Unit-5

Chemistry of materials for sensors, water treatment and E-waste management

Sensors: Introduction, Construction, working and applications of conductometric sensors,

Electrochemical sensors, Optical sensors, Gas sensors.

Water treatment - Introduction, hardness of water, types, determination of hardness by EDTA

method, disadvantages of hard water, removal of hardness by ion exchange method, Desalination of
water – Electrodialysis. BOD and COD - introduction and their significance in waste water
treatment, experimental determination of COD of waste water - numerical on hardness & COD.

E-Waste: Introduction, sources of e-waste, Composition, Characteristics, and Need of e-waste

management. Toxic materials used in manufacturing electronic and electrical products; Recycling
and Recovery: Different approaches of recycling (separation, thermal treatments, hydrometallurgical
extraction, pyrometallurgical methods, direct recycling). Recycling of Li-Ion batteries. Extraction of
copper from E-waste.

Sensors:
Introduction

A sensor is a device that detects changes in a physical stimulus and provides a corresponding output
signal that can be measured.

Commonly Detectable Phenomena using sensors include Biological, Chemical, Electric,

Electromagnetic, Heat/Temperature, Magnetic, Mechanical motion, Optical, Radioactivity.

A sensor contains the following basic components

Analyte receptor - Binds to the analyte utilizing a chemical reaction for recognition.
Transducer - A device that converts receptor–analyte interaction into a readable value or
measurable physical quantity such as thermal, electromagnetic or optical signal.
Quantification & output - Consists of microchips and micro circuits that convert these signals to a
graphical output. There are several types of sensors available depending on type of transducer is
 used like Electrochemical sensors, Conductometric sensors, Thermometric sensors, and Optical
sensors etc.
Conductometric sensors
Definition - A device used to measure the conductivity of various solutions whose ionic movement
is induced by an electrical field applied across two electrodes.
Principle - The transducer in these sensors measures conductivity of the electrolyte layer on the
electrode surface. The conductivity is measured as a function of change in electrolytic
conductance of the solution during replacement of ions of a particular conductivity by ions of
different conductivity.
Construction - These electrodes used in conductivity sensor are called as conductivity cell. It is
made of two platinum foils with unit cross sectional area and unit distance between them. Volume
between two electrodes is I cm3. Conductance of unit volume of the solution is called as specific
conductance. There will be change in specific conductance of solution when there is change in
number of ions or type of ion. This change is measured using conductivity cell. The conductivity
cell is dipped in the electrolytic solution taken in a beaker and it is connected to a conductance
measuring device called as conductivity meter.

where l/A is known as cell constant and

„R‟ is the resistance of the solution.
 Applications of Conductometric sensors
1. Conductometric sensor can be used to monitor any chemical which can change
the electrolytic conductance of solution on chemical reaction.
2. It is used to estimate acids, bases and their mixtures in a sample.
3. It is used to check the amount of ionic impurities in water samples.
4. It is used in measuring acidity or alkalinity of sea water and fresh water.
5. Conductometric biosensors are used in biomedicine, environment monitoring,
bio technology and agriculture related applications.

Electrochemical sensors
Definition - A class of chemical sensors in which an electrode is used as a transducer element in the
presence of an analyte.
Principle – The change in the potential difference between 2 electrodes is a function of
concentration of the analyte.
Let us consider Potentiometric sensor as an example for electrochemical sensor
Construction of Potentiometric sensor – Electrochemcical sensor is a combination of an indicator
electrode and a reference electrode. Commonly, Platinum is used an inert indicator electrode
whereas saturated calomel electrode is used as a reference electrode. Indicator electrode is used to
measure change in potential due to redox reaction occurring on the surface of the electrode.
Applications of Electrochemical sensors
1. Alternative to manual visual color change titration.
2. Low-cost detection of analytes in agriculture, food, and oil industries.
3. Used in the characterization of acids.
4. Detects components of the analyte gas or solution.
5. Identification of drug molecules in body fluids.
6. Automated clinical analyzers for determination of electrolytes and blood gases.

Optical sensors
Definition – Device used to convert the light rays into electronic signals and
measures the physical quantity of light which is translated to a form that is
readable as electronic signals.

Principle – The interaction of light with matter such as absorption, emission,

scattering, or reflection of light is converted into an electro-optical signal.
It is governed by Beer- Lamberts law.
A = log Io/It = €Ct
Where C is the concentration, t is the path length. € is a molar extinction
coefficient for a
given solution at a given wavelength.

Let us consider Colorimetric sensor as an example for Optical sensor

Construction and working -

 A beam of light reaches the sample where it is transmitted, reflected, and
absorbed by the solution. The transmitted ray falls on the photodetector system
where it measures the intensity of transmitted light. It converts it into the
electrical signals and sends it to the galvanometer.

Applications of optical sensors

1. Optical sensors can be used in the determination of any chemical
species which can interact with electromagnetic radiation.
2. Optical sensors have been developed for a number of different types of
chemical and biochemical molecules and ions. For example, ions in solution
(e.g., pH, metal ions, and anions), gases (e.g., CO2, O2, NH3, SO2, NO2, NO,
etc.), vapors (e.g., moisture, volatile organic compounds, etc.), and molecules
(e.g., glucose, pesticides, DNA, bacteria, etc.) can be determined using optical
sensors.
3. Optical sensors find important and varied uses in environmental,
biotechnological, food, pharmaceutical, medical, and related applications.
4. Optical fiber based (bio)sensors are used in screening of drugs, detection
of food- borne pathogens, detection of explosives and environmental
monitoring.

Gas sensors
Gas sensor is used in monitoring of concentration of gaseous analytes. They are used
mainly to monitor the concentration of air pollutants, detection of leakage of chemicals
in industries, and in defense, military and space applications.
Electrochemical Gas sensors

Working of Electrochemical Gas sensors

Step 1: Adsorption of analyte gas molecule on the surface of sensing electrode.
The surface of sensing electrode is the active part of the electrode which may be is
modified by coating with appropriate catalysts which can selectively interact with
analyte gas.
Step 2 : Oxidation of analyte on the surface of sensing electrode, liberating electrons.
Transfer of liberated electrons from anode to cathode through external circuit.
Step 3 : Desorption of the products from the electrode surface.

ELECTROCHEMICAL GAS SENSORS FOR NOx

The receptor coated on surface of sensing electrode (working electrode) is different for each toxic
Nitrogen oxide gas.

1. Detection of NO2 –
Sensing electrode - Au, Pt/Nafion
Electrolyte - 10 M H2SO4
𝑁𝑂2 + 2 𝐻+ + 2 𝑒− → 𝑁𝑂 + 𝐻2𝑂
2. Detection of NO –
Sensing electrode - Au/NASICON
Electrolyte -NaNO2
Au/NASICON 𝑁𝑂 + 2 𝐻2𝑂 → 𝑁𝑂2 + 4 𝐻+ + 3 𝑒−
 Water treatment
Water is the most wonderful and precious gift from nature to all the living beings on the earth. It is
an essential element for the existence of human beings, animals and plants. Water rated to be of the
greatest importance. It is the most abundant and useful compound on the earth. It covers nearly 72%
of the earth‟s surface. Water gets evaporated continuously from ocean, rivers and lakes which goes
into the atmosphere as clouds and comes down to the earth surface in the form of rain.

Water distributed throughout the world as follows: 97 % locked in the oceans, 2.1 % is present in the
form of Ice, 0.6 % of water abundant in the form of fresh water in lakes, rivers and underground, and
remaining 0.1 % in the form of well water and salty water.

 Water is the most widely used chemical compound in earth

 Its one of the most essential requirements in life (Air, Food and Water)
 It is not only essential for human beings, but also for animals and plants
 Human body containing about 65% by weight of water in the form of blood and other fluids
 The average intake of water per day to a human body is nearly 2.5 to 3 litres.

Water is most needful element for many domestic usages such as “Drinking, cooking, washing and
agriculture and Industrial processes and productions and power generators.
Health and wealth of the nation depends the resources and abundant of quality of water.

Hardness of Water:

Hardness in water is that characteristics, which “prevents the lathering of soap” this is due
to presence of certain salts of calcium, magnesium and other heavy metals dissolved in water.
Hard water does not give lather easily with soap but produces a white scum or precipitate with
soap.
This because of the fatty acid of the soap in presence of calcium and magnesium ions in hard
water, quickly replaces the sodium ions forming calcium and magnesium salts of fatty acid.
Neither calcium nor magnesium are strongly attracted to water and so they precipice out as
soap scum.

Hence it requires large quantity of soap to produce lather.

Type of Hardness
Hardness classified into two types (1) Temporary Hardness (2) Permanent Hardness
The amount of temporary and permanent hardness of water is referred to as the
total hardness of water.

Units of Hardness:
It is expressed in the term of equivalent of calcium carbonate (One mole of any hardness
causing salt of Calcium and Magnesium is equivalent of one mole of CaCO3)
(1) Parts per million (ppm): It is the number of parts of equivalents of CaCO3 hardness causing
salt present in one million parts (106 parts) of water.
(2). Milligram per litre(mg/L): It is the number of milligrams of equivalent of CaCO3 per
litre of hard water. E.g.: 1mg/Litre means 1 mg of equivalentCaCO3 present in one litre of
hardwater.
(3) Degree Clarke (oCl): It is the number of gains of (1/7000 l b) of CaCO3 equivalents of
hardness per gallon (10 l b) of water. (Or) It is parts of CaCO3 equivalent hardness causing salt
in 70,000 parts of water.
(4) Degree French (o Fr): It is a French unit. The number of parts of CaCO3 equivalent
hardness causing substance in 105 parts of water.
(5) Milliequivalent per litre (meq/L) : Is the number if milli equivalent of hardness present per
litre.
1 meq/L = 1 meq of CaCO3 per litre of Water
= 10-3 × 50 g of CaCO3 eq/L
= 50 mg of CaCO3 eq per litre
= 50 mg/L of CaCO3 eq = 50 ppm.
Inter conversion: - 1ppm =1mg/L = 0.07 o Cl = 0.10 Fr = 0.02 meq/L
Determination of total hardness of water in given water sample by EDTA method
This is a complexometric titration method. Ethylene diamine tetra acetic acid (EDTA)

In the form of its sodium salts yields the anion:

[2(-OOC.CH2)-N-CH2-CH2-N-(CH2-COO- )2 ]
The above EDTA anion forms complex ions with Ca2+ and Mg2+

[Where M = Ca or Mg. It may be pointed the EDTA is employed as its disodium salt.]
(Molecular weight = 372.24, Eq. weight = 186.14)
To determine hardness of given water, hard water is buffered to a pH value of 10, for that
reason using NH4OH-NH4Cl buffer and few drops of Erichrome black -T indicator (EBT) are
added. EBT forms a weak unstable wine-red complex with metal ions.
M2+ + EBT = (M-EBT) complex
(Blue) (Unstable complex) Wine red colour
Where M = Ca and Mg ions.
During titration of water sample against EDTA, EDTA combines with free Calcium and
Magnesium ions to give very stable metal Metal -EDTA complex which is colourless.
(M-EBT) complex + EDTA = (M-EDTA)complex + EBT
Wine red colour Stable complex (Blue colour)
Thus, at equivalent point, there is a change in colour from wine red (due to M-EBT complex)
to blue complex (Due to free EBT).
Various steps involved in this titration method, Refer to Lab manual for detail procedure.
Disadvantages of Hard water
Domestic Usages
 Washing: Hard water, when used for washing purposes, does not producing lather
freely with soap. As a result, cleaning quality of soap is decreased and a lot of it is
wasted. Hard water reacts with soap it produces sticky precipitates of calcium &
Magnesium soaps. These are insoluble formations.
 Bathing: Hard water does not produce lather freely with soap solution but produces
sticky scum on the bath-tub and body. Thus, the cleaning quality of soap is depressed
and a lot of it is wasted.
 Cooking: The boiling point of water is increased because of presence of salts. Hence
more fuel and time are required for cooking.
 Drinking: Hard water causes bad effects on our digestive system. Moreover, the
possibility of forming calcium oxalate crystals in urinary tracks is increased.
Industrial usages
 Textile Industry: Hard water causes wastage of soap. Precipitates of calcium and
magnesium soaps adhere to the fabrics and cause problem.
 Sugar Industry: Water containing sulphates, nitrates, alkali carbonates etc. if used in
sugar refining, causes difficulties in the crystallization of sugar. Moreover, the sugar
so produced may be de-liquescent.
 Dyeing Industry: The dissolved salts in hard water may reacts with costly dyes
forming precipitates.
 Paper Industry: Calcium, magnesium, iron salts in water may affect the quality of
paper.
 Pharmaceutical Industry: -Hard water may cause some undesirable products while
preparation of pharmaceutical products.
 Concrete making: Water containing chlorides and sulphates, if used for concrete
making, affects the hydration of cement and the final strength of the hardened
concrete.
 Laundry: Hard water, if used in laundry, causes much of the soap used in washing to
go as waste iron salts may even causes coloration of the cloths.
Ion exchange Softening Process:
In ion exchange process the impure water is pass through cation exchange resin and
anion exchange resin. Cation exchange resin is capable of exchanging cations present
in water for H+ ions, i.e., when the water passes through the cation exchanger, the
cations present in the water as impurities are retained by the resin and H+ ions are
released into water.
Anion exchange resin is capable of exchanging anions present in water for OH- ions.
i.e., when water passes through anion exchanger, the anions present in the water are
retained by the resin and OH ions are released in to water.
Function of Cation exchanger: Water is passed through a tank having cation exchanger
which absorbs all the cations present in water and leaves behind the hydrogen. [Cation
exchange resin is expressed in RH]

The water coming out of the cation exchange resin is acidic as H+ ions introduced into
water in place of metal ions.
Function of anion exchanger: The anion resins are copolymers styrene and divinyl
benzene containing active quaternary amino groups these resins are represented as ROH
and they exchange anions present in water for OH- ions.
As cations are replaced by H+ ions and anions by OH-, the net effect is introduction of water
in place of metal salts presents in water.

The arrangement for demineralization of water shown the below figure.

Ion exchange Process: The raw water is first passed through the column containing cation
exchanger resin, in which the cations present in water are retained and H+ ions are released into
water. The water coming out of the cation exchanger is acidic. The effluent from the cation
exchanger column is then passed through the anion exchange column. The column retains the
anion present in water releasees OH ions.
Advantages:
 The apparatus once gets installed, is easy to operate and control
 Acidic and alkaline water can be softened
 Residual hardness is very low and thus water is suitable for high pressure boiler
Disadvantages:
 Equipment and process is costly and Turbid water needs to be filtered first before softening.
Desalination of water:
It is the process of removal if dissolved salts present in water. The process of partial or complete
removal of NaCl salt from highly saline water such as sea water is known as desalination.
Desalination can be carried out by different techniques such as Electro dialysis

Electrodialysis:
In this method, salts present in water are removed using ion selective membranes by applying
direct current. An electro dialysis unit consists of several compartments partitioned by
alternating cation and anion selective membranes. These membranes specifically allow the
passage of either cations or anions. These membranes are selective as they are made up of
materials containing fixed functional groups. Two electrodes, a cathode and an anode are
placed at two extreme ends. Salt water is taken in the compartments and direct current is applied
under the influence of electric current anions move towards anode through anion selective
membrane and are passed on to next compartment. However, these anions cannot pass through
next immediate membrane which is permeable to only cations.
Similarly, cations move towards cathode through cation selective membrane and are passed on
to next compartment. These cations cannot pass through next membrane which is permeable
to only anions. Thus, each alternate compartment gets concentrated with anions and cations.
Meanwhile, other adjacent alternate compartments get filled with desalination water. Finally,
concentrated water and desalinated water are removed separately as shown in the diagram.

Chemical Oxygen Demand (COD)

COD is defined as “the amount of oxygen required to oxidize all oxidizable
impurities present in 1 litre o waste water using a strong oxidizing agent such as acidified
K2Cr2O7”
Potassium dichromate is a strong oxidizing agent under acidic conditions. Acidity is usually
achieved by the addition of sulfuric acid. The reaction of potassium dichromate with organic
compounds is given by

Ag2SO4 is used as catalyst for the oxidation of straight chain aliphatic compounds. However,
Ag2+ ions become ineffective in the presence of chloride ions (present in waste water) due their
precipitation as silver halide (ex: AgCl, AgBr). This difficulty is overcome by treating the waste
water with mercuric sulphate. Mercuric sulphate binds the halide ions and makes them
unavailable.

Determination of COD of a Waste Water Sample:

A known volume of the waste water sample is refluxed with K2Cr2O7 solution in
sulphuric acid medium. K2Cr2O7 oxidizes oxidizable impurities. The amount of unreacted
K2Cr2O7 is determined by titration with standard solution of ferrous ammonium sulphate. The
amount of K2Cr2O7 consumed corresponds to the COD of the waste water sample. To find out
this, a blank titration without waste water sample is carried out.
Procedure:
Back Titration: Pipette out 25 cm3 of the waste water sample and 25 cm3 of K2Cr2O7into a 250
cm3 conical flask. Add one test tube full of 1:1 sulphuric acid (containing Silver sulphate and
Mercuric sulphate). Reflux the mixture for half an hour and cool. Add 2 -3 drops of ferroin
indicator and titrate against the standard ferrous ammonium sulphate solution until the colour
changes from bluish green to reddish brown.
Let the normality of the FAS solution be „z‟ N
Let the volume of FAS solution consumed in titration be „y‟ cm3 .
Blank Titration: Pipette out 25 cm3 of K2Cr2O7 solution. Add one test tube full of 1:1 H2SO4
followed by 2-3 drops of ferroin indicator and titrate against the standard FAS solution till the
colour of solution turns bluish green to reddish brown.
Let the volume of FAS solution consumed in titration
Calculation:
1 cm3 of 1N FAS solution = 1 milli equivalent of oxygen = 8 mg of oxygen
(x-y) cm3 of z N FAS solution = 8 × (x-y) × z mg of Oxygen
i.e., 25 cm3 of waste water sample = 8 × (x-y) × z mg of Oxygen
1000 cm3 of the waste water sample = 8 × (x-y) × z × 1000/25 mg of Oxygen
COD of waste water sample = 8 × (x-y) × z × 1000/25 mg of O2/dm3
Comparison between BOD and COD
➢ BOD is a slower process. It takes more than five days for estimation of BOD value of
water sample. Where as COD value can be estimated in about 3 hours.
➢ Any water sample COD value is always greater than its BOD values. Because BOD
is the measure of only biologically oxidizable impurities present in water whereas
COD is the measure of all oxidizable impurities
➢ Bothe BOD and COD are expressed in mg of O2/dm3 of waste water.
 E-WASTE

INTRODUCTION

In the new world of materials, usage of electrical and electronic items has been
increasing rapidly year by year. These materials have lesser life span and also used for
lesser duration due to fast change in features and the capabilities. Cumulative result of
increased manufacturing, usage and discarding is rapid increase the amount of end-of-
life electronics and electrical items. All electronic and electrical items which are
discarded on completion of their useful life together is called as e-waste. There is rapid
growth in e-waste generation since 1990s and will continue at faster rate in future. As
per an estimate, the average annual global E- waste volume is about 65.4 million tons
in the year 2017.
SOURCES OF E-WASTE

Main sources of e-waste are:

1. Computer peripherals: Monitor, key board, mouse, mother board, lap tops,
CDs etc.

2. Telecommunication devices: phones, cell phones, routers, pagers, fax machine

etc.
3. Household appliances: TV, fridge, washing machine, video players, ovens etc.
4. Industrial electronics: Sensors, medical devices, automobile devices etc.
5. Electrical devices: switches, wires, bulbs etc.

COMPOSITION OF E-WASTE

E-waste is characterized by more than 1000 hazardous and non-hazardous materials.

1. E-waste contains about 65 % of iron, steel and other metallic materials including
costly metals like platinum, gold, silver and toxic metals like lead, mercury,
cadmium, chromium etc.
2. E-waste contains about 21 % of polymeric non-biodegradable materials including
Poly vinyl chlorides (PVCs), polychlorinated biphenyls, and brominated flame
retardant plastics.
3. E-waste also contains about 11.8% of CRT and LCD screens and other
materials like glass, wood, plywood, and ceramics.
Most of these products are ended up in landfills, rubbish dumps, and recycling centers
creating several complications for waste management officials, policy makers, and
residents.

TOXIC MATERIALS USED IN MANUFACTURING

ELECTRONIC AND ELECTRICAL PRODUCTS

According to toxicity, the types of substances in E-waste can be categorized into

Hazardous and Non-hazardous substances. Hazardous substances are toxic, and can
affect the quality of the ecosystem and can have detrimental effects on human health.
These include:

1. Heavy metals like Cd, Cr. Pb and Hg,

2. Organic compounds like chlorofluorocarbon. polycyclic aromatic hydrocarbons
(PAHs), polybrominated diphenyl ethers (PBDES), polychlorinated biphenyls
(PCBs). and polychlorinated dibenzo-p-dioxin furans (PCDD/Fs).

Toxic materials in e-waste

Toxic elements disturb the nitrogen and potassium absorption by plants which
are important component in plant growth and development. Toxic substances
gradually through crops enter in to ecosystem.
 Heavy metals such as Lead (Pb), Mercury (Hg), Cadmium, Chromium(Cr),
Nickle (Ni) exceeding the maximum value of 0.01% by weight causes neural
disorders, skin damages, headache, vertigo, chronic gastritis, gastric
ulcers, and duodenal ulcers.
 Poly Vinyl chloride exposure is associated with an increased risk of a rare form
of liver cancer (hepatic angiosarcoma), as well as primary liver cancer
(hepatocellular carcinoma), brain and lung cancers, lymphoma, and leukemia.
 Excessive exposure to Gold (Au) and Copper (Cu) can also lead to hypotension,
melena, jaundice and GI distress.
RECYCLING AND RECOVERY OF E-WASTE
In E-waste, among various constituents, metals contribute to the significant economic
value, and the efforts are focused on extracting those metals during recycling
operations by the following steps.

Step 1: Separation –

(a) Manual separation - dismantling and separation of components such as PCBs,

monitors, batteries, etc. into various fractions like metals, ceramics, plastics,
wood, and paper using hammers, screwdrivers, and conveyer beds for
disassembling.

(b) Electrical and magnetic separation - Separates metallic, non-metallic and

magnetic components to separate ferrous metals.

(c) Gravity separation - to separate Al metal.

Step 2: Thermal or Pyrometallurgical process

This method requires elevated temperatures to reduce/extract metals, and therefore
require high amount of energy input. Smelting, combustion, pyrolysis, and
molten salt processes are the main pyrometallurgical methods employed for recovery
of metals from E –waste.
(a) Smelting - Copper smelting is commonly used for recovery of nonferrous
metal fractions from e- waste. The processed scrap after preliminary stage
contains mainly iron (Fe), aluminum (Al), copper (Cu), lead (Pb), tin (Sn),
antimony (Sb), zinc (Zn), and precious metals as metallic constituents. This
mixture is fed into copper smelters. During smelting, Pb, Sn, Sb, and
precious metals are collected in the copper parent phase. This is casted in to
anode slab and refined by electrometallurgy. Here, the anode is dissolved and
pure (99.99 %) copper is deposited over cathode leaving a slurry residue.
This slurry residue is called anodic slime and contains undissolved metallic
fractions. It is rich in valuable metals like Au, Pt, lead, tin, and antimony.
These metals are recovered from slurry with high recovery rates, of over 90%
using hydrometallurgical techniques
 (b) Combustion - Low-technology, low cost, straightforward operation
focusing only on the recovery of valuable metals. Here, E-waste is subjected
to open burning in uncontrolled manner which releases all sorts of pollutants
in to atmosphere. Hence, this method is highly dangerous for the
environment and also increases the health risk of the workers.

(c) Incineration - Incineration is a controlled combustion of the waste with

suitable emission units. The incinerator has two connected furnaces. In the
first furnace, e-waste is burnt at tem- peratures above 800°C and in the
second stage for the gaseous products of the first incinerator are further
oxidized above 1100°C. Heavy metals are collected in the bottom and fly ash.
Hydrometallugical processes are used for further recovery of metals.

Both methods of Combustion and Incineration are not advisable, due to

pollutant gas emission and low metal recycling performance.

Step 3: Hydrometallurgical process

Traditional hydrometallurgical process which have been used from so many years
for metal extraction from mineral ores are used for the recovery of metals from E-
waste.

There are three stages in metal recovery by hydrothermal method:

(a) Pretreatment stage.
(b) Chemical treatment stage.
(c) Metal recovery stage

(a) Pretreatment stage - Metals are recovered from the leached solutions using
through electro-refining, precipitation, cementation, adsorption, solvent
extraction, and ion exchange methods.

(b) Chemical treatment

Cyanide Leaching – Ex- Alkali cyanide like KCN with 3-nitrobenzene sulfonic
acid sodium salts are used to dissolve gold under aerated condition
Acid and Alkaline Leaching – Ex - Li is leached from Lithium ion battery waste
by treatment with citric acids and hydrogen peroxide as reducing agent
Thiourea Leaching - Ex -Thiourea is a sulfur-based organic complexing agent
that forms a cationic soluble complex with the target metal.
Halide Leaching- Ex -Chloride, bromide, and iodide ions can be used to leach
gold from the PCB waste

(c) Metal recovery

Pure metal is recovered from leached metal solution using methods such as
solvent extraction, ion exchange, adsorption, precipitation, and cementation are
 available. Method employed depends upon the nature of leached solution.

(i) Solvent extraction - Ex - Leaching solution is treated with an organic

solvent in a separating funnel. It results in two phase system. Metal is
extracted from leached solution phase to organic phase. Different
extractants such as anionic, cationic, or solvating-type are employed.

(ii) Electrodeposition - Ex - Pure metal is obtained from leached solution

by electrodeposition. Pure metal same as metal to be extracted is
taken as cathode and inert metal is used as anode. They are dipped in
leaching solution. When current is applied, pure metal is
electrodeposited on cathode

(iii) Adsorption - Ex - Activated carbon is found to be effective adsorbent

of gold from leached cyanide solutions.

Recycling of Li-Ion batteries

Step 1 – Pretreatment - Disassembly, crushing, screening and magnetic separation.

Step 2 - Hydrometallurgical Process – Acid leaching

OR
Step 2 - Direct recycling - It is a process of recovering useful components from spent
Lithium batteries without using chemical methods. The used batteries are
disassembled, crushed and heated to 650°C and extract Li using supercritical CO2.

Extraction of copper from e-waste

OR
Extraction of copper from e-waste (Printed circuit board as an example)

Step 1 – Pyrolysis - The waste printed circuit board is heated to 550°C to remove
the organic components.
Step 2 – Leaching the waste printed circuit boards in acid or base
Base leaching –

OR
Acid leaching

Step 3 – Ion exchange, solvent extraction or chemical precipitation method to

extract metal
 ADDITIONAL MATERIAL

DIRECT RECYCLING OF E-WASTE

In the previous sections, various methods available for scientific processing of e-waste
to recover useful chemical components from it were discussed. These techniques are
used to prevent disposal of e-waste by means of dumping or landfilling. Because, this
results in waste of valuable materials and can also cause environmental problem due to
contamination by heavy metals. But, all those processes require lot of energy and
money. Another cost effective method for recycling of e-waste is by direct recycling.

Direct Recycling means harvesting electronic components directly from e-waste without
breaking them further into small components. Harvested materials are further
processed with healing methods to regenerate recycled materials. The regenerated
materials have performance equivalent to originally manufactured materials. Thus, in
this method, all the complicated chemical and metallurgical steps involved in
conversion of e-waste components into original chemicals are avoided. Recycling loop is
shortened. Hence, it requires less amounts of energy and reagents and hence it is the
most environmentally friendly method. However, there are few problems associated
with direct recycling method. Direct regeneration of components depends on state-of-
health of used electronic materials. Defects and impurities accumulated during usage
could affect the quality of the refurbished active material. And also direct recycling
may not restore the initial properties of pristine active materials.

Presently, direct recycling of lithium ion batteries is studied extensively. Here, the
battery is discharged first to avoid short circuiting and self-ignition of battery and
dismantled to separate anode, cathode, electrolyte and separated. These components
are not dismantled further, but each component is regenerated by appropriate process
to recover its function. These components are reassembled for reuse.
HEALTH HAZARDS DUE TO EXPOSURE TO E-WASTE

Major problem with the e-waste is passing of toxic metals and organic compounds
present in e-waste in to ecosystem that is air, water and soil and ultimately to living
beings. Contamination of ecosystem by e-waste hazards is mainly due to:

1. Informal E-waste recycling techniques employed for metal recovery from printed
circuit boards. Although the recycling is responsible to remove or delay the
release of contaminants into the environment. Unscientific ways used for
recycling may result in accumulation in landfills and end up within the
environment.
2. Open burning of printed circuit boards and electric cables to recover copper. This
releases dioxins, persistent organic pollutants, PAHs, PCBs, persistent
halogenated compounds in to the environment.
3. Unscientific dumping of e-waste. The effluents from E-waste recycling centres
and the dumping sites are rich with heavy metals and suspended particulate
matters.
4. The use of primitive methods to process E-waste has resulted in contamination
of the soil. Many of the effluents are acidic and responsible for changing the pH
of the natural soil and results in reduction of harvest in commercial agricultural
systems. Concentration of Pb. Ba,Cd, Hg, Cr, and Zn is found to be very much
higher near dumping sites. Toxic elements were found to disturb the nitrogen
and potassium absorption by plants which are important component in plant
growth and development. Toxic substances gradually through crops enter in to
ecosystem.
5. Waste water from E-waste recycle or dumping sites is another major transport
pathway for contamination of aquatic systems. Open burning sites of e-waste for

metal recovery is the major contributor for release of different contaminants

from E-waste to atmosphere. Toxic substances are entering human body from
air, water and soil through inhalation, ingestion, and dermal contact pathways.
They are having different types of serious health impacts.
6. Most of these heavy metals are carcinogenic. Particulate matter released from
open burning can adsorb metal particles and enter in to human body.
7. People living nearby to E-waste collection, dumping, and incineration sites are
direct victims for the toxic contaminants. There are higher number of incidences
 with skin damages, headache, vertigo, chronic gastritis, gastric ulcers, and
duodenal ulcers.
8. Contaminants such as heavy metals, dioxins, furans, PAHs, PCBs, and
polybrominated diphenyls are able to create human gastrointestinal irritation
and laxative effects, abnormal sperm quality, chromosome aberration, DNA
damage, reduced fecundity, and adverse birth effects.
9. Cd metal can damage Kidneys and Pb metal has a direct influence toward
central nervous system as well as deterioration of intelligent quotient in
children. Mercury is a potential mutagenic compound and can greatly affect
neurons.
10. Placentas collected from mothers who live near e-waste dumping sites have
shown very high concentration of toxic chemicals.
11. Different hazardous chemicals can accumulate in human blood, serum and
urinary tract and finally show synergic effects with a cumulative impact.