CHAPTER XVI VOLUMETRIC METHODS

A. Fundamentals of Volumetric Analysis

Volumetric or titrimetric analyses are quantitative analytical
techniques which employ a titration in comparing an unknown with a
standard. In a titration, a volume of a standardized solution containing a
known concentration of reactant "A" is added incrementally to a sample
containing an unknown concentration of reactant "B". The titration proceeds
until reactant "B" is just consumed (stoichiometric completion). This is known
as the equivalence point. At this point the number of equivalents of "A"
added to the unknown equals the number of equivalents of "B" originally
present in the unknown. Volumetric methods have the potential for a
precision of up to 0.1%.
For volumetric methods to be useful, the reaction must reach 99%+
completion in a short period of time. In almost all cases, a buret is used to
meter out the titrant. When a titrant reacts directly with an analyte (or with a
reaction the product of the analyte and some intermediate compound), the
procedure is termed a direct titration. The alternative technique is called a
back titration. Here, an intermediate reactant is added in excess of that
required to exhaust the analyte, then the exact degree of excess is
determined by subsequent titration of the unreacted intermediate with the
titrant. Regardless of the type of titration, an indicator is always used to
detect the equivalence point. Most common are the internal indicators,
compounds added to the reacting solutions that undergo an abrupt change
in a physical property (usually absorbance or color) at or near the
equivalence point. Sometimes the analyte or titrant will serve this function
(auto indicating). External indicators, electrochemical devices such as pH
meters, may also be used. Ideally, titrations should be stopped precisely at
the equivalence point. However, the ever-present random and systematic
error, often results in a titration endpoint, the point at which a titration is
stopped, that is not quite the same as the equivalence point. Fortunately, the
systematic error, or bias may be estimated by conducting a blank titration. In
many cases the titrant is not available in a stable form of well-defined
composition. If this is true, the titrant must be standardized (usually by
volumetric analysis) against a compound that is available in a stable, highly
pure form (i.e., a primary standard). The basic requirements or components
of a volumetric method are:
1. A standard solution (i.e., titrant) of known concentration which
reacts with the analyte with a known and repeatable
stoichiometry (i.e., acid/base, precipitation, redox,
complexation)

2. A device to measure the mass or volume of sample (e.g., pipet,

graduated cylinder, volumetric flask, analytical balance)
3. A device to measure the volume of the titrant added (i.e., buret)
4. If the titrant-analyte reaction is not sufficiently specific, a
pretreatment to remove interferents
5. A means by which the endpoint can be determined. This may be an
internal indicator (e.g., phenolphthalein) or an external
indicator (e.g., pH meter).
Table 16.1
Volumetric Methods for Environmental Analysis

Analyte

Titrant

Indicator

Pretreatme Method
nt

Acid/Base
Alkalinity
Acidity
N(-III)

HCl
NaOH
H2SO4

methyl orange
phenolphthalein
methyl red

none
none
digest/distill (N
NH4OH)

Volatile
NaOH
Acids
Precipitation
Chloride
Ag

phenolphthalein

distillation

Chloride

Hg

potassium
chromate
diphenylcarbazo
ne

MacroKjeldahl &
Acidimetric
Distillation

Mercuric
Nitrate

Complexation or Chelation
Ca
EDTA
Eriochrome Blue
Black R
Eriochrome Black
Hardness
EDTA
T

CN

Ag

pdimethylamino
benzalrhodanin
e

Oxidation/Reduction
Dissolved O2 Na2S2O3
Ca
MnO4

starch
auto

Mn(+II), I(-I)
oxalate

Chlorine/ClO

starch

I(-I)

Na2S2O3

Winkler
Permanganat
e Titr
Iodometric

SO3-2
Chlorine/ClO

Na2S2O3
FeSO4

starch
DPD

I(-I)

Fe(NH4)2(SO4)2

ferroin

K2Cr2O7

COD

Iodometric
DPD Ferrous
Titr.

Volumetric methods may be based on acid/base reactions.

precipitation reactions, complexation reactions and redox reactions. Table
16.1 presents a summary of the volumetric methods commonly used for
environmental analysis. The acid/base methods generally use a strong acid
or base as a titrant with methyl orange/red (acid titration) or
phenolphthalein (base titration) as the indicator. For all but acidity and
alkalinity determinations, the analyte must be separated from the major
cations and anions prior to titration. Precipitative volumetric analysis relies
on the formation of solid phase with a very low solubility product constant.
In environmental analysis, it may be used for chloride determination.
Specific indicators are used to detect excess silver or mercury.
Complexometric titrations often employ ethylenediaminetetraacetic acid or
EDTA [HOOCCH2)2NHCH2CH2NH(CH2COOH)2]. This is a hexadentate ligand
which binds very strongly to many metals. For calcium and total hardness
determination, a couple of specific dyes are used to determine the presence
of excess cation. Many oxidation/reduction based volumetric methods
employ the iodometric method. This involves the oxidation of iodide to
iodine and subsequent titration with sodium thiosulfate using starch as an
indicator. Many of these employ a series of redox reactions. The
permanganate method for calcium is somewhat unique in that the calcium is
precipitated as the oxalate, and it is the solid-phase oxalate group which
participates in the redox reaction, not the calcium.

B. Acid/Base Titrations
1. ALKALINITY & ACIDITY
a. Environmental Significance
Alkalinity is a measure of a water's ability to neutralize strong acids.
It reflects the water's buffer capacity or resistance to a drop in pH upon
addition of acid. Conversely, acidity is a measure of a water's ability to
neutralize strong bases.
Alkalinity is important in assessing the need for additional buffering
or pH control with pH-sensitive operations. For example, the alkalinity of a
water must be known in order to calculate lime and soda ash doses for
precipitative softening. Species responsible for either alkalinity or acidity can
affect rates of corrosion, the speciation of metals and organic compounds,
the rates of certain types of reactions, and numerous biological processes.

Alkalinity and acidity might also correlate with other properties of a water
such as hardness and TDS.
b. Species Responsible for Alkalinity and Acidity in Waters
Alkalinity and acidity can be interpreted in terms of concentrations of
specific constituents only when the chemical composition of the water is
known. Species that impart alkalinity to a water are bases. Species that
impart acidity to a water are acids. In unpolluted fresh waters, hydroxide,
carbonate and bicarbonate are the most important bases. Therefore, total
alkalinity is often interpreted as the sum of the number of equivalents of
these bases (minus the hydrogen ion concentration). Thus, alkalinity can be
expressed in terms of eq/L or meq/L, but not moles/L or mmoles/L.
Alktot = [HCO3-] + 2[CO3-2] + [OH-] - [H+]
(16.1)
In rare cases other bases may also be important such as the silicates,
ammonia, phosphates, borates and organic bases. For example, extremely
soft waters (< 10 mg/l as CaCO3) contain so little bicarbonate that ammonia
and silicate concentrations become important. Aside from H and OH -, the
nonmetals found in fresh waters in order of importance are the carbonates,
sulfate, chloride, silicate, organic anions, nitrate, fluoride, boron, bromide,
ammonia and phosphate. Of these, sulfate, chloride, nitrate, fluoride and
bromide are insufficiently basic to contribute alkalinity regardless of their
concentration. Similarly, most of the major cations such as calcium, sodium,
magnesium, potassium and strontium do not hydrolyze to a sufficient extent
within the pH range of interest to account for much alkalinity. The remaining
species of interest are listed in Table 16.2. Based on the average
concentrations shown here, the practice of interpreting fresh water alkalinity
in terms of the carbonate system is justified.
It is important to point out here that although carbonates contribute
to alkalinity, the addition of carbon dioxide to a water will not alter its
alkalinity. This is true, because carbon dioxide consumes one hydroxide
molecule for each bicarbonate molecule formed.
CO2(aq)
(16.2)

OH-

HCO3-

The addition or loss of carbon dioxide might, however, result in a change in

pH.
In contrast to fresh waters, seawater has such high concentrations of
other bases that the following chemical interpretation is commonly used (Alk
& Acy are always in units of equivalents/liter):

Alktot = [HCO3-] + 2[CO3-2] + [B(OH)4] + [HPO4-2] + [H3SiO4] +

[MgOH-] + [OH-] - [H+]
(16.3)
Important acids that contribute to acidity are the hydrogen ion,
bicarbonate and dissolved carbon dioxide. Organic acids may also contribute
acidity in highly colored waters.
Acytot =
(16.4)

2[H2CO3]

[HCO3-]

[H+]

[OH-]

Table 16.2

Chemical Species Which May Contribute to the Alkalinity of Fresh

Waters
Species

pKa

Average
Conc.
(M)

Equilibria

Carbonates
Silicates
Organics
Borates
Ammonia
Iron
Aluminum

10.3/6.4
9.8
3 to 10
9.2
9.2
6.0/4.6
8.0/5.7
4.3/5.0
7.2
14.0
9.8/7.3
6.9
7.6
6.2
7.0
6.1/9.0

1x10-3
2x10-4
1x10-4
1x10-6
2x10-6
2x10-6
2x10-6

CO3-2 + 2H+ = HCO3- + H+ = H2CO3

H3SiO4 + H+ = H4SiO4
R-COO- + H+ = R-COOH
B(OH)4- + H+ = B(OH)3 + H2O
NH4OH + H+ = NH4+ + H2O
Fe(OH)4- + 3H+ = Fe(OH)2+ + H+ = Fe(OH)+2
Al(OH)4- + 2H+ = Al(OH)3 + H+ = Al(OH)2+
Al(OH)2+ + 2H+ = Al(OH)+2 + H+ = Al+3
HPO4-2 + H+ = H2PO4OH- + H+ = H2O
Cu(OH)3- + 3H+ = Cu(OH)++ H+= Cu+ + H2O
Ni(OH)2 + H+ =NiOH+
Cd(OH)+ + H+ = Cd+2 + H2O
Pb(OH)+ + H+ = Pb+2 + H2O
HS- + H+ = H2S
Zn(OH)2+ 2H+= Zn(OH)++ H3O+=Zn+2+
2H2O

Phosphates
Hydroxide
Copper
Nickel
Cadmium
Lead
Sulfides
Zinc

7x10-7
2x10-7
1x10-7
2x10-8
1x10-8
1x10-8
variable
variable

c. Notes on the determination of alkalinity & acidity

i. Principles All waters undergo some drop in pH with the addition of
strong acids, and some rise in pH with the addition of strong bases. The
greater the alkalinity or acidity, the smaller the shifts in pH, however, they
never completely disappear. Thus, alkalinity and acidity cannot be

determined by the addition of an acid or base until a pH change occurs,

because the first drop will always result in some change. Instead, samples
are commonly titrated to a pre-determined pH. By convention, the pH is
usually about 4.5 for the alkalinity titration and 8.3 for acidity. However,
these are not purely arbitrary choices. Titration to pH 8.3 corresponds to the
point where the quantity of base added equals the sum of the strong acid,
carbon dioxide and bicarbonate originally present. Because this pH
represents the approximate point of color change for the indicator,
phenolphthalein, the amount of titrant required to reach this pH is often
referred to as the phenolphthalein acidity. Similarly, titration to pH 4.5
corresponds to the point where the quantity of acid added equals the
amount of strong base, carbonate and bicarbonate originally present. Since
this pH represents the approximate point of color change for the indicator,
methyl orange, the amount of titrant required to reach this pH is often
referred to as the methyl orange alkalinity.
Methyl orange is an azo dye that changes color from yellow to red as
the pH is lowered below about 4.5. It is also known as pdimethylaminoazobenzene-p'-sulfanilic acid.

Phenolphthalein is a polyphenolic compound which loses both a

water molecule and a hydrogen ion at high pH. As the deprotonation occurs
the color changes from colorless to bright red.

ii. Choice of Titration Flasks It is good practice to have as little space

between the sample and the buret (and pH electrode) as practical. With
conventional-sized electrodes, the 200 mL tall form Berzelius beaker is a
good choice. For miniature combination electrodes and for the colorimetric
method, an erlenmeyer flask (125 mL or 250 mL) is recommended. In
general a magnetic stirrer is recommended for proper mixing and electrode
response, however the speed should be kept low to minimize exchange with
the atmosphere. A rubber stopper with holes for the electrode(s) and buret
may be used to further reduce atmospheric contact. For the colorimetric
method, manual agitation of the erlenmeyer flask via a swirling wrist motion
may be used.
iii. Sampling Procedures
1. Handle carefully to avoid loss of carbon dioxide
2. Analyze promptly after opening to avoid loss of volatiles (carbon
dioxide, ammonia, hydrogen sulfide)
3. Collect samples in polyethylene or glass bottles and keep cool to
avoid changing gas solubilities.
iv. Colorimetric vs Potentiometric Methods
In the vast majority of cases both the colorimetric and potentiometric
methods are acceptable. However, there are certain circumstances where
one might be preferred over another. For example, some highly colored or
turbid samples may mask the color of indicators, and render it impossible to
use the colorimetric method. If free residual chlorine is present, it will have to
be removed by addition of 1 drop of 0.1M sodium thiosulfate solution prior to
using the colorimetric method. This is necessary to avoid bleaching of the
indicators. With some very dilute waters, this type of sample pretreatment
may effect the results and the potentiometric method is recommended. For
greatest accuracy, the potentiometric method is recommended. Under ideal
conditions this method allows one to graphically determine a sample's

equivalence point. Otherwise, one must rely on some predetermined

endpoint which has been found to correspond to the equivalence point in
many samples of the same alkalinity. Unfortunately, the potentiometricgraphical method is more time-consuming, and it requires a great deal more
analyst experience.
The potentiometric method also suffers from some disadvantages. For
example, it may not be a convenient method for rapid on-site analysis.
Potentiometric determination relies on the proper operation of a sensitive
instrument (i.e., the pH meter). Harsh conditions in the field or the lack of
electrical power may preclude its use. Even in the laboratory the
potentiometric method may be subject to certain types of interferences. With
some waters, surfactants and precipitates which coat the pH electrode will
impede its response. These substances must not be removed as they may
contribute to acidity or alkalinity. Instead, the electrode should be cleaned
frequently, or the colorimetric method should be employed.
d. Analytical Procedures
1.Alkalinity
a. HCl standardization
1. Add 15 ml of the primary standard sodium carbonate
solution to the titration vessel with about 60 ml of CO 2free water and 5 drops of methyl orange or bromcresol
green-methyl red indicator solution. Alternatively,
potentiometric pH determination may be used (~pH 4.3).
2. Fill buret with HCl stock using a 250 ml beaker as a
transfer vessel and note starting point (you should keep
the solution in the transfer beaker covered with a watch
glass during titrations). Titrate, while stirring, until a pH of
about 5 is reached or until the first signs of a color change
appear.
3. Remove electrodes, cover the sample with a watch glass
and boil slowly for 3-5 minutes. Allow solution to return to
room temperature and resume titration to endpoint.
4. Repeat this procedure (steps a-c) until 2 titrations give
results that agree within 2%. Rinse the buret and 250-ml
beaker thoroughly with distilled water.
5. Calculate the normality of the titrant, N t, from the
concentration of the primary standard sodium carbonate
solution, Nps, the volume of the sodium carbonate solution
used, Vps, and the volume of hydrochloric acid titrant
used, Vt. It should be close to 0.02N.
Nt = NpsVps/Vt

b. Sample Titration (Alkalinity)

1. Choose a sample volume that is expected to contain less
than 50 mg of alkalinity as CaCO 3. For most waters, 100
ml is a convenient volume.
2. Add 2 drops of either methyl orange or bromcresol greenmethyl red indicator solution or insert electrodes and
titrate with the HCl titrant to the endpoint. The first
potentiometric endpoint is pH 8.3 and from this the
phenolphthalein alkalinity (Alkph) is calculated. The second
endpoint (Alktot) depends somewhat on the alkalinity
range. Experience has shown the following pHs may be
used to establish an endpoint in lieu of a potentiometric
determination of the inflection point:
Alkalinity Potentiometri
c
(mg/L)
(pH)
30
150
500

4.9
4.6
4.3

Colorimetric
(from greenish blue
to)
light blue & lavender
light pink
red

Caution: Excessive agitation or prolonged titrations may

lead to loss of volatiles (e.g., carbon dioxide) or significant
uptake of atmospheric carbon dioxide. Avoid heating the
sample above room temperature by a magnetic stirrer.
2. Acidity
a. NaOH Standardization
1. Add 15 ml of the primary standard KHP solution to the
titration vessel with about 60 ml of CO 2-free water and 5
drops of phenolphthalein indicator solution. Alternatively,
potentiometric pH determination may be used (~pH 8.7).
2. Fill burette with NaOH stock using 250 ml beaker and note
starting point. As before, you must keep the solution
covered with a watch glass during titrations. Titrate, while
stirring, until the endpoint is reached.
3. Repeat this procedure (steps a-b) until 2 titrations give
results that agree within 2%. Rinse the buret and 250-ml
beaker thoroughly with distilled water.
4. Calculate the normality of the titrant, N t, from the
concentration of the primary standard KHP solution, N ps,
the volume of the KHP solution used, Vps, and the volume
of sodium hydroxide titrant used, Vt. It should be close to
0.02N.

Nt = NpsVps/Vt
b. Sample Titration (Acidity)
1. Choose a sample volume that is expected to contain less
than 50 mg of acidity as CaCO3. For most waters, 100 ml
is a convenient volume.
2. Add 2 drops of phenolphthalein indicator solution or insert
electrodes and titrate with the NaOH titrant to the
endpoint. The potentiometric endpoint is pH 8.3. For some
highly acidic waters (e.g., acid mine drainage) the volume
of titrant required to reach pH 3.7 should also be recorded
for determination of mineral acidity.
e. Reagents
1. Alkalinity
a. Primary Standard Sodium Carbonate Solution.
1. Dry at least 10 g of anhydrous sodium carbonate at 250
degrees C for at least 4 hours and allowed to cool in a
desiccator charged
with "Drierite".
2. Tare a piece of weighing paper.
3. Open the desiccator and place about 2.5 g sodium
carbonate on the paper, close the desiccator and quickly
re-weigh paper + primary standard to the nearest
milligram. Subtract combined weight from the tare weight
and record.
4. Gently pour the sodium carbonate into a 1-liter volumetric
flask. Fill to the mark with distilled water. You may wish to
use a distilled water wash bottle for the final few ml.
5. Calculate the normality of the primary standard, Nps, from
the mass in grams of the primary standard sodium
carbonate added, mps, and the gram equivalent weight of
the sodium carbonate (GEWps= 52.99). It should be close
to 0.05 N.
Nps = mps/GEWps
b. Hydrochloric Acid Stock Solution (about 0.1N)
1. Add 9 mls of reagent-grade HCl (11.6 M) to a 1-liter
volumetric flask and fill to the mark with distilled water.
c. Hydrochloric Acid Titrant (about 0.05N) - dilute stock
appropriately
d. Mixed Bromcresol Green-Methyl Red Indicator Solution.
1. Dissolve 20 mg methyl red sodium salt and 100 mg
bromcresol green sodium salt in 100 ml distilled water

2. Acidity
a. Primary Standard Potassium Hydrogen Phthalate Solution.
1. Dry at least 15 g of potassium hydrogen phthalate (KHP)
at 120 degrees C for at least 2 hours and allowed to cool
in a desiccator charged with "Drierite".
2. Tare a piece of weighing paper.
3. Open the desiccator and place about 10 g Potassium Acid
Phthalate (KHP) on the paper, close the desiccator and
quickly re-weigh paper + primary standard to the
nearest milligram. Subtract combined weight from the
tare weight and record.
4. Gently pour the KHP into a 1-liter volumetric flask. Fill to
the mark with distilled water. You may wish to use a
distilled water wash bottle for the final few ml.
5. Calculate the normality of the primary standard, Nps, from
the mass in grams of the primary standard KHP added,
mps, and the equivalent weight of the KHP (GEW ps=
204.10). It should be close to 0.05 N.
Nps = mps/GEWps
b. Sodium Hydroxide Stock Solution (about 0.1N)
1. Add 5.8 mls of a commercial 50% NaOH solution (19.1 M)
to a 1-liter volumetric flask and fill to the mark with
distilled water.
c. Sodium Hydroxide Titrant (about 0.05N) - dilute stock
appropritately
3. General
a. Carbon dioxide-free water: Use freshly distilled water or distilled
water that has been freshly boiled for 15 min and cooled to
room temperature. Conductivity should be less than
2umhos/cm.
f. Data Analysis
i. Calculation of Alkalinity If a water contains only hydroxide,
bicarbonate and carbonate as significant bases, then the amount of acid
(represented here by H+ or a proton) required to reach the Phenolphthalein
endpoint is equal to the amount of hydroxide originally present plus the
amount of carbonate originally present:
H+
(16.5)

OH-

H2O

H+
(16.6)

CO3-2

HCO3-

This is true, because at the pH where phenolphthalein changes color (8.3)

most of the alkalinity will be in the form of bicarbonate. Also, any remaining
under-protonated forms (i.e., hydroxide or carbonate) would be exactly
balanced by an equivalent amount of over-protonated forms (i.e., carbon
dioxide).
To reach the final, methyl orange or methyl red, endpoint one must
add an additional amount of acid equivalent to the amount of bicarbonate
present at the phenolphthalein endpoint:
HCO3-

H
+
(16.7)

H2CO3

CO2

H2O

This will be equal to the amount of bicarbonate initially present in the sample
plus the amount of carbonate originally present since carbonate was entirely
converted to bicarbonate in the first stage.
Theoretically AlkOH can be calculated directly from the starting pH
(pHi) by the following:
AlkOH
=
50,000(10pHi-14)
(16.8)
However, in practice, small errors in initial pH result in large errors in Alk OH.
Thus it is best to use the following scheme:
If Alkph > 0.5* Alkmo
AlkOH
(16.9a)
AlkCO3
(16.9b)
AlkHCO3
(16.9c)
If Alkph _< 0.5* Alkmo
AlkOH
(16.10a)
AlkCO3
(16.10b)
AlkHCO3
(16.10c)

2*Alkph

Alkmo

2(Alkmo

Alkph)

=
=

Alkmo

2*Alkph
-

2*Alkph

Where:
Alkph = 50,000VphNt/Vs

(16.11a)

Alkmo = 50,000VmoNt/Vs

(16.11b)

The factor of 50,000 is used because alkalinities are commonly expressed in

terms of milligrams per liter of equivalent calcium carbonate. Calcium
carbonate has a formula weight of 100g/mole. Since it has two equivalents
per mole we must divide this by two to get 50 g/equivalent or 50,000
mg/equivalent.
Presuming that all of the alkalinity is due to carbonate species and
hydroxide, one can use the values determined in equations 16.9 or 16.10 to
calculate molar carbonate and bicarbonate concentrations.
[HCO3-]
(16.12a)

AlkHCO3/50,000

[CO3-2]
(16.12b)

AlkCO3/100,000

g. Chemical Interpretation of Potentiometric Titration Curves

i. General Features The significance of the preceeding calculations is
best illustrated with a complete titration curve. Figure 16.1 shows a titration
of an extremely alkaline water where the pH was measured continuously as a
function of titrant added. Curve B corresponds to a water containing 1.5mM
hydroxide plus 1.0mM carbonate. Curve A shows what one would obtain with
a similar water containing only the 1.5mM hydroxide. The titrant is 0.100M
HCl and the sample volume is 1000 mL
The carbonate water curve (B) is composed of three plateaus and two
points of inflection, and the hydroxide solution (A) gives two plateaus and
one point of inflection. A point of inflection is one where the second
derivative of the curve equals zero. In other words it occurs where the slope
is a maximum and the curve goes from concave to convex. We will now
describe the significance of each of these features.
First, consider curve A. The upper plateau represents the
neutralization of hydroxide by the strong acid (equation #16.5). At the point
of inflection all of the initially present hydroxide has been consumed and H +
begins to accumulate in solution. As a result, the inflection point is often
termed the equivalence point. This means that at this stage in the titration,
an amount of acid has been added that is equivalent to the starting
concentration of base. Since we're plotting pH versus added acid the curve
beyond the equivalence point is not linear.

Figure 16.1
Acid Titration Curve for a Water Containing
Hydroxide and Carbonate Alkalinity
Near neutrality (pH 7) only very small amounts of acid (~10 -6 M) are required
to lower the pH by one unit, however, at pH 3 one must add 10,000 times as
much to drop one pH unit (i.e., to reach pH 2). Therefore, this semi-log plot
gives us a sloping curve beyond the equivalence point even though little or
no reaction is occurring.
For curve B, the first plateau corresponds to both the neutralization of
hydroxide and the protonation of carbonate (equations #16.5 and #16.6).
Here the point of inflection or equivalence point occurs at pH of about 8.4
rather than 7 for the hydroxide solution. At this point in the titration the
amount of acid added equals the molar amount of carbonate and hydroxide
originally present. With the exhaustion of the original carbonate (most
hydroxide would have been neutralized well before this point), H + begins to
accumulate in solution until it reaches a certain level where it becomes
favorable to combine with bicarbonate to give carbonic acid and carbon
dioxide. This then gives rise to the second plateau and a second equivalence
point. Equations 16.9a-16.9c should be used with sample B, because the
volume to reach the first endpoint is greater than half the volume to reach
the second.

Figure 16.2
Acid Titration Curve for a Water Containing
Carbonate and Bicarbonate Alkalinity
Figure 16.2 shows a titration curve of a less alkaline water. This one
contains significant amounts of carbonate alkalinity, but little or no hydroxide
alkalinity. Let's assume the starting solution contains "Y" moles of carbonate
and "Z" moles of bicarbonate. At the first equivalence point all of the initial
carbonate has been protonated to give bicarbonate. Thus, the volume to
reach this point (Vph) is equal to "Y" times the sample volume divided by the
titrant normality. This volume is clearly less than half of the final titrant
volume (Vmo), and thus equations 10a-10c must be used. Across the second
plateau, bicarbonate is converted to carbonic acid and aqueous carbon
dioxide. Since at the start of the plateau we had "Y+Z" bicarbonate, this
addition titrant volume (Vmo-Vph) will be equal to "Y+Z" times V s/Nt. The
original amount of carbonate, "Y", is obtained simply from the first titration
(see equation 16.10b), and the original amount of bicarbonate, "Z" is
obtained from the final titrant volume minus two times the volume to reach
the first equivalence point (equation 16.10c).

Figure 16.3
Acid Titration Curve for a Water Containing
Only Bicarbonate Alkalinity
Figure 16.3 shows titration curves from three waters containing
varying amounts of bicarbonate alkalinity. In each case the upper plateau
and first equivalence point is completely gone. The lower plateau
(bicarbonate to carbonic acid) and final equivalence point remain. As a
result, Vph=0, and equations 16.10a-16.10c should be used with these
samples. Note that as the bicarbonate concentrations increase from curve D
to curve F, the final equivalence points decrease.
ii. General Mathematical Solution The titration curve of a water
dominated by the carbonate system will be defined by three equilibrium
expressions:

(16.13)

(16.14)

(16.15)
In addition we need to consider a couple of mass balance equations. First,
the total concentration of carbonate species, C T, is assumed to be unchanged
during the titration. Rather they are just converted from one form into
another. Note that in contrast to alkalinity, C T must always be expressed on
terms of moles/L or mmoles/L, and not eq/L or meq/L.

(16.16)
A mass balance must also be written for electrical charge. The starting
solution is neutral and it must remain electrically neutral throughout the
titration. Equation #16.17 indicates that the sum the the positive charges
must equal the sum of the negative charges. Initially the water contains
carbonate and an equivalent concentration of counter ions such as calcium
or sodium. The charge (i.e., equivalent concentration) of these counter ions,
CB, remains constant throughout the titration since only HCl is being added.
Similarly, the hydrochloric acid has negative counter ions (chloride) whose
concentration, CA, increases as more acid is added. These charges must also
be included in equation #16.17,

(16.17)
where CA is approximately equal to the ratio of acid titrant added, V t, to
sample volume, Vs, times the titrant concentration:

(16.18)
Equation 16.16 can be rewritten:

(16.19)
This can then be combined with the carbonic acid-bicarbonate equilibrium
expression (equation 16.13) to get:

(16.20)
The bicarbonate-carbonate equilibrium expression (equation 16.14) can be
rearranged to get:

(16.21)
and then inserted into equation 16.20:

(16.22)
This may be rearranged to get an expression for bicarbonate concentration
exclusively in terms of hydrogen ion and base cation concentration:

(16.23)
And now combining equations 16.23 and 16.21 we get an analogous
expression for carbonate concentration exclusively in terms of hydrogen ion
and base cation concentration:

(16.24)
Note that the right-hand side of equations 16.23 and 16.24 are commonly
represented as 1CT and 2CT respectively (e.g., see Stumm & Morgan, 1981).
The hydroxide concentration may also be expressed in terms of the hydrogen
ion concentration by rearranging equation 16.15:

(16.25)

Finally these last three equations may be combined with the charge balance
(equation 16.17) to get the full equation describing the carbonate titration
curve:

(16.26)
This is a very cumbersome equation that must be solved by trial and error or
by some numerical technique. There are, however, some simplifying
assumptions that one can make to facilitate its solution.
iii. Titration Midpoint By definition, at the midpoint of the first plateau:
(@MP)
(16.27)
and according to equation 16.14 this must take place at the following pH.
[H+] = K2 = 4.7x10-11
(16.28)

(@MP)

pH = pK2 = 10.33
(16.29)

(@MP)

or

At this point carbonic acid (or carbon dioxide) concentration is insignificant.

Therefore half of the total carbonate, CT, is bicarbonate and half is carbonate.
This means that the last two terms in the final modified charge balance
(equation 16.26) become CT/2 and CT.

(@MP)
(16.30)
This can be rearranged to get the quantity of acid required to reach this
midpoint:
(@MP)
(16.31)
Combining equation 16.28 and 16.13 with this we calculate:

(@MP)
(16.32)
iv. Equivalence Point Perhaps the most significant feature on the
alkalinity titration curve is the equivalence point. This is defined as the point
where the number of equivalents of acid added just equals the number of
equivalents of alkalinity originally present, or:
CA = CB
(16.33)

(@EP)

For greatest accuracy in the determination of total alkalinity, this should be

the endpoint of the titration. Under ideal conditions the equivalence point
may be located on a titration curve as the point of inflection. In practice it is
difficult to place the point of inflection with any accuracy. As a result, most
alkalinity titrations are carried out to a pre-determined endpoint pH which
depends on the initial alkalinity. At the equivalence point, it follows from the
charge balance (equation 16.17) and equation 16.33 that:
(@EP)
(16.34)
Because we know that the equivalence point will be well below neutrality,
the carbonate and hydroxide concentrations should be insignificant
compared to the bicarbonate and hydrogen ion concentrations. Thus,
equation 16.34 reduces to:
(@EP)
(16.35)
And substituting from equation 16.23 we get an expression in terms of C B and
the equilibrium constants only.

(@EP)
(16.36)
Once again we can simplify based on the anticipated low pH. Since we
expect the equivalence point to be well below the pK 1, the first term, [H ]/K1,
should be much greater than the other two terms in that set of brackets.
Thus we can eliminate the others and rearrange.

[H+] = CTK1/[H+]
(16.37)

(@EP)

and solving for the hydrogen ion concentration:

[H+] = (CTK1)0.5
(16.38)

(@EP)

If we assume that natural waters are dominated by bicarbonate, the number

of moles of total carbonate (i.e., CT) will be approximately equal to the
number of equivalents of alkalinity. So if we express alkalinity in mg/l as
CaCO3 this becomes:
CT
(16.39)

Alktot/50,000

Finally combining this with equation 16.38 and taking the negative logarithm
of both sides we get the following expression for the pH at the final
equivalence point in an alkalinity titration:
(@EP)
(16.40)
Note that equation 16.40 predicts equivalence points very close to the pHs
where they have been observed experimentally (i.e., compare with table in
section on analytical procedures).
h. Calculation of Acidity
The mineral acidity, also known as the methyl orange acidity, is
equivalent to the amount of base (i.e., the titrant) required to bring the pH
up to 4.5 (methyl orange endpoint). It is so named, because mineral acids
such as HCl, when present at significant concentrations, are almost
completely neutralized before the pH reaches 4.5. The carbon dioxide acidity
is the additional base required to raise the pH from 4.5 or the initial pH,
whichever is higher, to pH 8.3 (phenolphthalein endpoint). Likewise carbon
dioxide does not begin to become neutralized until pH 4.5 is passed, and its
neutralization reaches completion (equivalence point) at pH 8.3. Finally, the
total acidity, or phenolphthalein acidity, is the sum of the mineral acidity and
the carbon dioxide acidity.

(16.41)

(16.42)

(16.43)
As before, the factor of 50,000 is used because acidities as well as
alkalinities are commonly expressed in terms of milligrams per liter of
equivalent calcium carbonate.
i. Correlations With Other Water Quality Parameters
i. Total Dissolved Solids Since alkalinity is dominated by the major
anion, bicarbonate, it is possible to relate alkalinity to the total concentration
of dissolved solids. If we assume that fresh waters are composed exclusively
of calcium and bicarbonate, for every mole of calcium bicarbonate
(Ca(HCO3)2) we will have two equivalents of alkalinity. Since one mole of
calcium bicarbonate should weigh 162 grams and one equivalent of alkalinity
is equal to 50 g as CaCO3, the mass ratio should be 100/162 or 0.62.
Alktot
(16.44)

0.62(TDS)

Such relationships are inherently site specific and they must be verified with
each new water.
ii. Conductivity Alternatively, alkalinity might be expected to correlate
with conductivity. Since the equivalent ionic conductances at infinite dilution
are 59.5 mho-cm2/equivalent for calcium and 44.5 mho-cm 2/equivalent for
bicarbonate, the total solution equivalent conductance at infinite dilution, G o,
is 104 mho-cm2/equivalent (at 25oC). While this value will decrease some
with increasing concentration, it may be considered constant for solutions up
to 200 mg/l alkalinity (as CaCO 3) without introducing too much error. The
equivalent conductance, , is related to the conductivity according to:
Conductivity
(16.45)

C(1000)

when conductivity is in umho/cm. Here "C" represents the equivalent

concentration of the salt. For a pure solution of calcium and bicarbonate this
would just be equal to the alkalinity (in mg/L as CaCO 3) divided by 50,000.

Also as previously stated we will assume that the equivalent conductance, G,

is equal to the limiting equivalent conductance at infinite dilution G o. Thus
equation 16.45 can be rearranged to get:
Alktot
(16.46)

0.50(Conductivity)

In practice this relationship is not useful below 50 mg/l alkalinity as the

presence of other non-alkalinity anions contributes significantly to the overall
conductivity. Thus, with soft waters equation 16.46 overestimates the
alkalinity.
j. Special Considerations for Samples of Low Ionic Strength
It is important to avoid streaming potential effects in dilute solutions.
Therefore, such samples should be allowed to stand quiescently for several
minutes before measuring (McQuaker et al., 1983).
RESEARCH TOPIC
2. DETERMINATION OF ORGANIC FUNCTIONAL GROUPS
The determination of organic functional groups is useful for research
on natural organic matter (NOM), its behavior in engineered systems (e.g.,
drinking water treatment) and its behavior in natural systems. Unfortunately,
all titrimetric methods for total functional group content and for speciation of
these groups in NOM (especially humic materials) are inherently operational
(Perdue, 1985).
a. Direct Method for Total Carboxyl and Phenolic Content
Carboxyl and phenolic groups can be determined by direct
potentiometric titration. For best results, the samples should be free from
acidic inorganic species and hydrogen saturated. The sample is titrated with
NaOH to a carboxyl end point of pH 8. The titration can be continued to pH
10 where roughly half of the phenolic groups are deprotonated. One may
then estimate the phenolic content by doubling the amount of base required
to change the pH from 8 to 10. Thurman (1985) points out that since ortho
substituted carboxyl groups render the phenolic-OH groups very weakly
acidic (pKa of about 13), these may be missed by such a titration.
Problems inherent in direct titrations of natural organic matter may
limit their usefulness. A slow pH drift (downwards in alkaline titrations) and
hysteresis often accompanies these measurements. The reasons for this are
not clear, but alkaline hydrolysis (of organic matter, Me-org complexes, and
metals), conformational changes, alkaline oxidation, biodegradation may be

responsible (Perdue, 1985). In order to minimize oxidation and

biodegradation, these titrations should be carried out under nitrogen.
Another problem arises from the difficulty in accurately measuring high pH
values. This is in part due to the high concentration of alkali metal ions which
interfere with potentiometric pH measurements.
b. Barium hydroxide method for total acidity.
A popular method for the determination of total acidity in terrestrial
humic materials utilizes barium hydroxide. The addition of an excess of
Ba(OH)2 to a sample containing organic matter brings the pH up to about 13 where nearly all acidic protons are removed. The
high concentration of barium coupled with the high complexation constants of barium-organic salts, leads to nearly complete binding
by barium of the charged functional groups. In the process, the complexed organic matter is rendered less soluble and must be
physically removed by filtration. Then, the protons originally liberated from the organic matter upon addition of the hydroxide may be
determined by back titration of the residual hydroxide in the filtrate. Unfortunately, this method has some serious weaknesses for
analysis of aquatic organic matter. First, for efficient separation, it is critical that the barium-complexed organic matter rapidly
precipitate. However, the greater hydrophilic nature and lower molecular weight of aquatic organic matter as compared to terrestrial
matter makes precipitation of this material less complete. Second, any functional groups that are not protonated at the start (i.e.,
anionic or complexed by metals) are not likely to be measured by this technique. Lowering the starting pH would minimize the
problems of incomplete titration, however, this would introduce additional uncertainties from the difficulty of accurately measuring
high concentrations of hydrogen ions.

C. Complexation Titrations
Complexation or complexometric titrations are based on the
formation of a complex. Commonly, a metal is the analyte to which some
ligand is added. This ligand must be chosen so that complexation is quick,
has a well defined stoichiometry, and goes very nearly to completion. The
most frequently used ligand is ethylenediaminetetraacetic acid or EDTA
[HOOCCH2)2NHCH2CH2NH(CH2COOH)2]. This is a hexadentate ligand which
binds very strongly to many metals giving a 1:1 stoichiometry. It has been
applied to the determination of many metals (for example see: Flaschka,
1959; Schwarzenbach & Flaschka, 1969). Table 16.3 shows some stability
constants for EDTA complexes based on formation only with the fully
deprotonated species, Y-4.
M+n
(16.47)

Y-4

and:
K
(16.48)

MYn-4

[MYn-4]/[M+n][Y-4]

Table 16.3
EDTA Stability Constants
(from Martell & Smith, 1974)

Metal

Log
K

Metal

Log
K

K (+I)
0.8
Pb (+II)
18.04
Na (+I)
1.66
Sn (+II)
18.3
Li (+I)
2.79
Ni (+II)
18.62
Ba (+II)
7.86
Cu (+II)
18.80
Mg (+II)
8.79
Hg (+II)
21.7
Ca (+II)
10.69
Al (+III)
16.3
Cr (+II)
13.6
Cr (+III)
23.4
Mn (+II) 13.87
Mn (+III)
25.3
Fe (+II)
14.32
Fe (+III)
25.1
Note that these constants are quite large indicating that complexation goes
very nearly to completion. The strong binding of metals by EDTA is due in
part to its ability to completely surround the metal, often forming a sixcoordinate species. In general, the more coordinating sites a ligand has, the
stronger the metal binding. Also, the high the charge on the metal, the
stronger the binding is with EDTA.
Since its only the Y-4 species of EDTA that is considered to form strong
complexes, one must take into account the speciation of this ligand. EDTA
has the following dissociation constants:
Carboxylic groups
pK1 = 0.0 pK2 = 1.5 pK3 = 2.0 pK4 = 2.66
Amine groups
pK5 = 6.16 pK6 = 10.24
Therefore, at neutral pH all four of the carboxyl groups are deprotonated, and
one of the amine groups is partially deprotonated (HY -3 form). The fraction of
the total EDTA that is in the Y -4 form at any pH is given by the 6 (loss of 6
protons from the fully-protonated H6Y+2 form).

= 1/{[H ]6/K1K2K3K4K5K6 + [H+]5/K2K3K4K5K6 + [H+]4/K3K4K5K6

+
[H+]3/K4K5K6
+
[H+]2/K5K6
+
[H+]/K6
(16.49)
6

1}

Substitution of the appropriate acidity constants into equation 16.49 gives an

estimate of fraction of EDTA that is in the appropriate form for complexation
(Table 16.4)
The endpoint of complexometric titrations may be detected by either
an ion-selective electrode sensitive to the metal being analyzed, or a metal
ion indicator. This latter method employs a chelating ligand which changes
color in going from the complexed to the uncomplexed form. For a metal ion
indicator to be effective, it must bind the metal less strongly than EDTA does
at the given pH. Also, it must not be affected by other metal ions in the
sample.
Table 16.4
Values
for
EDTA
as a function of pH
6
pH
1
3
5
7
9
11

6
1.9x10-18
2.6x10-11
3.7x10-7
5.0x10-4
0.054
0.85

pH
2
4
6
8
10
12

6
3.3x10-14
3.9x10-9
2.3x10-5
5.6x10-3
0.36
0.98

For calcium and total hardness determinations, a couple of specific

dyes, Eriochrome black T (Figure 16.4) and Eriochrome blue black R, are used
as metal ion indicators. These dyes do not bind magnesium and calcium as
strongly as EDTA. However, Eriochrome black T will bind Cu(+II), Ni(+II),
Co(+II), Cr(+III), Fe(+III) and Al(+III) more strongly than EDTA. It is said to be
blocked by these metals, and cannot be used for their direct determination
with EDTA as a titrant.

Figure 16.4. Eriochrome black T

1. TOTAL HARDNESS
A. Definition and Environmental Significance
Hardness is a term used for the total concentration of divalent cations
in water. These may include Ca(+II), Mg(+II), Sr(+II), Ba(+II), Fe(+II) and
Mn(+II), although the last four are usually negligible. It is a parameter of
concern in drinking waters, and sometimes industrial process waters and
agricultural waters. Hardness is considered a nuisance, because divalent
cations will bind (complex) with the carboxyl groups in soap and cause its
precipitation. In this way is inhibits its action (sudsing), and is often said to
"consume" soap. In addition, hardness species may cause severe hydraulic
problems in pipes by precipitating as metal carbonates. This is especially
true when the water is heated such as in home water-heaters, and boilers.
On the other hand, hardness has been associated with lower incidences of
cardiovascular disease. This last point is controversial, however.
Hardness is derived from limestone and related minerals. Highest
concentrations in US surface waters are found in the mid-west and southwest. Hardness has historically been expressed as a mass concentration of
equivalent calcium carbonate. This is done, because calcium is the dominant
hardness species and carbonate-bicarbonate is the most prevalent counter
ion. Therefore, the conversion factor is just the molecular weight of CaCO3.
1 mole/L of Hardness = 100 g/L of hardness as CaCO 3
(16.50)
1 equivalent/L of Hardness = 50 g/L of hardness as CaCO 3
(16.51)
Hardness may be categorized by the constituent anions (i.e., calciumhardness, magnesium-hardness) or by the counter ions (i.e., carbonate and
non-carbonate hardness). The carbonate hardness is the maximum amount
of hardness that could possibly be precipitated as carbonates. Such a

precipitation might occur if the sample were to be heated, evaporated or if

the pH was raised. Carbonate hardness is equal to the alkalinity (in mg/L as
CaCO3) when the alkalinity is less than the total hardness. The remaining
hardness is referred to as non-carbonate. When the reverse is true (i.e.,
hardness < alkalinity), the carbonate hardness is equal to the total hardness,
and non-carbonate hardness is zero.

hardness

Total
hardness
(16.52)
Total hardness =
(16.53)

Ca-hardness

Carbonate

hardness

Mg-hardness

non-carbonate

Hardness is commonly removed in drinking water treatment plants by

alkaline precipitative softening. In order to calculate chemical requirements
for precipitative softening, it is necessary to know both the total hardness,
and the calcium hardness (i.e., calcium concentration). Point of use
treatment systems generally use cation exchange to remove hardness.

B. Principle
Eriochrome black T is added to the sample at high pH (about 10). The
high pH causes the metal ion indicator to partially deprotonate, giving a form
that is effective as a chelating agent (pKs are 6.3 and 11.6). A deep red
complex then forms with calcium and magnesium present in the sample.
Also at this pH the color change experienced by the indicator is most easily
seen (e.g., at lower pH the uncomplexed, protonated Eriochrome black T is
also somewhat reddish). Furthermore, the EDTA is most effective at high pH
(recall Table 16.4). On the other hand, calcium and magnesium as well as
many other metals, will hydrolyze and precipitate at high pH. This is
undesirable as it would take them out of solution and prevent their
determination. To avoid this problem an auxiliary complexing agent is added.
These are ligands that bind strongly enough with the analyte to out-compete
hydroxide binding, and thereby prevent its precipitation, but not so strongly
as to interfere with binding by the EDTA or metal ion indicator. In the case of
total hardness, triethanolamine and ammonia are used, but other types of
titrations might also use citrate or tartrate. Whether or not the auxiliary
complexing agent reacts with metal ions other than the analyte is not
important.
In all but the softest of waters, calcium and magnesium will be
present in large excess as compared to the metal ion indicator. When EDTA is
titrated, it ties up this excess magnesium and calcium. Once the excess
hardness is exhausted, the EDTA begins stripping the Eriochrome black T of
its calcium and magnesium. The indicator then loses its intense red color (to
blue color) and the titration is at its endpoint. The presence of magnesium

improves the sharpness of the endpoint. To ensure that some magnesium will
be present, a small amount of Mg-EDTA is added along with the buffer.
Because both analyte and titrant are added in a 1:1 ratio, this does not effect
the final determination. The moles of EDTA added as titrant are equal to the
moles of calcium and magnesium originally present. This type of procedure is
referred to as a direct complexometric titration.
In a back complexometric titration, EDTA is added in excess and a
metal other than the analyte metal is used as the titrant. For this type of
titration it is important that the titrant metal bind less strongly to EDTA than
does the analyte. A back titration is useful under conditions where the metal
cannot be kept in solution in the absence of EDTA, where the analyte blocks
the indicator, or where complexation kinetics with EDTA are slow.
When high concentrations of interfering metal are present, certain
inhibitors must be added prior to titration. These are ligands that will
strongly bind the interfering metal, such as cyanide, sulfide, and
hydroxylamine. A large interlaboratory study found a relative standard
deviation of 2.9% and a relative bias of 0.8% for a synthetic sample
containing 610 mg/L total hardness as CaCO3.
C. Procedures
1. Place exactly 50 ml of the sample into a 125 ml erlenmeyer
flask.
2. Add 1-2 ml of the buffer solution
3. Add 5-6 drops of the EBT indicator.
4. Titrate with the EDTA solution until all reddish coloration
disappears. Maintain constant stirring during this
operation. For best results the titration should be
completed within 5 minutes.
D. Reagents
1. Buffer Solution - Dissolve 16.9 g ammonium chloride in 143
ml conc ammonium hydroxide. <caution: avoid inhalation
of fumes!> Add 1.25 g Mg-EDTA and dilute to 250 ml with
distilled water.
2. Hardness Indicator Solution (approx. 0.011M) - Dissolve 0.5 g
of Eriochrome Black T (1-(1-hydroxy-2-naphthylazo)-5nitro-2-naphthol-4-sulfonic acid) in 100 g triethanolamine
(2,2',2''-nitrilotriethanol).
3. EDTA Titrant Solution (approx. 0.01M) - dissolve 3.723 g NaEDTA (sodium ethylenediaminetetraacetate dihydrate) in
1000 ml distilled water. Determine titer by standardizing
agaist the standard calcium solution (follow steps 1-4).
4. Standard Calcium Solution (5.00 mM) - Weigh 0.5005 g
anhydrous calcium carbonate (primary standard grade)
and place in a 500-ml erlenmeyer flask. Carefully add

small amounts of 6 M HCl (approx 50% of conc.) until

CaCO3 just dissolves. Add 200 ml distilled water and boil
for a few minutes to expel dissolved CO 2. Cool, add a few
drops of methyl red indicator and adjust to the
"intermediate" orange color by adding 3N NH 4OH or 6M
HCl as needed. Transfer quantitatively to a 1-liter
volumetric flask and dilute to the "mark" with distilled
water.

2. CALCIUM
A. Principle
Calcium can be determined by atomic absorption spectrophotometry,
by a redox titrimetric method and by a complexometric method. The
complexometric procedure outlined here is quite similar the the total
hardness method. Several modifications must be made however, to make
the analysis specific for this one hardness species. First, a metal ion indicator
that complexes with calcium, but not magnesium (Eriochrome blue black R)
is used. Second magnesium is partially removed by using a higher pH (about
12) which results in precipitation as Mg(OH) 2. Note that auxiliary complexing
agents are not used in this procedure. Calcium hydroxide does not
precipitate at this elevated pH. In addition, EDTA binds preferentially with Ca
by virtue of its larger stability constant. An extensive interlaboratory study
found a standard deviation of 9.2%, and a relative bias of 1.9% for a
synthetic water containing 108 mg/L calcium and 82 mg/L magnesium.
B. Procedures
1. Place exactly 50 ml of the sample into a 125-ml erlenmeyer
flask.
2. Add 3 ml of NaOH solution. If the pH is still below 12, add
more base.
3. Add 1 scoop of Eriochrome Blue Black R indicator (0.1-0.2 g)
4. Titrate with the EDTA solution until the color changes
completely from red to royal blue. Maintain continuous
stirring throughout.
C. Reagents
1. EDTA Titrant Solution (approx. 0.01M) - (same as with
hardness determination) dissolve 3.723 g Na-EDTA
(sodium ethylenediaminetetraacetate dihydrate) in 1000
ml distilled water. Determine titer by standardizing
against the standard calcium solution (follow steps 1-4).
2. Sodium Hydroxide Solution (1N) - Dilute 40 g NaOH to 1 liter
with distilled water.
3. Eriochrome Blue Black R indicator - Grind together in a
mortar 200 mg powdered dye [sodium-1-(2-hydroxyl-1naphthylazo)-2-naphthol-4-sulfonic acid] and 100 g solid
NaCl to about 40-50 mesh. Store in a tightly stoppered
bottle.
4. Standard Calcium Solution (5.00 mM) - Weigh 0.5005 g
anhydrous calcium carbonate (primary standard grade)
and place in a 500-ml erlenmeyer flask. Carefully add
small amounts of 6 M HCl (approx 50% of conc.) until

CaCO3 just dissolves. Add 200 ml distilled water and boil

for a few minutes to expel dissolved CO 2. Cool, add a few
drops of methyl red indicator and adjust to the
"intermediate" orange color by adding 3N NH 4OH or 6M
HCl as needed. Transfer quantitatively to a 1-liter
volumetric flask and dilute to the "mark" with distilled
water.

D. Redox Titrations
Redox titrations are based on oxidation-reduction reactions between
the analyte and the titrant or some intermediate redox carrier. Common
oxidants used in redox titrations include dichromate (Cr 2O7-2), iodate (IO3-),
iodine (I2), and permanganate (MnO4-). Common reducing agents are arsenite
(AsO3-3), ferrocyanide (Fe(CN)6-4), ferrous (Fe+2), sulfite (SO3-2) and thiosulfate
(S2O3-2). Although many of the oxidizing agents are relatively stable, the
reducing agents are often susceptible to oxidation by atmospheric oxygen,
and therefore their titer must be checked regularly against a standard.
Many redox titrations utilize iodine. When a reducing analyte is added
to I2 to form I-, the process is called Iodimetry. Instead, when an ozidizing
analyte converts I- to I2, it is Iodometry. In the presence of iodide (I -), iodine
(I2) will form a triiodide complex (I 3-) which greatly enhances its solubility in
water. For the determination of triiodide, sodium thiosulfate is almost always
used as the titrant. Although triiodide can be self-indicating, starch is
generally used as an end point indicator. It forms an intense blue color with
triiodide which can increase the sensitivity of endpoint detection by a factor
of ten. It is important not to add starch until just before the endpoint. This
allows one to see a more more gradual color change in the early part of the
titration, and it avoids problems with excessively strong triiodide binding by
the starch and over shoot.
Thiosulfate reacts with triiodide rapidly under neutral or acidic
conditions to give iodide and titrathionate. Commercial thiosulfate is not of
sufficient purity to be a primary standard. Instead, it must be titrated against
a standard triiodide solution prepared by reaction of iodide with some
primary standard oxidant (e.g., KIO3). Thiosulfate is also readily oxidized by
atmospheric oxygen at neutral to acidic conditions. It must be stored in a
slightly alkaline buffered solution; often carbonate is used for this purpose.

1. RESIDUAL CHLORINE (DPD Titrimetric Method)

A. Principle
Either chlorine or triiodide react with N,N-Diethyl-p-phenylene
diamine (DPD) to form a relativly stable free radical species with an intense
red color. This is then back titrated to the original colorless form with ferrous
iron. The detection limit is about 18 ug/L. Oxidized manganese species will
interfere. The DPD methods are the most widely used of the chlorine residual
procedures (Gordon et al., 1988).
Free residual chlorine is measured first via direct reaction with DPD.
Monochloramine will react slowly with DPD through a direct pathway at a

rate of about 5% per minute depending on concentration. For this reason

mercuric chloride is added (HgCl2). It apparently inhibits the reaction
between monochloramine and DPD. Although the reaction mechanisms isn't
known, it is presumed to act by formation of an unreactive complex with
monochloramine.
Combined residuals are measured after addition of iodide.
Monochloramine will react quickly with trace quantities of iodide to form
triiodide which then reacts with the DPD. For dichloramine, the reaction is
much slower, and relatively large amounts of iodide are needed for the
reaction to go to completion. Both hydrogen peroxide and persulfate will also
oxidize iodide, and can therefore interfere with the combined residual
chloring determination.
The DPD reagent is also subject to base catalyzed oxidation by
atmospheric oxygen. For this reason it is kept in an acidified state, and
replaced every month. Since the reaction with chlorine and triiodide is best
when carrier out at neutral pH, a neutral buffer is used and the DPD must be
stored separately from the buffer and added at the last minute.

Figure 16.5
DPD Titrimetric Determination of Chlorine
B. Procedure
1. Place 5 ml of both the buffer reagent and the DPD indicator
solution in the titration flask and mix.
2. Add 100 ml sample and mix.

3. Free Residual Chlorine (FRC): Titrate rapidly with standard

ferrous ammonium sulfate (FAS) titrant until the red color
disappears (Reading A).
4. Monochloramine (MCA): Add one very small crystal of
Potassium Iodide (KI) to solution from step 3 and mix.
Continue titration until the red color again disappears
(Reading B).
5. Dichloramine (DCA): Add several crystals of KI (about 1 g) to
the solution titrated in step 4 and mix to dissolve. Allow to
stand for 2 minutes and then continue titration until the
red color is again discharged (Reading C). For very high
dichloramine concentrations, allow an additional 2 minutes
standing time if color driftback indicates incomplete
reaction. When dichloramine concentrations are not
expected to be high, use half the specified amount of
potassium iodide.
6. CALCULATIONS
The various forms of chlorine residual are best calculated
according to the following scheme. Note that for a 100 ml
sample, 4.00 ml standard FAS titrant = 1.00 mg/l residual
chlorine.
Species
HOCl + OCl
NH2Cl
NHCl2

Formula
A/4
(B-A)/4
(C-B)/4

C. REAGENTS
1. Phospate buffer solution: Dissolve 24 g anhydrous Na 2HPO4,
and 46 g anhydrous KH2PO4 in distilled water. Combine
this solution with 100 ml distilled water in which 800 mg
Na2EDTA have been dissolved. Dilute to 1 liter with
distilled water and add 20 mg HgC12 to inhibit biological
growth and to control iodide interferences in the FRC
titration.
2. DPD Solution: Dissolve 1 g N,N-diethyl-p-phenylenediamine
oxalate in distilled water containing approximately 2 ml
conc. H2SO4 and 200 mg Na2EDTA dihydrate. Make up to 1
liter, store in a brown glass-stoppered bottle.
3. Standard ferrous ammonium sulfate (FAS) titrant: Dissolve
1.106 g Fe(NH4)2(SO4)2 . 6H20 in distilled water containing
1/4 ml of conc. H2SO4 and make up to 4 liters with distilled
water.

4. Potassium Iodine Crystals

2. OZONE (iodometric method)

Gas-phase concentrations of ozone are most easily measured
iodometrically. A portion of the gas stream is directed to a gas bubbler filled
with 2% KI solution for an exact period of time. Ozone reacts
stoichiometrically to form an equivalent amount of iodine.
O3 +
(16.55)

2KI

H2O

--------->

I2

O2

2OH-

2K+

The iodine formed is then titrated with sodium thiosulfate using starch as an
indicator to accentuate the endpoint (APHA et al., 1985).

3. DISSOLVED OXYGEN
A. Significance to Environmental Engineering
Dissolved Oxygen (D.O.) is an important water quality parameter for
natural aquatic systems. A minimum concentration is required for the
survival of higher aquatic life. In particular, the larval stages of certain coldwater fishes are quite sensitive. Significant discharges of organic wastes may
depress the D.O. concentrations in receiving waters. This occurs due to the
rapid, microbially-mediated oxidation of these wastes upon discharge. For
this reason each state has established ambient dissolved oxygen standards
that must not be violated. These standards effectively limit the organic waste
loading and spatial distribution of these loads to natural waters.
Another use of D.O. is the assessment of oxidation state in
groundwaters and sediments. As samples are collected deeper into the
subsurface or into aquatic sediments, the D.O. often drops. Eventually the
level is low enough so that anaerobic process predominate.
Dissolved oxygen is also a very important parameter in biological
treatment processes. In a gross sense, D.O. concentrations indicate when
aerobic and anaerobic organisms will predominate. However, more
commonly, dissolved oxygen determinations are used to assess the
adequacy of oxygen transfer systems to aerobic suspended culture
operations such as activated sludge. It may also be used to indicate the
suitability for the growth of such sensitive organisms such as the nitrifying
bacteria.
Finally, dissolved oxygen is used in the assessment of the strength of
a wastewater through either the Biochemical Oxygen Demand (BOD) or
respirometric studies. Briefly, the BOD test employs a bacterial seed to
catalyze the oxidation of 300 mL of full-strength or diluted wastewater. The
strength of the un-diluted wastewater is then determined from the dilution
factor and the difference between the initial D.O. and the final D.O.
Oxygen is a rather insoluble gas, and as a result its is often the
limiting constituent in the purification of wastes and natural waters. Its
solubility ranges from 14.6 mg/l at 0 oC to about 7 mg/l at 35 oC. In addition to
temperature, its solubility varies with barometric pressure and salinity. The
saturation concentration of oxygen in distilled water may be calculated from
the following empirical expression:

(16.56)

where:
Pvw = water vapor partial pressure (atm)
= 11.8571 - (3840.70/Tk) + (216,961/Tk2)
P = total atmospheric (barometric) pressure (atm), which may be
read directly or calculated from a remote reading at
the same time from:
= Po - (0.02667)H/760
H = Difference in elevation from the location of interest (at P) to
the reference location (at Po) in feet.
Po = Simultaneous barometric pressure at a nearby reference
location
= pressure/temperature interactive term
= 0.000975 - (1.426x10-5T) + (6.436x10-8T2)
T = Temperature in degrees centigrade
Cs1 = Saturation concentration of oxygen in distilled water at 1
atmosphere total pressure.
ln(Cs1) = -139.34411 + (1.575701x105/Tk) - (6.642308x107/Tk2) +
(1.243800x1010/Tk3) - (8.621949x1011/Tk4).
(16.57)
Tk = Temperature in degrees Kelvin (Tk = T + 273.15)
Under most circumstances (elevation less than 1000 ft, average weather)
the pressure may be assumed to be 1 atm, and C s can be approximated by
Cs1 using only the above equation. One might also turn to any one of a
number of tabulations of Cs1 (as a function of temperature) such as is found
on pg 413 of the 16th edition of Standard Methods for the Examination of
Water and Wastewater.
Dissolved oxygen may be measured by two common methods, the
Winkler titrimetric method and the Membrane Electrode method. The
Winkler method, like all classical methods of analysis, measures dissolved
oxygen concentration. The electrode method measures dissolved oxygen
activity. The two are related by the activity coefficient, O2:

(16.58)
where the square brackets ([....]) indicate concentration (Moles/liter) and
the curved brackets ({....}) indicated activity. For most unpolluted or
moderately polluted waters, the activity coefficient will be very close to 1.0,
and concentration will equal activity. However, for some waters containing
high concentration of salinity, oxygen activities will be greater than
concentrations. Activity better describes the "availability" of oxygen, and is
therefore, more important in determining oxygenation kinetics.

Concentration better represents the "buffering capacity" against anoxic

conditions, and it is more important in stoichiometric calculations.
Nevertheless, with most engineering application, the two are essentially
equivalent. Other concerns and relative advantages of the two methods are
as follows:
Winkler
1. Does not require expensive or sophisticated equipment.
2. It is little hindered by surfactants and surface-coating species
3. Mixing intensity is of little concern

Figure 16.6
Chemical Scheme for the Winkler D.O. Analysis
Electrode
1. Final determinations can be readily made in the field
2. In situ D.O. measurements are easily made, because the electrodes
are generally immersible
3. It can be used for continuous monitoring

4. It is non-destructive. Thus, the sample may be returned or used for

additional analyses.
5. It may be used with highly-colored waters
B. Principles
Manganese is rapidly oxidized by dissolved oxygen at high pH. It then
oxidizes iodide to iodine at low pH, and the resulting iodine is titrated with
sodium thiosulfate. Starch is used to obtain a sharper endpoint.
Final acidification is employed to reach a pH below 5 where the proper
stoichiometry for the iodine/thiosulfate reaction is obtained, however, the pH
must not drop too low so that the decomposition of thiosulfate becomes
important. Under acidic conditions, the iodine will react with any residual
iodide to form triodide anion (I3). It is actually this species which reacts with
thiosulfate giving tetrathionate and three iodide anions.
The alkali azide iodide reagent also contains sodium azide, NaN 3. This
is a recent modification designed to eliminate interferences due to nitrite.
The azide will react with nitrite to give nitrogen gas and nitrous oxide,
neither of which cause interferences.
NaN3

+
(16.59)

HN3

+
NO2(16.60)

H+

------------->
H+

--------->

HN3
N2

Na+

+
N2O

H2O

Otherwise nitrite would oxidize iodide to iodine thereby raising the apparent
dissolved oxygen concentration.
2NO2-

+
2I(16.61)

4H+

------------->

I2

N2O2

2H2O

Note that the product, a nitric oxide species, can then scavenge any oxygen
introduced during titration and reform nitrite to start the cycle over again.
N2O2

+
1/2O2
(16.62)

H2O

----------------->

2NO2-

2H+

Other substances which may interfere include reducing agents such as

sulfite, thiosulfate, ferrous iron, and aldehydes.
Because thiosulfate often contains an ill-defined number of waters of
hydration, it is difficult to prepare an exact concentration by weight alone.
Thus, it is necessary to standardize this solution against a primary standard
such as potassium dichromate or potassium biniodate. Biniodate is preferred,

because the reaction with dichromate is slow and the color of trivalent
chromium may interfere with the endpoint. In either case, a known amount
of the primary standard is added to an excess of iodide.
2IO3-

+
(16.63)

10I-

Cr2O7-2

+
6I(16.64)

+
+

14H+

12H+
-------->

-------->
2Cr+3

6I2
+

+
3I2

6H2O
+

7H2O

The resulting equivalent concentration of iodine is titrated with the

thiosulfate solution. Thiosulfate solutions should be preserved with a small
amount of sodium hydroxide. This serves to discourage the growth of sulfur
bacteria which oxidize thiosulfate to sulfate. Also the high pH will retard
downward pH drift (from absorption of atmospheric carbon dioxide) and
thereby minimize the disproportionation of thiosulfate to sulfate and
elemental sulfur.
Duplicate analyses using the Winkler method (with azide
modification) should agree within a standard deviation of 20 ug/l for distilled
water and 60 ug/l for wastewater. Samples containing high concentrations of
interfering substances may show greater variabilities. Negative systematic
errors can occur due to the loss of iodine prior to (or during) titration through
volatilization or reaction with organic matter. Positive systematic error may
result from a small amount of air oxidation of iodide also during titration.
C. Sampling
It is important to limit contact of the sample with air. Where possible
use a Kemerer or Van Dorn-type sampler. Specialized D.O. samplers are also
available that passively flush the sample bottle with 1 or 2 volumes of
sample before taking the final sample. A typical field sampling procedure
using a Van Dorn sampler would be:
1. Prepare Van Dorn sampler by pulling back the plungers and
setting their lines in the triggering mechanism.
2. Lower sampler to the desired height and release messenger.
3. Raise sampler, insert rubber tube deep into a BOD bottle,
release clamp and open vent. Allow the BOD bottle to
overflow by two full volumes.
4. Remove rubber tube, cap the BOD bottle and close the tube
clamp.
5. Repeat until the desired number of samples have been taken.
It is common practice to "fix" (add all three reagents) in the field for later
titration. However, this may tend to give negative bias due to loss of iodine.
An alternative is to add 0.7ml sulfuric acid, 0.02g sodium azide to each
sample, keep cold and away from light for complete analysis up to 6 hours

later. In this case it would be necessary to add additional 2 ml of the

manganous sulfate reagent, 3 ml of the alkali-iodide-azide reagent and 2 ml
of the sulfuric acid.
D. Procedures
1. To a 300 ml BOD bottle filled with sample add 1 ml
manganous sulfate solution and 1 ml alkali-iodide-azide
reagent, cap and shake. Be careful to avoid trapping any
air bubbles. If this occurs, remove cap, add a small
amount of distilled water and re-cap.
2. Allow precipitate to settle to about half the hight of the bottle
and add 1 ml conc. sulfuric acid. Re-stopper and mix.
3. Titrate 200 ml of this sample with the 0.025M sodium
thiosulfate solution until a very pale yellow color is
obtained. Add a few drops of the starch solution and
titrate until the blue color disappears.
E. Winkler Reagents
1. Manganous surfate solution - Dissolve 400 g MnSO 4.2H2O in
distilled water and dilute to 1 liter.
2. Alkali-iodide-azide reagent - Dissolve 500 g NaOH and 150 g
KI in distilled water and dilute to 1 liter. Add 10 g NaN 3
dissolved in 40 ml distilled water.
3. Sulfuric acid concentrated
4. Sodium Thiosulfate titrant - (0.025M) Dissolve 6.205 g
Na2S2O3.5H2O in distilled water. Add 0.4 g NaOH and dilute
to 1 liter. Standardize with the primary-standard
Potassium Biniodate or Potassium Dichromate solution
using starch to define the endpoint.
5. Starch Solution - Dissolve 2g soluble starch and 0.2g salicylic
acid (preservative) in 100ml of hot distilled water.

4. CHEMICAL OXYGEN DEMAND

The chemical oxygen demand (COD) of a waste is measured in terms
of the amount of potassium dichromate (K2Cr2O7) reduced by the sample
during 2 hr of reflux in a medium of boiling, 50% H 2SO4 and in the presence
of a Ag2SO4 catalyst.
The stoichiometry of the reaction between dichromate and organic
matter is:

(16.65)
where:
(16.66)
The oxidation is accompanied by the reduction of dichromate:
6e- + 14H+ + Cr2O7-2 -----------> 2Cr+2 + 7H2O
Eo = 1.33 volts

(16.67)

Chloride ion interferes, being precipitated as AgCl and subject to

unpredictable oxidation when Ag2SO4 is used as a catalyst, or being oxidized
to Cl2 when Ag2SO4 is not used:
6Cl- + 14H+ + Cr2O7-2 -----------> 3Cl2 + 2Cr+2 + 7H2O

(16.68)

Free chloride is largely removed by complexation with mercury as HgCl 2(aq).

Autooxidation of Cr2O7-2, and organic impurities in the reaction system can be
accounted for by running a blank with distilled water.
Upon completion of the reaction with organic matter, it is necessary
to determine the residual dichromate in the reaction flask. A reducing agent,
in this case Fe+2, can be used to titrate the dichromate.
Fe+2 ------------> Fe+3 + eEo = -0.77 volts

(16.69)

However, because of the various ionic interactions which occur in electrolyte

solution, the oxidation potential for iron in 1M sulfuric acid is -0.66 volts
(formal potential). The endpoint of the ferrous titration of dichromate can be
determined colorimetrically using Ferroin indicator. Ferroin contains 1,10phenanthroline, which forms a colored complex with the ferrous ions. At the
endpoint after the dichromate has been reduced, the color changes from
blue-green to reddish brown (Fe-phenanthroline complex).
The COD test is faster than BOD analysis, so it is commonly used as a
quick assessment of wastewater strength and treatment performance. Like
the BOD, it does not measure oxidant demand due to nitrogeneous species.
However, it cannot distinguish between biodegradable and nonbiodegradable organic matter. As a result COD's are always higher than
BOD's.

REFERENCES
APHA, AWWA, and WPCF, Standard Methods for the Examination of Water
and Wastewater, APHA, Washington (14 ed) pp. 273-282, or (15 ed) pp.
249-257, or (16 ed) pp. 265-273.
Flaschka, H.A. (1959) EDTA Titrations, Pergamon Press, New York.
Kramer, J.R. (1982) "Alkalinity and Acidity", Chapter 3 in Water Analysis:
Volume 1, Inorganic Species, R.A. Minear & L.H. Keith editors, Academic
Press, pp.85-135.
McQuaker et al. (1983) Environ. Sci. & Technol., 17:431-435.
Perdue, E.M. (1985) Acidic Functional Groups of Humic Substances, in Humic
Substances in Soil, Sediment and Water: Geochemistry, Isolation, and
Characterization, Aiken et al., eds., Wiley, Publ., New York, pp. 493-526.
Sawyer, C.N. and P.L. McCarty (1978) Chemistry for Environmental
Engineering, 3rd Edition, McGraw-Hill Publ., pp. 24-29, 168-188, 343-376.
Schwarzenbach, G & H.A. Flaschka (1969) Complexometric Titrations,
Methuen, London.
Snoeyink, V.L. and D. Jenkins (1980) Water Chemistry, Wiley, pp. 86-145,
156-196.
PROBLEMS
16.1 An EDTA solution is added to water sample containing a low
concentration of calcium (20oC). If the total EDTA concentration (all
forms) in the water is 0.1M, and all metal species that might form
complexes are several orders of magnitude lower in concentration
that this. What percentage of the calcium is complexed with the
EDTA at:
a) pH 4?
b) pH 10?
16.2 A sample of Wisconsin River water at Muscoda (May, 1952) gave the
following analysis (Hem, 1959). Calculate the total hardness,
Calcium hardness, magnesium hardness, carbonate hardness, and
non-carbonate hardness in mg/L as CaCO3.
Constituent

Concentration (mg/L)

Silica (SiO2)o
Aluminum (Al)+3
Iron (Fe) total
Calcium (Ca)+2
Magnesium (Mg)+2
Sodium (Na)+
Potassium (K)+
Bicarbonate (HCO3)Sulfate (SO4)-2
Chloride (Cl)Fluoride (F)Nitrate (NO3)Total Solids (measured)
Specific Conductance
(umhos/cm)
pH
Color (Co-Pt Units)

4.2
trace
trace
18
8.5
2.5
2.4
90
9.5
1.5
trace
0.8
106
165
7.0
35

Conductivity = Alktot
In order to account for changes in ionic conductances with changing
concentrations, the Onsager equation may be employed:
A = Ao - (60.2 + 0.229Ao)C0.5

(4)

Here "C" represents the equivalent concentration of the salt. For a pure
solution of calcium and bicarbonate this would just be equal to the alkalinity
(in mg/l as CaCO3) divided by 50,000. Also, the equivalent conductance, A, is
related to the conductivity according to:
Conductivity = CA(1000)

(5)

when conductivity is in umho/cm. We can combine equations 4 and 5 to get

an expression for conductivity in terms on alkalinity only.
Conductivity = 2.08(Alktot)-1.68(Alktot)1.5

(6)

Over the concentration range from 0-200 mg/l alkalinity, this relationship is
nearly linear, so that :
Alktot = (Conductivity)/2

(7)

For pure solution of carbonate (e.g., Na 2CO3) the counter ion concentration
will be twice the molar carbonate concentration. When titrating a pure
carbonate solution of known concentration, CB will be know.
CB = 2CT

(19)