Most rivers and freshwater lakes are about 0.001
Seawater = 0.7
Oilfield brines = 5
Ionic strength is often unitless in books, but if you work out the units, it should be
molality, m.
As mentioned earlier, concentrations may be readily measured in a laboratory, but
activities are more difficult to determine. The ionic strength of an aqueous solution may
be used to calculate the activity coefficients () for various chemical species in a sample.
The activities are then calculated with:
activity of the species = concentration of species

(a = m).

Two equations are most often used to determine activity coefficients in low TDS
solutions. One is the Debye-Hckel equation (Faure, 1998 equation 10.46, p. 140),
which works for solutions with I < 0.1 m:
__
__
2
log i = (-Az i I ) / (1 + BaI )
where:
log i = log of the activity coefficient for a particular ionic
species, such as Na+ or SO 4 2-.
z i = charge on the ion.

I = ionic strength.
A, B = different variables related to temperature and the dielectric
constant of the solvent, see Table 10.3 in Faure (1998, p. 140) for
some values.
a = the effective diameter of the ionic species in , see Table
10.4 in Faure (1998, p. 141) for some values. There are some
controversies over the values of a for some chemical species.
Drever (1997, p. 28) uses more recent references than Faure (1998,
Table 10.4, p. 141) and lists the following values for a:
Mg2+ = 5.5
Na+ = 4.0
K+, Cl- = 3.5
Ca2+, Sr2+, Ba2+, SO 4 2+ = 5.0
HCO 3 -, CO 3 2- = 5.4
NH 4 + = 2.5
Fe2+, Mn2+, Li+ = 6.0
H+, Al3+, Fe3+ = 9.0
The second equation, the Davies equation, is effective in estimating activity coefficients
in solutions with I < 0.5 m. There are different forms of the Davies equation. The
following form from Drever (1997, p. 28) appears to be more accurate than equation
10.47 from Faure (1998, p. 141):
__
__
log i = [(-Az i 2 I ) / (1 + BaI )] + bI
where:
b usually equals 0.3. Some other values for b from Drever (1997, p. 28)
are:
Ca2+ = 0.165
Mg2+ = 0.20
Na+ = 0.075

K+, Cl- = 0.015

SO 4 2+ = -0.04
HCO 3 -, CO 3 2- = 0.0
The other variables are the same as in the Debye-Hckel equation.
Unfortunately, the Debye-Hckel and Davies equations do not work with seawater and
brines. As discussed on page 141 in Faure (1998) and his references, there are methods
for estimating activity coefficients in seawater and brines. However, they involve
complex mathematics and the equations require values for the different chemical species,
which are often unknown.

Some examples:
Calculate the ionic strength of an aqueous solution with 0.04 M NaCl and 0.01 M
MgSO 4 .
This solution would have the following concentrations:
Na+ = 0.04 moles/liter
Mg2+ = 0.01 moles/liter
Cl- = 0.04 moles/liter
SO 4 2- = 0.01 moles/liter
Assume M = m.
I = 1/2 m i (z2)
I = 1/2 [0.04 (1)2 + 0.04 (-1)2 + 0.01 (2)2 + 0.01 (-2)2]
I = 1/2 [0.04 + 0.04 + 0.04 + 0.04] = 0.08
Whats the of Mg2+ for the solution at 25oC using the Davies equation?
Using the equation from Drever (1997):
__
__
2
log i = [(-Az I ) / (1 + BaI )] + bI

I = 0.08
A at 25oC from Table 10.3 (Faure, 1998, p. 140): 0.5085
z for Mg2+ = +2
b for Mg2+ from Drever (1997, p. 28) = 0.20
B at 25oC from Table 10.3 (Faure, 1998, p. 140): 0.3281
a for Mg2+ from Table 10.4 (Faure, 1998, p. 141): 8; Drever (1997, p. 28) says 5.5

Using Drever's value for a:

log i = -0.36
i = 0.43
Since a = m, the activity of Mg2+ is 43% of the concentration. Using a = 8 from Faure
(1998, p. 141), i = 0.48.

References:
Drever, J.I., 1997, The Geochemistry of Natural Waters, 3rd ed., Prentice Hall,
Upper Saddle River, NJ 07458.
Krauskopf, K.B. and D.K. Bird, 1995, Introduction to Geochemistry, 3rd ed., McGrawHill, Boston.
Langmuir, D., 1997, Aqueous Environmental Geochemistry, Prentice Hall, Upper Saddle
River, NJ.