Analytical Chemistry & Exercise for

Environmental Science
(LIET233)
Week 9-12: Titrations
Chapter 13: Titrations in
Analytical Chemistry
 Titrations
Titrations are widely used in analytical chemistry to
determine acids, bases, oxidants, reductants, metal ions,
proteins, and many other species.
Titrations are based on a reaction between the analyte and a
standard reagent (titrant).
Volumetric titrations: measuring the volume of a solution
of known concentration that is needed to react completely
with the analyte
Gravimetric titrations: the mass of the reagent is measured
instead of its volume
Coulometric titrations: the reagent is a constant direct
electrical current of known magnitude that consumes the
analyte
 Titrations
Titration end point: the point in a titration when a physical
change occurs that is associated with the condition of
chemical equivalence
Titration error, Et = Vep Veq
Indicators are often added to the analyte solution to
produce an observable physical change (signaling the end
point) at or near the equivalence point.
 Back-titration
It is sometimes necessary to add an excess of the
standard titrant and then determine the excess
amount by back-titration with a second
standard titrant.
Example)
Amount of phosphate (PO43) is determined by
adding a measured excess of standard silver nitrate
(AgNO3) to a solution of the sample, forming
insoluble silver phosphate (Ag3PO4(s))
3Ag+ + PO43 Ag3PO4(s)
The excess silver nitrate is then back-titrated with a
standard solution of potassium thiocyanate
Ag+ + SCN AgSCN(s)
 Primary standards
A primary standard is a highly purified compound that
serves as a reference material in titration and in other
analytical methods.
Important requirements for a primary standard are
High purity. Established methods for confirming purity should be
available
Atmospheric stability
Absence of hydrate water so that the composition of the solid does
not change with variations in humidity
Modest cost
Reasonable solubility in the titration medium
Reasonably large molar mass so that the relative error associated
with weighing the standard is minimized
 Standard solutions
The ideal standard solution for a titration method will
1. be sufficiently stable so that it is necessary to determine its
concentration only once;
2. React rapidly with the analyte so that the time required
between additions of reagent is minimized;
3. React more or less completely with the analyte so that
satisfactory end points are realized;
4. Undergo a selective reaction with the analyte that can be
described by a balanced equation.
 Volumetric calculations
Molar concentration (c): the number of moles of
reagent contained in one liter of solution
Normal concentration (cN): the number of
equivalents of reagent in one liter of solution
mass A (g)
Amount A = g
molar mass A (mol)

Amount A = V (L) cA (mol A/L)

 Example 13-1
Describe the preparation of 2.000 L of 0.0500 M AgNO3 (169.87
g/mol) from the primary-standard-grade solid.
 Example 13-2
A standard 0.0100 M solution of Na+ is required to calibrate an
ion-selective electrode method to determine sodium. Describe
how 500 mL of this solution can be prepared from primary
standard Na2CO3 (105.99 g/mol)
 Example 13-3
How would you prepare 50.0-mL portions of standard
solutions that are 0.00500 M, 0.00200 M, and 0.00100 M in Na+
from the solution in Example 13-2?
 Example 13-4
A 50.00-mL portion of an HCl solution required 29.71 mL of
0.01963 M Ba(OH)2 to reach an end point with bromocresol
green indicator. Calculate the molar concentration of the HCl.
 Example 13-5
Titration of 0.2121 g of pure Na2C2O4 (134.00 g/mol) required
43.31 mL of KMnO4. What is the molar concentration of the
KMnO4 solution? The chemical reaction is
2MnO4 + 5C2O42 + 16H+ 2Mn2+ + 10CO2 + 8H2O
 Example 13-6
A 0.8040-g sample of an iron ore is dissolved in acid. The iron is
then reduced to Fe2+ and titrated with 47.22 mL of 0.02242 M
KMnO4 solution. Calculated the results of this analysis in terms
of (a) % Fe (55.847 g/mol) and (b) % Fe3O4 (231.54 g/mol).
 Example 13-7
A 100.0-mL sample of brackish water was made ammoniacal,
and the sulfide it contained was titrated with 16.47 mL of
0.02310 M AgNO3. The analytical reaction is
2Ag+ + S2 Ag2S(s)
Calculate the concentration of H2S in the water in parts per
million, cppm.
 Example 13-8
The phosphorus in a4.258-g sample of a plant food was
converted to PO43 and precipitated as Ag3PO4 by adding 50.00
mL of 0.0820 M AgNO3. The excess AgNO3 was back-titrated
with 4.06 mL of 0.0625 M KSCN. Express the results of this
analysis in terms of %P2O5.
 Example 13-9
The CO in a 20.3-L sample of gas was converted to CO2 by
passing the sample over iodine pentoxide heated to 150C:
I2O5(s) + 5CO(g) 5CO2(g) + I2(g)
The iodine was distilled at this temperature and was collected
in an absorber containing 8.25 mL of 0.01101 M Na2S2O3.
I2(g) + 2S2O32(aq) 2I(aq) + S4O62(aq)
The excess Na2S2O3 was back-titrated with 2.16 mL of 0.00947
M I2 solution. Calculate the concentration of CO (28.01 g/mol)
in mg per liter of sample.
 Gravimetric titrations
Mass (weight) or gravimetric titrations differ from
volumetric titrations in that the mass of titrant is measured
rather than the volume
Weight molar concentration = no. mol A / no. kg solution
Advantages of gravimetric titrations
Calibration of glassware and tedious cleaning to ensure proper
drainage are completely eliminated
Temperature corrections are unnecessary
Mass measurements can be made with considerably greater precision
and accuracy than can volume measurements
Gravimetric titrations are more easily automated than are volumetric
titrations
 Titration curves
Two types of titration curves
 Titration curves
Concentration changes during a titration
Chapter 14: Principles of
Neutralization Titrations
 Standard solutions in neutralization titrations

Strong acids or strong bases are used as standard

solutions in neutralization titrations
Standard solutions of acids are prepared by diluting
concentrated hydrochloric (HCl), perchloric (HClO4),
or sulfuric acid (H2SO4)
 Acid/base indicators
An acid/base indicator is a weak organic acid or a
weak organic base whose undissociated form differs
in color from its conjugate base or its conjugate acid
form
HIn + H2O In + H3O+
In + H2O InH+ + OH
 Working range of a pH indicator
Human eyes are not very sensitive to color
differences in a solution containing a mixture of HIn
and In
HIn exhibits its pure acid color when [HIn]/[In] 10
It exhibits its base color when [HIn]/[In] 0.1
Thus,
pH(acid color) = log(10Ka) = pKa + 1
pH(base color) = log(0.1Ka) = pKa 1
indicator pH range = pKa 1
The common acid/base indicators
 Titration of strong acids and bases
The hydronium ions (H3O+) in a aqueous solution of
a strong acid have two sources:
the reaction of the acid with water
the dissociation of water itself
For a solution of HCl with a concentration > 106 M,
[H3O+] = cHCl + [OH] cHCl
Titrating a strong acid with a strong base; Example
14-1
 Example 14-1
Generate the hypothetical titration curve for the
titration of 50.00 mL of 0.0500 M HCl with 0.1000 M
NaOH at 25C.
Using the charge-balance equation to construct
titration curves
An acid/base titration curve can be generated from the reaction
stoichiometry as in Example 14-1 as well as from the charge balance
equation
The charge balance equation in Example 14-1 is given by [H3O+] + [Na+] =
[OH] + [Cl]
[Na+] = cNaOH,0VNaOH / (VNaOH + VHCl)
[Cl] = cHCl,0VHCl / (VNaOH + VHCl)
Thus,
[H3O+] = [OH] + [Cl] [Na+]

When [OH] << [Cl]

[H3O+] [Cl] [Na+] cHCl
[H3O+] = cHCl,0VHCl / (VNaOH + VHCl) cNaOH,0VNaOH / (VNaOH + VHCl)
= (cHCl,0VHCl cNaOH,0VNaOH) / (VNaOH + VHCl)
Using the charge-balance equation to construct
titration curves
At the equivalence point, [Na+] = [Cl], and
[H3O+] = [OH]
[H3O+] = (Kw)1/2

Beyond the equivalence point, [H3O+] << [Na+], and the original equation
rearranges to
[OH] [Na+] [Cl] cNaOH
= cNaOH,0VNaOH / (VNaOH + VHCl) cHCl,0VHCl / (VNaOH + VHCl)
= (cNaOH,0VNaOH cHCl,0VHCl) / (VNaOH + VHCl)
 Example 14-2
Calculate the pH during the titration of 50.00 mL of 0.0500 M
NaOH with 0.1000 M HCl at 25C after the addition of the
following volumes of reagent:
(a) 24.50 mL, (b) 25.00 mL, (c) 25.50 mL
 Titration curves for weak acids
Four distinctly different types of calculations are needed to
compute values for a weak acid (or a weak base) titration
curve:
1. At the beginning, the solution contains only a weak acid or a weak base,
and the pH is calculated from the concentration of that solute and its
dissociation constant
2. After various increments of titrant have been added (up to, but not
including the equivalence point), the solution consists of a series of
buffers. The pH of each buffer can be calculated from the analytical
concentrations of the conjugate base or acid and the concentrations of
the weak acid or base that remains.
3. At the equivalence point, the solution contains only the conjugate of the
weak acid or base being titrated (that is, a salt), and the pH is calculated
from the concentration of this product.
4. Beyond the equivalence point, the excess of strong acid or base titrant
suppresses the acidic or basic character of the reaction product to such
an extent that the pH is governed largely by the concentration of the
excess titrant.
 Example 14-3
Generate a curve for the titration of 50.00 mL of 0.1000 M
acetic acid (HOAc) with 0.1000 M sodium hydroxide at 25C.
(see an separate Excel file)
 A master equation approach to weak
acid/strong base titrations
With a weak acid and strong base titrations, a single master equation is
used to find [H3O+]
The charge balance equation: [Na+] + [H3O+] = [A] + [OH]
Sodium ion concentration, [Na+], is expressed as the number of moles of
NaOH added divided by the total solution volume:
[Na+] = cNaOH,0VNaOH / (VNaOH + VHA)
Mass balance on A-containing species is expressed:
cT = [HA] + [A] = [A][H3O+] / Ka + [A]
Solving for [A] yields
[A] = cTKa / ([H3O+] + Ka)
Substituting these into the charge balance equation, we get
[Na+] + [H3O+] = cTKa / ([H3O+] + Ka) + Kw / [H3O+]
By rearranging this, we obtain the master equation:
[H3O+]3 + (Ka + [Na+])[H3O+]2 + (Ka[Na+] cTKa Kw)[H3O+] KwKa = 0
 Example 14-4
A 50.00-mL aliquot of 0.0500 M NaCN (Ka for HCN = 6.21010)
is titrated with 0.1000 M HCl. The reaction is
CN + H3O+ HCN + H2O
Calculate the pH after the addition of (a) 0.00, (b) 10.00, (c)
25.00, and (d) 26.00 mL of acid.
The composition of solutions during acid/base
titrations

Relative amounts of acetic

acid and acetate ion
during the titration of
50.00 mL of 0.1000 M
acetic acid.
Locating titration end points from pH
measurements
Titration curve for
the titration of 50.00
mL of 0.1000 M
weak acid (Ka =
1.0105) with
0.1000 M NaOH

Inflection point
 The Gran plot
Prior to the equivalence point of the titration of a weak acid
with a strong base, the concentration of acid remaining (cHA) is
0 0

=
+ +
0
: the initial analytical concentration of HA
0
: the initial concentration of base
Volume of NaOH at the equivalence point (Veq) is obtained
from stoichiometry, for which a 1:1 reaction
0 0
=
0

=
+
 The Gran plot
If Ka is not too large, the equilibrium concentration of acid in
the preequivalence point region is approximately equal to the
analytical concentration
0

[] =
+
0

=
+
[]
3 + = =
[ ]
Thus, we have
3 + =
Chapter 15: Complex Acid/Base
Systems
 Complex acid/base systems
Polyfunctional acids and bases play important roles
in many chemical and biological systems.
Complex acid/base systems in this chapter are
1. Two acids or two bases of different strengths
2. An acid or a base that has two or more acidic or
basic functional groups
3. An amphiprotic substance, which is capable of
acting as both an acid and a base
 Example 15-1
Calculate the pH of a mixture that is 0.1200 M in hydrochloric
acid and 0.0800 M in the weak acid HA (Ka = 1.00104) during
its titration with 0.1000 M KOH. Compute results for additions
of the following volume of base: (a) 0.00 mL and (b) 5.00 mL.
 Example 15-2
Calculate the pH of the resulting solution after the addition of
29.0 mixture that is 0.1200 M in hydrochloric acid and 0.0800
M in the weak acid HA (Ka = 1.00104) during its titration with
0.1000 M KOH. Compute results for additions of the following
volume of base: (a) 0.00 mL and (b) 5.00 mL.
Curves for the titration of strong/weak acid
mixture
 The phosphoric acid system
H3PO4 + H2O H2PO4 + H3O+
H3 O+ H2 PO
= 4
= 7.11103
H3 PO4
H2PO4 + H2O HPO42 + H3O+
H3 O+ HPO2
2 = 4
= 6.32108
H2 PO
4

HPO4 2 + H2O PO43 + H3O+

H3 O+ PO3
3 = 4
= 4.51013
HPO2
4
Distribution of phosphoric acid species as a
function of solution pH
The carbon dioxide/carbonic acid system
H2 CO3
CO2(aq) + H2O H2CO3 = = 2.8103
CO2 ()
H2CO3 + H2O HCO3 + H3O+
H3 O+ HCO
1 = 3
= 1.5104
H2 CO3
HCO3 + H2O CO32 + H3O+
H3 O+ CO2
2 = 3
= 4.691011
HCO
3

Because [CO2(aq)] >> [H2CO3], a more useful way of discussing

the acidity of solution of carbon dioxide is to combine the first
two reactions.
CO2(aq) + 2H2O HCO3 + H3O+
H3 O+ HCO
= 3
= 4.2107
CO2 ()
 Example 15-3
Calculate the pH of a solution that is 0.02500 M CO2.
 Example 15-4
Calculate the hydronium ion concentration for a buffer solution
that is 2.00 M in phosphoric acid and 1.50 in potassium
dihydrogen phosphate.
 Example 15-5
Calculate the hydronium ion concentration for a buffer that is
0.0500 M in potassium hydrogen phthalate (KHP) and 0.150 M
in potassium phthalate (K2P).
 Calculation of the pH of solutions of NaHCO3
When NaHCO3 dissolves in water, the pH of the solution is
determined by two equilibria:
HCO3 + H2O CO32 + H3O+
HCO3 + H2O H2CO32 + OH

Mass balance: cNa = [Na+] = [H2CO3] + [HCO3] + [CO32]

Charge balance: [Na+] + [H3O+] = [OH] + [HCO3] + 2[CO32]
[H3O+] = [OH] + [CO32] [H2CO3] (proton condition)
[HA] [H O +][HA ]
3
[H3O+]= +
[H3O+] [H3O+]
HA +
[H3 O+]=
1+[HA ]/
 Example 15-6
Calculate the hydronium ion concentration of a 1.00103 M
Na2HPO4 solution.
 Example 15-7
Find the hydronium ion concentration of a 0.0100 M NaH2PO4
solution.
 Example 15-8
Calculate the hydronium ion concentration of a 0.1000 M
NaHCO3 solution.
Titration curves for polyfunctional acids
 Example 15-9
Construct a curve for the titration of 25.00-mL of 0.1000 M
maleic acid, HOOCCH=CHCOOH with 0.1000 M NaOH.
We can write the two dissociation equilibria as
H2M + H2O = H3O+ + HM Ka1 = 1.3102
HM + H2O = H3O+ + M2 Ka2 = 5.9107
Because the ratio Ka1/Ka2 is large (2104), we can proceed using
the techniques just described.
 Composition of polyprotic acid solutions
as a function of pH
Alpha values for polyfunctional acids and bases can be
defined as
[2 ] [ ] [2 ]
0 = 1 = 2 =

where = 2 + + [2 ]
0 + 1 + 2 = 1
H 3 O+ 2
0 =
H3 O+ 2 +Ka1 H3 O+ +Ka1 Ka2
Ka1 H3 O+
1 =
H3 O+ 2 +Ka1 H3 O+ +Ka1 Ka2
Ka1 Ka2
2 =
H3 O+ 2 +Ka1 H3 O+ +Ka1 Ka2
 Logarithmic concentration diagrams
See attached Excel file
 Alkalinity Titration
(Chapter 18, Sawyer)
 Alkalinity
The akalinity (acid neutralizing capacity; ANC) of a
water us a measure of its capacity to neutralize
acids.
Bicarbonate (HCO3) represents the major form of
alkalinity. A few organic acids such as humic acids
are also responsible for alkalinity.
Alkalinity is thus a measure of buffer capacity of
water
 Method of determining alkalinity
Alkalinity is measured volumetrically by titration with 0.020
N H2SO4 and reported in terms of equivalent CaCO3.
In the first step, the titration is conducted until the pH is
lowered to 8.3, the point at which phenolphthalein indicator
turns from pink to colorless.
The second phase of the titration is conducted until the pH is
lowered to about 4.5, corresponding to the bromocresol
green (or methyl orange) endpoint.
When the pH is less than 8.3, a single titration is made to a
pH of 4.5
Method of determining alkalinity

Titration curve for a

hydroxide-carbonate
mixture
 Expressing alkalinity
OH & CO32
OH only CO32 only
Hydroxide
alkalinity

Hydroxide
alkalinity

Phenolphthalein endpoint (pH 8.3)

Carbonate
alkalinity
Carbonate Carbonate
alkalinity alkalinity

Bicarbonate Bicarbonate
alkalinity alkalinity

Methyl orange endpoint (pH 4.5)

 Calculating alkalinity from equilibrium
equations
Alkalinity = [HCO3] + 2[CO32] + [OH] + [H3O+]
[H3O+] and [OH] are determined by pH measurement
Carbonate alkalinity = (Alk + [H3O+] Kw/ [H3O+]) / (1 +
[H3O+]/2Ka2)
Bicarbonate alkalinity = (Alk + [H3O+] Kw/ [H3O+]) / (1 +
2Ka2/[H3O+])
The formula weight of CaCO3 is 100,000 mg/mol
By multiplying 50,000 to Alk in molar concentration,
we have alkalinity in mg CaCO3 equivalent per liter.
Chapter 17: Complexation and
Precipitation Reactions and
Titrations
 Formation of complexes
Most metal ions react with electron-pair donors to
form coordination compounds or complexes
The donor species (or ligand) must have at least
one pair of unshared electrons.
Most metal ions in aqueous solution exist as aquo
complexes (e.g., Cu(H2O)42+)
The number of covalent bonds that a cation tends to
form with ligands is its coordination number
Complexometric titrations are titrations based on
complex formation
 Complexation equilibria
M + L ML K1
ML + L ML2 K2
ML2 + L ML3 K3
MLn1 + L MLn Kn
or
M + L ML 1 = K 1
M + 2L ML2 2 = K1K2
M + 3L ML3 3 = K1K2K3
M + nL MLn n = K1K2K3Kn
Alpha values for metal complexes

1
=
1 + 1 + 2 []2 +3 []3 + + []

1
=
1 + 1 + 2 []2 +3 []3 + + []

2 []2
2 =
1 + 1 + 2 []2 +3 []3 + + []

[]
=
1 + 1 + 2 []2 +3 []3 + + []
 Complexation titrations
Complexometric titration curves are usually a plot
of pM (= log [M]) as a function of the volume of
titrant added

60.0 mL 0.020 M metal M with

(A) a 0.020 M solution of the
tetradentate ligand D to give MD
as the product
(B) a 0.040 M solution of the
bidentate ligand B to give MB2
(C) a 0.080 M solution of the
unidentate ligand A to give MA4
Complexation titrations
 Precipitation titrations
Precipitation titrations are based on reactions that
yield ionic compounds of limited solubility
Silver nitrate (AgNO3) is used as a titrant for
determining halogens or halogen-like anions (e.g.,
mercaptans, fatty acids, and several divalent anions)
 Example 17-1
Calculate the silver ion concentration in terms of pAg during
the titration of 50.00 mL of 0.05000 M NaCl with 0.1000 M
AgNO3 after the addition of the following volumes of
reagents: (a) in the preequivalence point region at 10.00 mL,
(b) at the equivalence point (25.00 mL), (c) after the
equivalence point at 26.00 mL. For AgCl, Ksp = 1.821010.
Example 17-1
 Ethylenediaminetetraacetic acid (EDTA)
EDTA is the most widely used complexometric titrant

Chemical structure of EDTA

Dissociation constants of EDTA:

K1 = 1.02102
K2 = 2.14103
K3 = 6.92107
K4 = 5.501011
Complexes of EDTA and metal ions

EDTA as a
hexadentate ligand
Complexes of EDTA and metal ions
[MY n4 + ]
Mn+ + Y4 MY(n4)+ K MY =
Mn+ [Y4 ]
 Equilibrium calculations involving EDTA
[MY n4 + ]
Mn+ + Y4 MY(n4)+ MY =
Mn+ 4
[Y4 ]
where 4 = and

= Y 4 + HY 3 + H2 Y 2 + H3 Y + H4 Y

Conditional formation constant

n4 +

[MY ]
= 4 =
M n+
 Example 17-2
Calculate the molar Y4 concentration in a 0.0200 M EDTA
solution buffered to a pH of 10.00.
 Example 17-3
Calculate the equilibrium concentration of Ni2+ in a solution
with an analytical NiY2 concentration of 0.0150 M at pH (a) 3.0
and (b) 8.0
 Example 17-4
Calculate the concentration of Ni2+ in a solution that was
prepared by mixing 50.0 mL of 0.0300 M Ni2+ with 50.00 mL of
0.0500 M EDTA. The mixture was buffered to a pH of 3.0.
 Example 17-5
Use a spreadsheet to construct the titration curve of pCa versus
volume of EDTA for 50.0 mL of 0.00500 M Ca2+ titrated with
0.0100 M EDTA in a solution buffered to pH 10.0.
 Redox Titration, Biochemical
Oxygen Demand (BOD) and
Chemical Oxygen Demand (COD)
Chapter 20 (Skoog)
Chapters 22-24 (Sawyer)
 Dissolved Oxygen (DO)
Many (aquatic) organisms use oxygen as the
terminal electron acceptor and they dominate in
aerobic aquatic systems
Related environmental issues
Depletion of dissolved oxygen (DO) by microbial
decomposition of organic matter
Depletion of DO causes fatality in higher level organisms
Level of DO is important in corrosion of metals (e.g.,
iron)
Dissolution of oxygen in water
 Collection of water samples
Should be cautious to get contacted with
atmospheric oxygen
No air bubbles are allowed!!
Chemical fixation: 0.7 mL conc. H2SO4, 0.02 g
sodium azide, 3 ml alkali iodide
Measurement:
Redox titration (Winkler method)
Polarographic method
 The Winkler method
Iodide (I) is oxidized to iodine (I2) by dissolved
oxygen.
Formed I2 is then reduced back to I using
thiosulfate (S2O32)
2S2O32 + I2 S4O62 + 2I
The Winkler method
Mn2+ + 2OH Mn(OH)2(s) (w/o oyxgen; white
precipitate)
Mn2+ + 2OH +1/2O2 MnO2(s) + H2O (w/ oxygen;
brown precipitate)
MnO2(s) + 2I + 4H+ Mn2+ + I2 + 2H2O (acidic condition)
I2 + I I3 (Iodine complex forms)
 The azide modification
Inhibition by nitrite ion (NO2)
2NO2 + 2I + 4H+ I2 + N2O2 + 2H2O
N2O2 + 1/2O2 + H2O 2NO2 + 2H+
Iodine formed during the titration make errors
The azide modification
NaN3 + H+ HN3 + Na+
HN3 + NO2 + H+ N2 + N2O + H2O
 Degradation of organic matter in water
Under aerobic condition, decomposable organic matter is
mineralized.
Ultimate (stable) products are CO2, H2O, NO3, SO42, HPO42,
etc.
Aerobic decomposition:
Organic matter + O2 CO2 + H2O + new microorganisms + stable
products
Anaerobic decomposition:
Organic matter CO2 + H2O + new microorganisms + unstable
products (H2S, NH3, CH4, etc.)
Biochemical Oxygen Demand (BOD): Amount of oxygen
required to oxidize organic matter under aerobic condition
 Example 23.1 (Sawyer)
The concentration C0 of biodegradable organic matter in a
water sample is 47 mg/L and can be represented by the
empirical molecular formula C6H11ON2. Estimate the oxygen
equivalent concentration L0 of this organic matter.
 5-day BOD test
BOD5: Amount of oxygen consumed during the first
5 days under aerobic condition
BOD5 = (DOi DOf)/P (P: a dilution factor)
Cautions:
To prohibit photosynthesis by blocking light exposure
To maintain temperature at 20C
To maintain the microbial activity constantly
To seal the bottle completely to inhibit transfer of oxygen
To determine the dilution factor to have the final
dissolved oxygen concentration > 0
First order reaction model of a BOD test

dLt
= k Lt
dt

Lt = L0 e k t

( ) (
y = (L0 Lt ) = L0 1 e k t = L0 1 10 kt )

kT = k 20 (T 20 )
 Nitrification
Ammonia in wastewater is oxidized to NO2 by nitrosomonas
and further oxidized to NO3 by nitrobacter
Amount of oxygen consumed during nitrification is called
nitrification biochemical oxygen demand (NBOD)
 Chemical oxygen demand (COD)
Organic matter is oxidized by chemical
oxidants
Advantages:
Oxygen demand can be analyzed in a short time
Chemical oxidants can oxidize organic matter
resistant to biodegradation and COD method can
be used for toxic wastewater to microorganisms
Disadvantages:
COD cannot differentiate biologically stable
organic matter and available organic matter
 Dichromate method for the determination of COD

Organic matter is oxidized at 150C and

acidic condition
CnHaObNc + dCr2O72 + (8d+c)H+ nCO2 + (a+8d-
3c)/2 H2O + cNH4+ + 2dCr3+
After the completion of oxidation reaction,
excess oxidant is determined using ferrous
ammonium sulfate (Ferroin indicator)
6Fe2+ + Cr2O72 + 14H+ 6Fe3+ + 2Cr3+ + 7H2O
 Dichromate method for the determination of COD

Inhibition by chloride ion

6Cl + Cr2O72 + 14H+ = 3Cl2 + 7H2O + 2Cr3+
HgSO4 is used to remove chloride ion
Hg2+ + 2Cl HgCl2(aq) (2 = 1.71013)
Oxidation of nitrite (NO2) to nitrate (NO3)
sulfamic acid