Professional Documents
Culture Documents
.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.
1. Inhalation.
Eleme
nt
cadmi
um
Acute exposure
xposure
Chronic exoposure
(lung inflammation)
(softening of bones)
(excess protein in urine; possible
kidney damage) lung cancer
Lead
(brain dysfunction)
Nausea
Vomiting
Chromium
(bleeding)s(redblood
celldestruction)
Nausea
Vomiting
Diarrhea
Arsenic
0
Multi-organeffects
Pulmonary
fibrosis ,,lung cancer
Diabetes,,cancerof
organs
Heavy metals
&Environment
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
Lead Pb
Environmental
effect of heavy
Environmental metals
effects of mercury
Environmental effect of
cadmium
Cadmium can be transported over great distances
Environmental effects of
chromium
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
maximum admissible
limit set by different national and international
organizations. (For health risk and aesthetic value)
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
Causes of dissolution
below 0.1mg/L
Hexavalent chrome
compounds
Plating,printing,chromium ore
below 0.5mg/L
Cyanogen compounds
Chemical fiber,plating,tire
below 1mg/L
Thermometer, fluorescent
below 0.005mg/L
Alkyl mercury
Fertilizer, medicine,agricultural
chemical
undetectable level
Electronic parts,pigment,
medical agent
below 0.1mg/L
below 0.1mg/L
below 0.1mg/L
Rocket fuel
Semiconductor, acoustic
equipment, medicine
Semiconductor, acoustic
equipment, medicine
Second-class specified
toxic substance
Applications
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
Thermometer, fluorescent
below 0.0005mg/L
below 0.005mg/L
Alkyl mercury
Fertilizer,
medicine,agricultural
chemical
undetectable level
undetectable level
below 150mg/L
below 0.01mg/L
below 0.3mg/L
below 150mg/L
below 0.01mg/L
below 0.3mg/L
Medicine, agricultural
chemical
below 150mg/L
below 0.01mg/L
below 0.3mg/L
Rocket fuel
below 4,000mg/L
below 0.8mg/L
below 24mg/L
Semiconductor, acoustic
equipment, medicine
below 4,000mg/L
below 1mg/L
below 30mg/L
below 15mg/L
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
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
Heavy metals
analysis in the
environmental
samples
Sample treatment
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.
Example:
Reagent
Solid Product
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.
Disadvantages of
gravimetric method
1.
2.
3.
4.
Atomic absorption-2
spectroscopy (AAS)
1.
2.
3.
4.
5.
6.
Principles
AAS
Monochromator
Atom
cell
detector
Light source
1.
Working of HCL
Aspirator
tube
sucks
the
sample
into the
flame in
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
Input data
1.
2.
3.
4.
5.
6.
Measure mode
Number of samples
Wavelength (nm)
Lamp current
Name of metal be measured
Dilution factor
Summery in lab
1.
2.
3.
4.
Easy to use
High precision
Inexpensive technique
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
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
Cu2+ + 4 NH3
Cu(NH3)4 2+
Examples:
.1
2.
.Ethylenediamine complexed with zinc ion
NB
"
EDTA
The most commonly used chelon
Colorimetric indicators
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.
Mg +
(red)
EDTA
(colorless)
MgEDTA
In
(blue)
Calmagite/calgamite Similar in
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
kf2 =
[M(NH3)2+]/[M(NH3)+]
[NH3]
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)
Titration
Curve
The
The
EDTA Titration
Techniques
Back Titration
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)
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:
Iodometry-4
Principle
considered to be oxidation
reduction
reaction using iodine that
librated
through the chemical
reaction
Example
Pb
(determination of lead)
The
till faint
yellow color
Add 2ml Starch Solution (as
indicator)
Na2S2O3
Na2S2O3
oxidant
+
KII2
Add starch
Colorless E.P.
Disadvantages
4-Oxidation reduction
reaction using potassium
dichromate as titrant
1.
Internal indicator
External undicator
2.
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+++
PH
[O]
PH
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.
References
Akan, J.C., F.I. Abdulrahman, O.A. Sodipo & P.I. Akandu. 2009. Bioaccumulation of
some heavy metals of six fresh water fishes caught from lake chad in Doron
Buhari, Maiduguri, Bornno State Nigeria.Nig. J. App. Sci. Environ. Manag. 4:
103-114. [Links]
Allen, G.T. & R.M. Wilson. 1991. Metals and organic compounds in fish of the
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Manhattan, Kansas, USA. [Links]
Allen-Gill, S.M. &. V.G. Martynov. 1995. Heavy metals burdens in nine species of
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