Prepared by :

.Ch/Mohammed Kaheil M

Introduction

Definition
The termheavymetalrefers to any
metallicchemical element that has a
relatively highdensity and istoxic,
highly toxic orpoisonous at
lowconcentrations
Examples
mercury (Hg), cadmium (Cd), arsenic
(As), chromium (Cr), thallium (Tl), and
lead (Pb).

Properties of heavy
metals
1.
2.
3.
4.

5.

6.

Occure near the button of the periodic table

High density (above 3.5 g/cm3to above 7 g/
cm3 )
Toxic in nature (poisonous trace elements)
Non Degradable

Atomic weight definitions start at greater

thansodium(22.98) to greater than 40
Atomic numbers of heavy metals are
generally given as greater than 20;
As is not accurately metal it is semimetal
and its properties are intermediate between
metals and non metals

Routes of entry (exposure)

Heavy metal exposure occurs through

three primary routes ,

1. Inhalation.

Common examples include

workers scraping or sanding lead paint
and workers in factories where heavy
metals are melted and processed. In
the days before leaded gasoline was
banned, those living alongside heavily
traveled roads faced significant
exposure through tailpipe emissions.

2-Ingestion. The leading cause of lead

poisoning in children is eating old paint
chips. A major source of elevated
mercury levels in humans comes from
eating contaminated fish. And people
can drink arsenic from wells
contaminated by arsenic-containing
pesticides.
3-Skin absorption . Day to day contact
with heavy metals can cause poisoning.
Dermal exposure is a serious concern for
workers in fields where the irrigation
water contains naturally-occuring
arsenic (such as Asian rice paddies).

Effect of exposure to heavy

metals

Heavy metals "can bind to vital cellular

components, such asstructural proteins
,enzymes , andnucleic acids , and
interfere with their functioning
Symptoms and effects can vary
according to the metal or metalcompound, and the dose involved.
Broadly, long-term exposure to heavy
metals can have carcinogenic, central
and peripheral nervous system and
circulatory effects.

Eleme
nt
cadmi
um

Acute exposure
xposure

Chronic exoposure

(lung inflammation)

(softening of bones)
(excess protein in urine; possible
kidney damage) lung cancer

Mercu Diarrhoea ,,fever ,,

ry

Lead

(brain dysfunction)
Nausea
Vomiting

(nonspecific kidney disorder)

(neurotic disorder)
(pain and pink discoloration of
hands and feet)rDNA alteration
Anaemia ,,(kidney disease)

Chromium

(bleeding)s(redblood
celldestruction)

Nausea
Vomiting
Diarrhea
Arsenic
0
Multi-organeffects

Pulmonary
fibrosis ,,lung cancer

Diabetes,,cancerof
organs

Heavy metals
&Environment

Sources of heavy metals in environment

Mercury Hg
Air pollution
1- Fossil fuel combustion
2- Mining

3- Smelting
4- Solid waste combustion

Water pollution
the application of agricultural
fertilizers and industrial wastewater
disposal

Cadmium Cd
Human uptake of cadmium takes
place mainly through food
Foodstuffs that are rich in cadmium
can greatly increase the cadmium
concentration in human bodies (liver,
mushrooms, shellfish, mussels,
cocoa powder and dried seaweed)

Chromium Cr
Chromium(III) is an essential nutrient
for humans and shortages may cause
heart conditions, disruptions of
metabolisms and diabetes
But the uptake of too much
chromium(III) can cause health effects
as well, for instance skin rashes

Chromium(VI) is a danger to human

health, mainly for people who work
in the steel and textile industry
People who smoke tobacco also have
a higher chance of exposure to
chromium

Lead Pb

Foods such as fruit, vegetables,

meats, grains, seafood, soft drinks
and wine may contain significant
amounts of lead
Cigarette smoke also contains small
amounts of lead

Environmental
effect of heavy
Environmental metals
effects of mercury

Acidic surface waters can contain

significant amounts of mercury
When the pH values are between five and
seven, the mercury concentrations in the
water will increase due to mobilisation of
mercury in the ground
Once mercury has reached surface waters
or soils microorganisms can convert it
to methyl mercury, a substance that
can be absorbed quickly by most organisms
and is known to cause nerve damage

Fish are organisms that absorb

great amounts of methyl mercury
from surface waters every day
(mercury can accumulate in fish
and in the food chains)

Environmental effect of
cadmium
Cadmium can be transported over great distances

when it is absorbed by sludge

This cadmium-rich sludge can pollute surface waters
as well as soils
Cadmium strongly adsorbs to organic matter in soils
When cadmium is present in soils it can be extremely
dangerous, as the uptake through food will increase
Soils that are acidified enhance the cadmium uptake
by plants
This is a potential danger to the animals that are
dependent upon the plants for survival Cadmium can
accumulate in their bodies, especially when they eat
multiple plants
Cows may have large amounts of cadmium in their
kidneys due to this

In aquatic ecosystems cadmium can

bioaccumulate in mussels, oysters,
shrimps, lobsters and fish
The susceptibility to cadmium can
vary greatly between aquatic
organisms
Salt-water organisms are known
to be more resistant to cadmium
poisoning than freshwater
organisms

Environmental effects of
chromium

Chromium in soils strongly attaches to

soil particles and as a result it will not
move towards groundwater
In water chromium will absorb on
sediment and become immobile
Only a small part of the chromium that
ends up in water will eventually dissolve
Most of the chromium in air will
eventually settle and end up in waters or
soils

Chromium(III) is an essential
element for organisms that can
disrupt the sugar metabolism and
cause heart conditions, when the
daily dose is too low
Chromium(VI) is mainly toxic to
organisms - it can alter genetic
materials and cause cancer

Environmental effects of
lead

Lead accumulates in the bodies of water organisms

and soil organisms

Health effects on shellfish can take place even when

only very small concentrations of lead are present

Body functions of phytoplankton can be disturbed

when lead interferes. Phytoplankton is an important
source of oxygen production in seas and many larger
sea-animals eat it

That is why we now begin to wonder whether lead

pollution can influence global balances

Soil functions are disturbed by lead

intervention, especially near
highways and farmlands, where
extreme concentrations may be
present
Also soil organisms are suffered
from lead poisoning

maximum admissible
limit set by different national and international
organizations. (For health risk and aesthetic value)

Drinking water contaminants and

heavymetals(g/ L)

As

Cd

Co

Cr

Cu

Fe

Mn

Ni

Pb

Zn

,USEPA
2008

10

100

100

1300

300

50

100

15

5000

EU,
1998

10

NM

50

2000

200

50

20

10

NM

WHO
2008

10

NM

50

2000

NGL

400

70

10

NGL

,Iranian
1997

50

10

NM

50

1000

1000

500

NM

50

NM

Australi
,an1996

NM

50

2000

300

500

20

10

3000

,Indian
2005

50

10

NM

50

1500

300

100

20

100

5000

New
,Zealand
2008

10

NM

50

2000

200

400

80

10

1500

Wastewater quality standards based on the Water

Pollution Prevention Law (June 21, 1971, Prime
Minister's Office Ordinance 35)

Specified toxic substance

Causes of dissolution

Permissible limit (mg/L)

Cadmium and its compounds

Compound metals, pigment,

accumulator battery

below 0.1mg/L

Hexavalent chrome
compounds

Plating,printing,chromium ore

below 0.5mg/L

Cyanogen compounds

Chemical fiber,plating,tire

below 1mg/L

Mercury and its compounds

Thermometer, fluorescent

below 0.005mg/L

Alkyl mercury

Fertilizer, medicine,agricultural
chemical

undetectable level

Selenium and its compounds

Electronic parts,pigment,
medical agent

below 0.1mg/L

Lead and its compounds

Car battery, solder,plating

below 0.1mg/L

Arsenic and its compounds

Medicine, agricultural chemical

below 0.1mg/L

Fluorine and its compounds

Rocket fuel

below 8mg/L (public water area

excluding ocean area)
below 15mg/L (ocean area)

Boron and its compounds

Semiconductor, acoustic
equipment, medicine

below 10mg/L (public water

area excluding ocean area)
below 230mg/L (ocean area)

Boron and its compounds

Semiconductor, acoustic
equipment, medicine

below 10mg/L (public water

area excluding ocean area)
below 230mg/L (ocean area)

Specified toxic substance and the Environmental

Quality Standards for Soil Contamination
Environmental Quality Standards for Soil
Contamination

Second standard for

amount of dissolution
(mg/L)*3

Second-class specified
toxic substance

Applications

Cadmium and its

compounds

Compound metals,
pigment, accumulator
battery

below 150mg/L

below 0.01mg/L

below 0.3mg/L

Hexavalent chrome
compounds

Plating,printing,chromium
ore

below 250mg/L

below 0.05mg/L

below 1.5mg/L

Cyanogen compounds

Chemical fiber,plating,tire

below 50mg/L
(As a free cyanide)

undetectable level

below 1.0mg/L

Mercury and its

compounds

Thermometer, fluorescent

below 0.0005mg/L

below 0.005mg/L

Alkyl mercury

Fertilizer,
medicine,agricultural
chemical

undetectable level

undetectable level

Selenium and its

compounds

Electronic parts, pigment,

medical agent

below 150mg/L

below 0.01mg/L

below 0.3mg/L

Lead and its compounds

Car battery, solder, plating

below 150mg/L

below 0.01mg/L

below 0.3mg/L

Arsenic and its

compounds

Medicine, agricultural
chemical

below 150mg/L

below 0.01mg/L

below 0.3mg/L

Fluorine and its

compounds

Rocket fuel

below 4,000mg/L

below 0.8mg/L

below 24mg/L

Boron and its compounds

Semiconductor, acoustic
equipment, medicine

below 4,000mg/L

below 1mg/L

below 30mg/L

Standard for contained

amount in soil (mg/kg)*1

Standard for amount of

dissolution in soil
(mg/L)*2

below 15mg/L

Orders of heavy metals in different

In fish

In water
the order was found to be
Fe>Pb>Zn>Cu>Cr>Cd>Co;

1.

Surface water

2.

species

species
Cu>Fe>Zn>Cu>Pb>Cd>Co; the highest
mean
concentration of Copper (0.2970.022 g/g),
Cadmium (0.0110.007g/g), Iron (0.3710.489g/g),
Lead (0.0080.008g/g), were determined for the fish

the highest mean concentration

of Iron (0.0090.00g/g), Copper
(0.0150.01 g/g), Lead (0.00020.00g/g)
Cadmium (0.00060.001g/g), Zinc
(0.00360.003g/g), were observed in the
surface water, respectively.
Buttom water the highest mean concentration of

Iron (0.0090.00g/g), Copper (0.0150.01 g/g),

Lead (0.00020.00g/g) Cadmium
(0.00060.001g/g), Zinc (0.00360.003g/g), were
observed in the surface water, respectively.

Sediment
the concentration order found
was Zn>Fe>Cu>Pb>Co>Cd; the
highest mean concentration of
0.0570.04g/g, 0.0430.03g/g,
0.00060.00g/g,
0.00020.00g/g,
0.00090.00g/g,
0.0990.00404g/g in Iron,
Copper, Lead, Cobalt, Cadmium
and Zinc were observed in the
sediment, respectively

Benefits

of heavy
metals

Some elements regarded as heavy

metals are essential, in small
quantities, for human health. These
elements include vanadium,
manganese, iron, cobalt, copper, zinc,
selenium, strontium and molybdenum.
A deficiency of these essential metals
may increase susceptibility to heavy
metal poisoning.

Heavy metals
analysis in the
environmental
samples

Sample treatment

Sediment samples were oven dried to constant

weight at 105oC. The samples were grounded
using mortar and pestle and sieved through 2mm
mesh size to remove coarse materials
The fish samples were allowed to defrost and
then dried to constant weight in an oven at
105oC
Water samples were not subjected to any
further treatment and were sent directly
foranalysis (only add0.25HCL)to prevent
adsorbtion of valentmetal on the wall of the
vessel

Decomposition methods is to
convert organic metal to inorganic
form preparatory to estimation

1.

Photochemical method
by applying UV
+HNO3 or HCLO4 or K2Cr2O7 as
oxidizing agent

2-wet method
HNO3+HCL ( 3 : 1) percent and
this called aquaragia +heating 70-80
oc degradation occurred

Determination methods of
heavy metals

Gravimetric analysis
Atomic absorption spectroscopy
(AAS)
Compleximetric titration
Iodometry
Oxidation reduction titration
using internal indicator
Oxidation reduction titration
using external indicator

Gravimetric method-1

1.
2.
3.
4.
5.

6.

Ideal Properties of Precipitating

Reagents
Specific
Selective
Readily Filtered
Low Solubility
Known composition after being
heated
Un reactive with the atmosphere

 Example:

Determination of lead (Pb+2) in water

Pb+2
+
2Cl- pbcl2
Analyte

Reagent

Solid Product

by adding excess Cl- to the sample, essentially all of

the Pb+2. precipitate as PbCl2

Mass of PbCl2 is then determined.

- used to calculate the amount of Pb+2 in
original solution

Calculations of gravimetric
analysis
Ppt wt*gravimetric factor* 100
=
analyte%

sample wt
=

Analyte FW
Gravimetric factor
Ppt FW

Advantages of gravimetric
method
1.

2.

3.

4.

5.
6.

It is accurate and precise when using modern

analytical balance.
.
Possible sources of error are readily checked since
filtrates can be tested for completeness of
precipitation and precipitates may be examined for the
presence of impurities.
.
It is an absolute method; it involves direct
measurement without any form of calibration being
required.
.
Determination can be carried out with relatively
inexpensive apparatus ; the most expensive items are a
muffle furnace and sometimes platinum crucibles .
.
Gravimetric analysis was used to determine the
atomic masses of many elements .
.
Gravimetry provides very little room for
instrumental error and does not require a series of
standards for calculation of an unknown .

Disadvantages of
gravimetric method
1.

2.

3.

4.

The chief disadvantage is that it requires

meticulous time consuming.
.The chemist often prefers modern
instrumental methods when they can be
used
Gravimetric analysis usually only
provides for the analysis of a single
element, or a limited group of elements,
at a time.
Gravimetric analysis is based on the
measurement of mass.
.
.

Atomic absorption-2
spectroscopy (AAS)

1.

2.
3.

4.
5.
6.

Principles

In analytical chemistry , Atomic absorption spectroscopy

is a technique for determining the concentration of a
particular metal and few non metal
Cosidered to be an important manner in quantitative
analysis
can be used to analyze the concentration of over 62
different metals in a solution.
Atoms of different elements absorb characteristic
wavelengths of light. (the main idea)
Analyzing a sample to see if it contains a particular
element (means using light from that element ).
Highly senstive to ppm ranges

AAS consists mainly of four

units

AAS
Monochromator
Atom
cell
detector
Light source

1.

Light (radiation )source

(hollow cathode lamp
)(HCL)

The cathode lamps are stored in a **

compartment inside the AA
spectrometer. The specific lamp
needed for a given metal analysis is
rotated into position for a specific
.experiment
For example with lead, a lamp containing lead
emits light from excited lead atoms that
produce the right mix of wavelengths to be
absorbed by any lead atoms from the
sample

Working of HCL

Applying a potential difference

between the anode and the cathode
leads to the ionization of some gas
atoms .
The shape of the cathode which is
hollow cylindrical concentrates the
emitted radiation into a beam which
passes through a quartz window all
the way to the vaporized sample.

Atom cell (Atomization)

In which the elemental form of the

vapor transformed into atomic form
(so it is called atomizer unit )

Aspirator
tube
sucks
the
sample
into the
flame in

The blank ,standards and samples are

injected into the nabulizer tube and inter
the instrument in the form of spray
Vaporization occurred (vaporized sample)
A beam of the electromagnetic radiation
emitted from excited lead atoms is passed
through the vaporized sample. Some of the
radiation is absorbed by the lead atoms in
the sample. The greater the number of
atoms there is in the vapor , the more
radiation is absorbed

Atomizer may be

Flame

Graphite

Vapor generation

Flame

Graphite
Furnace

atomizer
Characterst Using
ic
C2H2 +air
features of (oxidizing
the way agent)
Heat (do
atomization
)
Measure
ppm ranges

1.

2.

3.

Graphite
tube
(50mm
in
L,10mm
inD)
vaporizati
on(5001200OC)
Ignition(2
400oc)
Can
measure
ppb
ranges

Vapor
(hydrate)
Vapor

generation
syst. Is
applied to
the AAS
Chemical

treatemement
for the sample
Volatile

Monochromator and
detector

monochromator- used for the

isolation of an absorption line from
the characteristic line spectra for
the analyzed element.
solid detector associated with an
electronic amplifying system and
measuring equipment.

The instrumental settings for the

flame atomic absorption spectrometer
Parameter
Lead Copper
Cadmium
Wavelength, nm 217
324.8
228.8
Lamp current, mA 5
3
3
Acetylene flow rate, dm3min-1 2. 1.5
5

Input data
1.
2.
3.
4.
5.
6.

Measure mode
Number of samples
Wavelength (nm)
Lamp current
Name of metal be measured
Dilution factor

Reagents and standards

All the reagents used were of analytical
reagent grade. -distilled water (DW) and
high purity reagents were used for the
preparations of all the standard and
sample solutions.
analyte were prepared from nitrate salts
of
Cd(II), Cu(II) and Pb(II) in 1 % of HNo3 in
1-L calibrated flasks (standard soln )

Summery in lab
1.

2.

3.

4.

Do blank using distilled water or

calibration blank (HNO3 0.2 %).
Do standards for different
concentrations
Insert the data (specific to each
heavy metal)
Sample injection

The main advantages of AAS are

given below:

High sample throughput

Easy to use

High precision

Inexpensive technique

The main disadvantages of AAS

are as follows:

only solutions can be analyzed

Injection of one sample only (manually)

relatively large sample quantities are

required (1-3 ml)

problems with refractory elements

Compleximetric-3
titrations
Compleximetry
A titration based on the formation of a
coordination complex is known as a compleximetric
titration.
Complex formation titrations are used to titrate
cations via complex formation reagents.
Most, if not all, metals form coordination
complexes with anions or molecules. For example,
Fe ++ + 6 CN 1-
Fe(CN)6 ---Molecules/anions that react with metal ions must
donate an unshared pair of electrons to form a
coordinate covalent bond

Molecules composed of metals and chelates or

metals and coordinating agents are known as
coordination complexes.
Chelating agents form strong 1:1 complexes with
metal ions.

The complex can form only

when
1. The central atom (a metal ion (or
cation) in a complex) accepts an
electron pair from one or more
ligands (ligand = electron-pair
donating species).
2. The ligand possesses at least one
electron pair to donate.
3. The bonding (coordinate covalent
bonding) occurs .

Types of ligands
1. Anionic ligands include
halides, CN 1-, OH 1-, RCOO
1-, S 2-, C2O4 2- (oxalate), etc.
2. Molecular ligands include
water, ammonia, RNH2
(amines) C5H5N (pyridine)
H2NCH2CH2NH2
(ethlenediamine), etc.

Ligands as a donating
species

unidentate

Ligands that have (or share) only one electron pair

ammonia is unidentate...

Cu2+ + 4 NH3
Cu(NH3)4 2+

Bidentate ligands share two electron pairs

Examples:

Glycine complexed with copper(II)

.1
2.
.Ethylenediamine complexed with zinc ion

Multidentate ligands complexed to metal ions are

called chelates. Chelates always have a "chelate ring."
For example, the zinc-8-hydroxyquinolate complex.

NB

"

Dentate" = a tooth-like projection

EDTA
The most commonly used chelon

(or titrant) in metal ion titrations

is EDTA
(ethylenediaminetetracetic acid).
Ethylene diamine tetraacetic acid.
H4EDTA => H4Y
ethylenediaminetetraacetate
anion
EDTA-4 => Y-4

EDTA is hexadentate, donating

one electron pair from each of
the two amine group and one
electron pair from each of the
four carboxylates to the bound
metal ion.
Virtually every element in the
periodic table can be
determined by titrating with
EDTA.

Colorimetric indicators

Also known as metallochromic

indicators.
This binding is pH dependent
Masking agents are often
used for compleximetric
titrations, which allow for the
removal of interferents.

Examples:

Erichrome Black T
Eriochrome Black T is an azo dye, best used
with Mg2+ and Zn2+ titrations.
Excess EDTA causes a red to blue color
change at near neutral pH.

Eriochrome Black solutions

decompose easily.

Mg +

(red)

EDTA

(colorless)

MgEDTA

In

(blue)

Calmagite/calgamite Similar in

structure to Eriochrome Black but does

not decompose as easily. Similar color
behavior to Eriochrome Black and more
stable.


CH3

OH

N
OH

OH

OH

O2N
O2N

SO3H
SO3H

Calgamite
Eriochrome Black T

OH
AsO3H2
N

CH3

OH

SO3

SO3

Arsenazo I

OH

HO2C
HO2C

CH3

N
SO3

Xylenol Orange

CO2H
CO2H

The tendency of complex formation is

controlled by the formation constant of the
reaction between the metal ion (Lewis
acid) and the ligand (Lewis base). As the
formation constant increases, the stability
of the complex increases.
Let us look at the complexation reaction of
M+ with NH3:
M+ + NH3 M(NH3)+
M(NH3)+ + NH3 M(NH3)2+

kf1 = [M(NH ) ]/[M ][NH ]

3

kf2 =

[M(NH3)2+]/[M(NH3)+]
[NH3]

Kf1 x kf2 = [M(NH3)2+]/[M+][NH3]2

Now look at the overall reaction:
M+ + 2 NH3 M(NH3)2+
kf = [M(NH3)2+]/[M+][NH3]2
It is clear fro inspection of the values of the kf that:
Kf = kf1 x kf2
For a multistep complexation reaction we will
always have the formation constant of the overall
reaction equals the product of all step wise
formation constants

Formation Constants for EDTA

Complexes
Cation

KMY

Cation

KMY

Ag
+
Mg2
+
Ca2
+
Sr2
+
Ba2
+
Mn2
+
Fe2
+
Co2
+
Ni2

x 107 2.1
x 108 4.9
x1010 5.0
x 108 4.3
x 107 5.8
x1013 6.2
x1014 2.1
x1016 2.0
x1018 4.2

Cu2
+
Zn2
+
Cd2
+
Hg2
+
Pb2
+
Al3
+
Fe3
+ 3
V
+
Th4

x 1018 6.3
x 1016 3.2
x 1016 2.9
x 1021 6.3
x 1018 1.1
x 1016 1.3
x 1025 1.3
x 1025 7.9
x 1023 1.6

EDTA Equilibria
EDTA can be regarded as H4Y where in
solution we will have, in addition to H 4Y,
the following species: H3Y-, H2Y2-, HY3-,
and Y4-. The amount of each species
depends on the pH of the solution where:
4 = [Y4-]/CT where:
CT = [H4Y] + [H3Y-] + [H2Y2-] + [HY3-] + [Y4-]
4 = ka1ka2ka3ka4/([H+]4 + ka1 [H+]3 + ka1ka2[H+]2 +
ka1ka2ka3[H+] + ka1ka2ka3ka4)

The species Y4- is the ligand species in

EDTA titrations and thus should be
looked at carefully.

 Titration

Curve

The

titration of a metal ion with EDTA is

similar to the titration of a strong acid
(M+) with a weak base (EDTA)

The

Titration Curve has three distinct

regions:

Before the equivalence point (excess

Mn+)

At the equivalence point

([EDTA]=[Mn+]

After the equivalence point (excess

EDTA)

EDTA Titration
Techniques

Direct Titration Many metals can

be determined by direct titrations
with EDTA.
Weak metal complexes such as
Ca2+ and Mg2+ should be titrated in
basic solution using EBT, Calmagite,
or Arsenazo I as the indicator.

Back Titration

Back titration can be performed for the

determination of several metal ions can
not be titrated directly but form stable
EDTA complexes.
Theprocedure, a known amount of EDTA
is added to the analyte sample solution
and the excess is back titrated with a
standard solution of weak metal ion,
Mg2+.
The weak metal ion will not displace the
analyte from its EDTA complex.
Calgamite can be used as an indicator for
the back titration of the excess EDTA with
standard magnesium ion solution.

Displacement Titration
MY2- or ZnY2- complex is added to the
solution of unknown metal ion
composition.
The unknown metal displaces the
Mg2+ or Zn2+, which is then back
titrated.
The technique only works when the
unknown metal has tighter binding to
EDTA than the Zn2+ or Mg2+.

1.

2.

3.

4.

Pb determination method
using complex titration
(EDTA titration)

Take 10 mL of water, acidified with a minimum

quantity of acetic acid (~300 g/l)
and then dilute to about 50 mL with distilled
water.
Add about 50 mg of xylenol orange indicator
and sufficient methenamine (about 5 g) to turn
soln red
titrate with disodium edetate (0.05 mol/l) VS
until the solution turns from deep violet to full
yellow.
HN=CH2
(METHENAMIN)

Results
Each mL of disodium edetate (0.05
mol/l) VS is equivalent to 10.35 mg of
Pb
NB ..the same method can applied to
determine but
. Each mL of disodium edetate (0.05
mol/l) VS is equivalent to 3.268 mg of
Zn.

Advantages:

1-Simple to do
2-Cost effective
3-Doesnot need great expertise but some
skill and practice.
4-Instruments are easily available
5-Common used method and one of the
oldest

Disadvantages:

1-Instruments have to be properly calibrated

since it will give affected the final result .
2- Reactivity of the elements to be titrated
should be well researched since this may
affect the end point.
3-Time consuming if done manually

Iodometry-4

Principle
considered to be oxidation
reduction
reaction using iodine that
librated
through the chemical
reaction

Example
Pb

(determination of lead)

is precepitated as pbCrO4 by adding pot.

Chromate(K2CrO4)

The

buffer used is CH3COONa &CH3COOH

pb(AC)2 + K2CrO4
PbCrO4+2K(AC )
Take ppt and water washing
Dissolve ppt in diluted HCL(1:1)
PbCrO4+2HCL
pbcl2+H2CrO4
Treat with KI solution(10%)
H2CrO4+6KI +12HCL
2CrCL3+6KCL+3I2+8H2O

Titrate the librated iodine against

0.1N sod.thiosulphate (Na2S2O3)
2NaS2O3+I2
Na2S4O6+2NaI

till faint

yellow color
Add 2ml Starch Solution (as
indicator)

Na2S2O3

Na2S2O3
oxidant
+
KII2

Add starch

Colorless E.P.

Detection of the end point in

:iodine titrations
Starch is used in the form of colloidal Solu
giving
a deep blue adsorbtion complex with traces I 2

In exx I2 an irreversible blue adsorption

complex
is formed which is not changed

Starch consists of amylase and amylopectin

I2 gives blue adsorption complex with
amylase.

Starch can not be used in alcoholic

solu.because
alcohol hinders the adsorption of I 2 on starch

The sensitivity of the blue color decreases

with
temperature due to gelatinization of starch
and
volatility of Iodine

Starch indicator solution must be

freshly prepared when it stands
decomposition takes place and its
sensitivity is decreased. A
preservative can be added

Disadvantages

Error due to starch:

Starch may be decomposed by

microorganisms
into products e.g.
glucose causes error due to its
reducing action

other products gives nonreversible

reddish color
with I2 which masks the true end point.

4-Oxidation reduction
reaction using potassium
dichromate as titrant

1.

Internal indicator
External undicator

2.

1-Determination of Fe2+ Iron

(internal indicator
(e.g)diphenylamin
also called redox indicator ,its
col. Differ in oxidizing med.and
in reduction med.
H3PO4
diphenyl
amine
H2SO4
Fe2+

Titrate with
Cr2O72-

Role of H3PO4
React with Fe+++ resulted from the reaction
forming complex then take them away
from the
reaction field and this help in
complete oxidation of Fe++ to Fe+++

End point ..the color of indicator change

from green to greenish blue to dark violet
that dont change what ever added titrant
due to formation of diphenylbenzidine
(violet) due to oxidation of diphenylamin
NH

PH

[O]
PH

1-Determination of Fe2+ Iron external

indicator

0.1%pot.Ferricyanideas indicator :Fe2+ is

titrated with dichromate in acidic
medium.Occasionally remove a drop from the
solution and add it to ferricyanide solu. a blue
color of ferrous ferricyanide is formed. At the
E.P. No more Fe2+ is present so no blue color is
formed.

K3[Fe(CN)6] + Fe++
Fe3[Fe(CN)6]+3K+
ferrous
ferricyanide(blue)

Diphenylcarbazide as indicator :
After oxidation of Fe2+ to Fe3+, the
first exx of dichromate oxidizes the
indicator and gives a red color.

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