ELECTROCHEMICAL SENSORS BY USING ZN

OXIDE/COPPER OXIDE NANOPARTICLES/NANO

RODS

NAME SEAT NO.

i. Nasir Hussain B1533026
ii. Syed Muhammad Ovais B1333067

SUPERVISED BY:
DR. MUHAMMAD YASIR KHAN
(Assistant Professor)

DEPARTMENT OF CHEMICAL ENGINEERING

UNIVERSITY OF KARACHI
KARACHI, PAKISTAN
2019
 TABLE OF CONTENT

1.0 Introduction
2.0 Project Planning and scheduling
2.1 Gantt chart
2.2 Program evaluation and review technique(PERT CHART)
2.3 Work break structure
3.0 Process details and equipment description
3.1 ZnO preparation
3.2 Sonication
3.3 Spin coating
3.4 Cyclic Voltametry
3.5 FET Sensing
4.0 Material and energy balances
4.1 Material Balances
4.2 Energy Balances
4.3 Reactor and Storage tank size
5.0 Hazards and environmental analysis
5.1 Introduction
5.2 Hazards of ZnO
5.3 OSHA
5.4 NIOSH
5.5 ACGIH
5.6 Health hazard information
5.7 Workplace controls and practices
5.8 Improper use of respirators is dangerous
5.9 Hazards of Methanol
5.10 Hazards of KOH
5.11 Hazards of Zinc acetate
6.0 Materials of construction
6.1 Selection variable
6.2 Corrosion resistant MOC option
6.3 Material Cost
6.4 Selection for corrosion resistance
7.0 Cost analysis
7.1 Costing for storage tanks
7.2 Cost for reactor
7.3 Cost of raw materials
7.4 Cost of services
7.5 Total costing
8.0 Nomenclature
9.0 Reference

Nomenclature
LOD Limit Of Detection
FET Field Effect Transistor
ASV Anodic Stripping Voltammetry
AAS Atomic Absorption Spectroscopy
ICP-MS Inductively Coupled Plasma Mass Spectroscopy
XFS X-ray Fluorescence Spectrometry
AU NP Aurum Nano Particle
RGO Reduced Graphene Oxide
SINWS Silicon Nano Wires
TCA Thioglycolic Acid Thiacalixarene
NAA Neutron Activation Analysis
SWCNTs Single Walled Carbon Nano Tubes
ICP-OES Inductively Coupled Plasma-Optical Emission Spectrometry

1. INTRODUCTION
a.1. RELEASE OF HEAVY METALS IN THE ENVIRONMENT
AND EXPOSURE TO HUMANS
Nanomaterial is a material with the size of nanoscale (1-100 nm). This
material has a unique properties and high value for commercial applications.
The key factors of nanoparticles are smallparticle size, narrow size
distribution, low agglomeration and high dispersion . Nanomaterial can be
applied in various fields such as cosmetics, paints, displays, batteries,
medicine, catalysis, gas sensor, food engineering (production, processing,
safety and packaging), agriculture, energy (storage and conversion) and
construction . ZnO is an excellent antibacterial agent because it has
photocatalytic properties. This material can be activated by UV and visible
light to form the electron-hole pairs. These holes can split the H2O molecule
(from suspension from ZnO) to OH- and H+. Dissolved oxygen molecules on
could be converted to superoxide radical anions (•O2) which react with H+ to
produce (HO2•) radicals. Thecollisions of (HO2•) with electrons produce the
hydrogen peroxide anion (HO2-). These species react with hydrogen ions to
produce H2O2 molecules that can penetrate the cell membranes and kill the
bacteria The advantage of ZnO is their photocatalytic ability that can
produce radical compounds. This material can be used as an antibacterial
agent . However, the ZnO material has large band gap as reported by
Vijayakumar et al. which can decrease the photocatalytic properties. Other
researchers reported that the ZnO have the band gap of 3.3 eV .
The addition of CuO to ZnO could form the CuO-ZnO composite that
increased particle size and decrease the band gap energy [6]. The higher
concentration of CuO in composites, the smaller band gap energy could be
obtained. The CuO percentage of 0.5%, 1%, 3%, 5% and 10 % on the CuO-
ZnO composite resulted in the band gap energy of 3.1, 3.0, 2.95, 2.75 and
2.65 eV respectively. The ZnO band gap energy before impregnated with
CuO was 3.20 eV . Other researchers reported [4] that the addition of CuO to
ZnO lowered the band gap energy from 3.3 eV to 3.1 eV. It increased the
stability of photocatalytic reaction and increased radical species such as
superoxide anion radical (•O2), (HO2•) and (HO2-) which can inhibit the
growth of bacteria. Sol-gel is a simple method for nanomaterial synthesis.
This method involves two stages of sol and gel formation. Many techniques
could be applied in the sol-gel technology such as the changing of initial
precursor, time of gel formation, type of catalyst, rate of solution formation
gel formation conditions and gel physical processing. Thus, the sol-gel
process enables the formation of solid material through gelation from a
solution . The main difference between gram-positive and gram-negative
bacteria is that the protein Grampositive bacteria have thicker cell wall
containing many layers (consisting of peptidoglycan and acid teichoic) while
protein Gram-negative bacteria have thinner cell wall that contain many
layers (consisting only of peptidoglycan). These cause the difference between
the gram-positive and gramnegative reaction to an antibiotic. Although the
cell walls are thicker, Gram-negative bacteria are more resistant to antibiotics
than Gram-positive bacteria because the bacteria can penetrate the lipid layer
on the outer membrane of the bacteria Based on the above description, the
authors synthesized the CuO-ZnO nanocomposite using solgel method to be
applied as antibacterial.
a.2. TYPES OF DETECTION TECHNIQUES OF HEAVY
a.3.
 a.4. METALS
Highly sensitive spectroscopic techniques like
a.4.1. ATOMIC ABSORPTION SPECTROSCOPY (AAS)

Atomic absorption spectrometry (AAS) is a technique in which free gaseous atoms

absorb electromagnetic radiation at a specific wavelength to produce a measurable
signal. The absorption signal is proportional to the concentration of those free
absorbing atoms in the optical path. Therefore, for AAS measurements the analyte
must be first converted into gaseous atoms, usually by application of heat to a cell
called atomizer. The type of atomizer defines the two main AAS-based analytical
techniques: flame AAS (FAAS) that provides analytical signals in a continuous
fashion and electrothermal AAS (ETAAS) delivering analytical signals in a
discontinuous mode (2–4 min per sample). In both cases, liquid (or dissolved)
samples are easily introduced into the analyzer, as an aerosol in the case of FAAS or
as well-defined low microliter volumes in ETAAS. Furthermore, the coupling
of hydride generation and cold vapor methods allow the introduction of analytes in
the atomizer as a gas phase.1 Also, especially in ETAAS, direct elemental analysis of
solids without previous dissolution is feasible.

In atomic absorption spectrometry (AA) the sample is vaporized and the element of

interest atomized at high temperatures. The element concentration is determined
based on the attenuation or absorption by the analyte atoms, of a characteristic
wavelength emitted from a light source. The light source is typically a hollow cathode
lamp containing the element to be measured. Separate lamps are needed for each
element. The detector is usually a photomultiplier tube. A monochromator is used to
separate the element line and the light source is modulated to reduce the amount of
unwanted radiation reaching the detector. Conventional AA instruments use a
flame atomization system for liquid sample vaporization. An air-acetylene flame
(2300 ° C) is used for most elements. A higher temperature nitrous oxide-acetylene
flame (2900 ° C) is used for more refractory oxide forming elements.
Electrothermalatomization techniques such as a graphite furnace can be used for the
direct analysis of solid samples.
Atomic absorption is used for the determination of ppm levels of metals. It is not
normally used for the analysis of the light elements such as H, C, N, 0, P and S,
halogens, and noble gases. Higher concentrations can be determined by
prior dilution of the sample. AA is not recommended if a large number of elements
are to be measured in a single sample. Although AA is a very capable technique and
is widely used worldwide, its use in recent years has declined in favor of ICP and
XRF methods of analysis for polymers. The most common application of AA is for
the determination of boron and magnesium in oils. Conventional AA instruments will
analyze liquid samples only. Dilute acid and xylene solutions are common. The
volume of solution needed is dependent on the number of elements to be determined.
AA offers excellent sensitivity for most elements with limited interferences. For some
elements sensitivity can be extended into the sub-ppb range using flameless methods.
The AA instruments are easy to operate with cookbook methods available for most
elements. The determination of several elements per sample is slow and requires
larger volumes of solution due to the sequential nature of the method. Chemical and
ionization interferences must be corrected by modification of the sample solution.
Chemical interferences arise from the formation of thermally stable compounds such
as oxides in the flame. The use of electrothermal atomization, a hotter nitrous oxide-
acetylene flame or the addition of a releasing agent such as lanthanum can help reduce
the interference.

a.4.2. INDUCTIVELY COUPLED PLASMA MASS SPECTROSCOPY

(ICP-MS)

Inductively coupled plasma-mass spectrometry (ICP-MS) is a powerful technique for

trace multi-element and isotopic analysis, because of its high sensitivity and ability to
determine the isotope composition of a sample using less cumbersome pretreatment
procedures than other mass spectrometry techniques.
However, ICP-MS is prone to interferences caused by sample matrix components.
The interferences may be caused by polyatomic ions having the same nominal mass
as the analyte, signal suppression or enhancement due to nonspectroscopic matrix
effects and blockage of the nebulizer and sampler. Therefore, in order to achieve
accurate and reliable results, matrix separation is needed when the matrix elements in
the prepared solution interfere with the determination. A detection limit of 4.8 μg
l−1 can be obtained.

a.4.3. X-RAY FLUORESCENCE SPECTROMETRY (XRF)

X-ray fluorescence spectrometry is a non-destructive instrumental method of

qualitatitive and quantitative analysis for chemical elements based on measurement of
the intensities of their X-ray spectral lines emitted by secondary excitation. The
primary beam taken from an X-ray tube irradiates the specimens, exciting each
chemical element to emit secondary spectral lines having wavelengths characteristic
of that element and intensities related to its concentration. The secondary radiation is
analysed by means of a crystal rotated in the plane of the radiation and its intensity
measured using a detector.
X-ray fluorescence spectrometry (XRF) and instrumental neutron activation
analysis (INAA) are commonly used for multi-element analysis of rock, soil, and
sediment samples since they do not require chemical dissolution. However, the
detection limit for arsenic using XRF is on the order of 5 mg kg−1 and is too high for
many environmental purposes. Once dissolved, arsenic can be determined using many
of the methods described above for aqueous samples, although the method of
digestion must be capable of destroying all solids containing arsenic.

a.4.4. NEUTRON ACTIVATION ANALYSIS (NAA)

Neutron activation analysis (NAA) is a state-of-the-art analytical technique used for
identification of elements and determination of the elemental concentration in
different applications. With the development of accurate and fast gamma
spectrometric techniques, advanced electronics and automation in data analysis, the
method has gained active application in diverse field of basic research. Non-
destructive or instrumental NAA has also become popular for varied industrial
application due to its ease in handling. With the development of high-power neutron
source, precise and fast neutron detectors and sophisticated electronics, NAA has
achieved ultralow minimum detection limit (MDL). As a result the method has turned
out to be one of the best choices for quantification of trace elements in a wide variety
of samples—geological, archaeological, biological and environmental samples.
Varied analysis devices for neutron activation studies have made it a preferred choice
for the analysis of construction material, coal, environmental, geological and
archaeological samples and biological material, security monitoring and academic
studies. Since its inception around the middle of last century, different variants of
NAA such as prompt gamma neutron activation analysis (PGNAA), pulsed fast
neutron analysis (PFNA), pulsed fast/thermal neutron analysis (PFTNA) and
associated particle imaging (API) have been developed. Non-destructive NAA is one
of the most preferred methods of sample analysis as it requires minimal processing of
the activated sample. In the semiconductor industry, NAA is used to determine ultra-
trace concentration of impurities, or dopant as impurity concentration even at 1 ppb
can affect the performance of the semiconductor. NAA-induced associated particle
imaging (API) efficiently used for security monitoring has several advantages over
other conventional scanning methods.
Different forms of NAA offer good choice over other techniques for application in
geology and medicine. NAA is used for quantitative analysis of trace elements in rock
samples which serves as an important tool for modelling geochemical processes and
also helps in sample selection for other applications. Pai et al have used instrumental
NAA (INAA) for trace element analysis in different rock samples to determine its
suitability for use in the coarse aggregate for concrete in shielding material. Over the
last several years, NAA has made important inroads in the field of medical science.
The method is used in production of radiotracers which are used in situ for evaluation
of new pharmaceuticals for their distribution, time release, clearance, etc. Neutron-
stimulated emission computed tomography (NSECT) is a newly developed imaging
method that non-invasively maps the concentration of an isotope in the body. Multiple
pencil beams of fast neutrons are developed for early diagnosis of breast cancer
through NAA using differential femto-oximetry (DFO). This chapter will discuss
application of different forms of NAA in geology and medicine and related recent
advancements.
a.4.5. INDUCTIVELY COUPLED PLASMA-OPTICAL EMISSION
SPECTROMETRY (ICP-OES)
Inductively coupled plasma atomic emission spectroscopy (ICP-AES), also referred to
as inductively coupled plasma optical emission spectrometry (ICP-OES), is an
analytical technique used for the detection of chemical elements. It is a type
of emission spectroscopy that uses the inductively coupled plasma to produce excited
atoms and ions that emit electromagnetic radiation at wavelengths characteristic of a
particular element. The plasma is a high temperature source of ionised source gas
(often argon). The plasma is sustained and maintained by inductive coupling from
cooled electrical coils at megahertz frequencies. The source temperature is in the
range from 6000 to 10,000 K. The intensity of the emissions from various
wavelengths of light are proportional to the concentrations of the elements within the
sample. The ICP-AES is composed of two parts: the ICP and the optical spectrometer.
The ICP torch consists of 3 concentric quartz glass tubes. The output or "work" coil of
the radio frequency (RF) generator surrounds part of this quartz torch. Argon gas is
typically used to create the plasma.
When the torch is turned on, an intense electromagnetic field is created within the coil
by the high power radio frequency signal flowing in the coil. This RF signal is created
by the RF generator which is, effectively, a high power radio transmitter driving the
"work coil" the same way a typical radio transmitter drives a transmitting antenna.
Typical instruments run at either 27 or 40 MHz The argon gas flowing through the
torch is ignited with a Tesla unit that creates a brief discharge arc through the argon
flow to initiate the ionization process. Once the plasma is "ignited", the Tesla unit is
turned off.
The argon gas is ionized in the intense electromagnetic field and flows in a particular
rotationally symmetrical pattern towards the magnetic field of the RF coil. A stable,
high temperature plasma of about 7000 K is then generated as the result of the
inelastic collisions created between the neutral argon atoms and the charged particles
A peristaltic pump delivers an aqueous or organic sample into an analytical
nebulizer where it is changed into mist and introduced directly inside the plasma
flame. The sample immediately collides with the electrons and charged ions in the
plasma and is itself broken down into charged ions. The various molecules break up
into their respective atoms which then lose electrons and recombine repeatedly in the
plasma, giving off radiation at the characteristic wavelengths of the elements
involved.
In some designs, a shear gas, typically nitrogen or dry compressed air is used to 'cut'
the plasma at a specific spot. One or two transfer lenses are then used to focus the
emitted light on a diffraction grating where it is separated into its component
wavelengths in the optical spectrometer. In other designs, the plasma impinges
directly upon an optical interface which consists of an orifice from which a constant
flow of argon emerges, deflecting the plasma and providing cooling while allowing
the emitted light from the plasma to enter the optical chamber. Still other designs use
optical fibers to convey some of the light to separate optical chambers.
Within the optical chamber(s), after the light is separated into its different
wavelengths (colours), the light intensity is measured with a photomultiplier tube or
tubes physically positioned to "view" the specific wavelength(s) for each element line
involved, or, in more modern units, the separated colors fall upon an array of
semiconductor photodetectors such as charge coupled devices (CCDs). In units using
these detector arrays, the intensities of all wavelengths (within the system's range) can
be measured simultaneously, allowing the instrument to analyze for every element to
which the unit is sensitive all at once. Thus, samples can be analyzed very quickly.
The intensity of each line is then compared to previously measured intensities of
known concentrations of the elements, and their concentrations are then computed by
interpolation along the calibration lines.
In addition, special software generally corrects for interferences caused by the
presence of different elements within a given sample matrix.
a.4.6. OPTICAL TECHNIQUES
The optical effects of the materials may be detected by conventional methods of
absorption, reflection or luminescence spectrometry, and in various formats such as
test strips and disposable tests, but also by making use of optical waveguides
including optical fibres, integrated optics, capillary-type devices, and the like. In
addition to the use of specific indicator dyes, methods such as multi wavelength
measurements and multivariate data analysis may further improve the quality of the
assay. Optical ion sensing, however, has its limitations : Despite the availability of
selective reagents, many optical indicators react with more than one metal ion,
whereby selectivity can often be enhanced by adjusting an adequate pH. Due to the
fact that many metal ion indicators also combine with hydrogen ion, pH has to be
controlled or measured so that an appropriate correction factor can be applied.
Because of the limited selectivity of most indicator dyes, masking agents such as
fluoride may be co-immobilized in sensor membranes so that undesired interferences
by other metal ions are suppressed. Some test strips also contain reducing agents in
order to convert the analyte into a species (or oxidation state) for which indicators (or
detection schemes) are known. Optical sensors and probes for HMs usually are based
on thin indicator-loaded polymer films or membranes, which is usually referred to as
the sensing "chemistry". Difficulties arising in the case of hydrophobic membranes
were discussed by Janata . Thermodynamic assumptions and existing limitations for
the description of electrochemical and optical sensors, sensors based on chromo-
ionophores and field-sensitive dyes, as well as problems related to membrane
thickness, solvation effects, and adsorption of ions on the membrane interface were
critically discussed as well
a.4.7. CHEMICAL SENSORS
A chemical sensor is a device that transforms chemical information (composition, presence
of a particular element or ion, concentration, chemical activity, partial pressure…) into an
analytically useful signal. The chemical information, mentioned above, may originate from a
chemical reaction of the analyte or from a physical property of the system investigated. They
can have applications in different areas such as medicine, home safety, environmental
pollut2.

COMPOSITION

Chemical sensors usually contain two basic components connected in series: a chemical
(molecular) recognition system (receptor) and a physicochemical transducer. In the majority
of chemical sensors, the receptor interacts with analyte molecules. As a result, its physical
properties are changed in such a way that the appending transducer can gain an electrical
hers.

Example
 Glucose Dectector
Blood glucose monitors are devices that are used to measure the concentration of glucose
within a person's blood. Along with the term blood glucose this reading is also often referred
to as blood sugar. Most basic blood glucose monitors have three separate parts that are
required for them to work properly: a lancer, a test strip and the meter itself. Blood glucose
monitors measure the amount of sugar in a sample of blood using a complex chemical
process. Within the test strip the blood is mixed with glucose oxidase, which reacts with the
glucose in the blood sample to create gluconic acid. Another chemical within the test strip,
called ferricyanide, then reacts with the gluconic acid to create ferrocyanide. The electrode

within the test strip then runs a current through the blood sample and the ferrocyanide
influences this current in such a way that the concentration of blood glucose within the
sample can be accurately measured within a fair margin o of error.

 Mosquito
Mosquitoes have a battery of sensors in their antennas and one of them is a chemical
sensor. They can sense carbon dioxide and lactic acid up to 36 meters away. Mammals and
birds release these gases when they breathe. Certain chemical in sweat also seem to attract
mosquitoes. This is the reason that those who sweat more easily will tend to attract more
mosquitoes.
 CLASSIFICATION OF SENSORS

The development of instrumentation, microelectronics and computers makes it

possible to design sensors utilizing most of the known chemical, physical and
biological principles that have been used in chemistry. Chemical sensors may be
classified according to the operating principle of the transducer.
1. Optical devices transform changes of optical phenomena, which are the result of an
interaction of the analyte with the receptor part. This group may be further subdivided
according to the type of optical properties which have been applied in chemical
sensors:
a) absorbance, measured in a transparent medium, caused by the absorptivity of
the analyte itself or by a reaction with some suitable indicator.
b) reflectance is measured in non-transparent media, usually using an
immobilized indicator.
c) luminescence, based on the measurement of the intensity of light emitted by a
chemical reaction in the receptor system
d) fluorescence, measured as the positive emission effect caused by irradiation.
Also, selective quenching of fluorescence may be the basis of such devices.
e) refractive index, measured as the result of a change in solution composition.
This may include also a surface plasmon resonance effect.
f) optothermal effect, based on a measurement of the thermal effect caused by
light absorption.
g) light scattering, based on effects caused by particles of definite size present in
the sample
 The application of many of these phenomena in sensors became possible because of
the use of optical fibres in various configurations. Such devices have also been called
optodes.
2. Electrochemical devices transform the effect of the electrochemical interaction
analyte - electrode into a useful signal. Such effects may be stimulated electrically or
may result in a spontaneous interaction at the zero-current condition. The following
subgroups may be distinguished:
a) Voltammetric sensors, including Amperometric devices, in which current is
measured in the D.C. or A.C. mode. This subgroup may include sensors based
on chemically inert electrodes, chemically active electrodes and modified
electrodes. In this group are included sensors with and without (galvanic
sensors) external current source.
b) Potentiometric sensors, in which the potential of the indicator electrode (ion-
selective electrode, redox electrode, metaVmeta1 oxide electrode) is measured
against a reference electrode.
c) Chemically Sensitized Field Effect Transistor (CHEMFET) in which the effect
of the interaction between the analyte and the active coating is transformed
into a change of the source-drain current. The interactions between the analyte
and the coating are, from the chemical point of view, similar to those found in
potentiometric ion-selective sensors.
d) Potentiometric solid electrolyte gas sensors, differing from class 2b) because
they work in high temperature solid electrolytes and are usually applied for
gas sensing measurements.
3. Electrical devices based on measurements, where no electrochemical processes
take place, but the signal arises from the change of electrical properties caused by the
interaction of the analyte.
a) Metal oxide semiconductor sensors used principally as gas phase detectors,
based on reversible redox processes of analyte gas components.
b) Organic semiconductor sensors, based on the formation of charge transfer
complexes, which modify the charge carrier density.
c) Electrolytic conductivity sensors.
d) Electric permittivity sensors.
4. Mass sensitive devices transform the mass change at a specially modified surface
into a change of a property of the support material. The mass change is caused by
accumulation of the analyte.
a) Piezoelectric devices used mainly in gaseous phase, but also in solutions, are
based on the measurement the frequency change of the quartz oscillator plate
caused by adsorption of a mass of the analyte at the oscillator.
b) Surface acoustic wave devices depend on the modification of the propagation
velocity of a generated acoustical wave affected by the deposition of a definite
mass of the analyte.
5. Magnetic devices based on the change of paramagnetic properties of a gas being
analysed. These are represented by certain types of oxygen monitors.
6. Thermometric devices based on the measurement of the heat effects of a specific
chemical reaction or adsorption which involve the analyte. In this group the heat
effects may be measured in various ways, for example in the so called catalytic
sensors the heat of a combustion reaction or an enzymatic reaction is measured by use
of a thermistor. The devices based on measuring optothermal effects (If) can
alternatively be included in this group.
7. Other physical properties as for example X-, p- or r- radiation may form the basis
for a chemical sensor in case they are used for determination of chemical compostion.
This classification represents one of the possible alternatives. Sensors have, for
example, been classified not according to the primary effect but to the method used
for measuring the effect. As an example can be given the so-called catalytic devices in
which the heat effect evolved in the primary process is measured by the change in the
conductivity of a thermistor. Also, the electrical devices are often put into one
category together with the electrochemical devices.
Sensors have also been classified according to the application to detect or determine a
given analyte. Examples are sensors for pH, for metal ions or for determining oxygen
or other gases. Another basis for the classification of chemical sensors may be
according to the mode of application, for example sensors intended for use in vivo, or
sensors for process monitoring and so on. It is, of course, possible to use various
classifications as long as they are based on clearly defined and logically arranged
principles. The biosensors are not presented as a special class because the process on
which they are based is, in general, common to chemical sensors. They may be also
differentiated according to the biological elements used in the receptor. Those may
be: organisms, tissues, cells, organelles, membranes, enzymes, antibodies, etc. The
biosensors may have several enzymatic systems coupled which serve for
amplification of the signal. Various sensors may be combined in sets which are often
called multisensors.

a.5. WHY CHOOSING ELECTROCHEMICAL TECHNIQUE

Electrochemical techniques on a contrary are more economic, user friendly, reliable
and suitable for in-field applications. These electrochemical techniques allow simple
procedures and well suited to fabricate on small circuits in the form of portable
devices for in-situ monitoring of contaminated samples. These techniques are also fast
in terms of short analytical time as compared to other spectroscopic techniques
allowing on-line monitoring of water samples. However, these electrochemical
techniques offer lower sensitivity and Limits of detection (LOD) as compared to other
spectroscopic and optical techniques and require developments in the design to
improve its performance in detection of heavy metal ions. Various electrochemical
techniques are coupled with different biosensing electrodes for enhancing their
sensitivity and limits of detection by modifying the electrode material. This paper
reviews various electrochemical techniques employed for detection of HMI in water
samples and recent advances in the development of various interface materials for
modifying electrodes employed in these techniques
Although these techniques are highly sensitive and selective, they require tedious
sample preparation and pre-concentration procedures, expensive instruments, and
professional personnel. Moreover, they cannot be used as portable devices for on-site
detection. In contrast, sensors have great potential in high throughput detection of
multiple heavy metals on-site. Rapid development of nanotechnology has provided
new opportunities for improving the performance of sensors in terms of sensitivity,
limit of detection, selectivity, and reproducibility. The recent progress in
nanostructured sensors for heavy metal detection. Study of sensor are based on
electrochemical, and field-effect transistor (FET) sensors 

a.5.1. ELECTROCHEMICAL SENSOR:

The electrochemical detection is normally performed with a three-electrode system

containing a working electrode (WE), a reference electrode (RE) and a count
electrode (CE) (Fig.1). The WE can be concentration of metal ions . The presence of
heavy metal ions causes the change of current, potential, electrochemical impedance,
capacitance or electrochemiluminescence, which can then be used for their detection .
In particular, due to their unique electronic, physical, chemical and mechanical
properties, nano- and bio-materials have been explored their extensive applications in
electrochemistry . The assembly of different materials can further improve the
electrochemical performance For example, polymers or biomaterials are frequently
assembled on inorganic nanomaterials to construct the highly sensitive
electrochemical sensors for heavy metal ions.
 a.5.2. NANOPARTICLE-MODIFIED ELECTRODES.
We report a new method for selective detection of D(+)-glucose using a
copper nanoparticles (Cu-NPs) attached zinc oxide (ZnO) film coated electrode.
The ZnO and Cu-NPs were electrochemically deposited onto indium tin
oxide (ITO) coated glass electrode and glassy carbon electrode (GCE) by layer-
by-layer. In result, Cu-NPs/ZnO composite film topography was characterized
by scanning electron microscopy (SEM) and atomic force microscopy (AFM),
respectively. SEM and AFM confirmed the presence of nanometer sized Cu-
NPs/ZnO composite particles on the electrode surface. In addition, X-
ray diffraction pattern revealed that Cu-NPs and ZnO films were attached onto the
electrode surface. Indeed, the Cu-NPs/ZnO composite modified electrode showed
excellent electrocatalytic activity for glucose oxidation in alkaline (0.1 M NaOH)
solution. Further, we utilized the Cu-NPs/ZnO composite modified electrode as
an electrochemical sensor for detection of glucose. This glucose sensor showed a
linear relationship in the range from 1 × 10− 6 M to 1.53 × 10− 3 M and the
detection limit (S/N = 3) was found to be 2 × 10− 7 M. The Cu-NPs/ZnO composite
as a non-enzymatic glucose sensor presents a number of attractive features such as
high sensitivity, stability, reproducibility, selectivity and fast response. The
applicability of the proposed method to the determination of glucose in human
urine samples was demonstrated with satisfactory results.
a.5.3. FET SENSORS
FET sensors have been used for detection of heavy metals by utilizing the interaction
between the analyte and semiconductor resistor. FET sensors are capable of real-time
label-free detection of heavy metals. One-dimensional and two-dimensional
semiconducting nanomaterials are especially attractive to the FET sensors because
they have very high surface-to-volume ratio, leading to high sensitivity. A Si
nanowire was used to construct a FET sensor for detection of heavy metals. This FET
sensor exhibited high sensitivity with a LOD of 10−7 M for Hg+2 and 10−4 M for Cd+2
Another example was a selective and sensitive FET sensor constructed with
singlewalled carbon nanotubes (SWCNTs), which was based on the conductance
change due to the selective redox reaction between SWCNTs and Hg+2. Reduction
from Hg+2 to HgO by the SWCNTs is thermodynamically favorable, while reduction
of other metal ions with SWCNTs is unfavorable due to their negative potentials. This
sensor exhibited a LOD of 10 nM, with a wide detection range from 10 nM to 1 mM,
and excellent selectivity toward Hg+2 over other metal ions in both aqueous solution
and drinking water. Nanomaterials usually require the surface functionalization for
specific detection of metal ions. Specific detection of mercury with a FET sensor has
been demonstrated by self-assembly of a 1-octadecanethiol monolayer onto graphene
due to high affinity of thiol to mercury. However, the LOD was high (∼0.5 μM). In
order to improve the sensitivity, Chen et al. have used the thioglycolic acid (TGA)-
functionalized reduced graphene oxide (rGO) to construct a FET sensor. This FET
sensor achieved a LOD of 2.5 × 10−8 M and responded to the analyte within a few
seconds with excellent selectivity over other metal ions. The improved sensing
performance was attributed to the chelation interaction of heavy metal ions with the
carboxyl group of TGA, rather than the selectively binding of thiol group to mercury.
In addition, the protein-functionalized rGO was employed in a FET sensor to detect
various metal ions with high sensitivity.
Field-effect transistors Field-effect transistors (FETs) often measure the flow
of the current across a transistor that links the source and drain electrodes. FETs use
to contain a semiconducting channel whose conductivity is affected by external fields
which in this case corresponds to a potential variation. This variation in the potential,
or field effect, is the reason why FETs are classified as potentiometric sensors.
Incorporation of nanostructured materials into FET designs allows to overcome
drawbacks such as the unstable response. The most used nanostructured materials for
FETs construction are carbon nanotubes and semiconductor nanowires owing to their
capability to form channels for the source and drain connection without being buried
underneath the dielectric layer. The main advantages coming from the nano-FETs can
be attributed to their ultra-low detection limits, possibility of direct functionalization
with the nanostructured material and easyminiaturization. Some nano-FETs have been
applied in the field of heavy metals sensing achieving very low detection limits.
SiNWs have been used by Bi et al. to construct a FET for copper ions detection.
SiNWs were modified with glycyl-glycylhistidine as a copper ion recognition
element. The measurement of Cu+2 concentration was performed by measuring the
change on the conductance of the SiNW upon the copper ions concentration Due to
the fact that copper ions are positively charged, they can act as positive gate potential
and increase the conductance of the n-type SiNWs which will be the final
measurement. Other works involving the use of modified SiNWs for Hg+2 and Cd+2
ions detection have been reported. Fig shows details on the design and the obtained
response of a SWCNT based FET developed by Kim et al. for the Hg+2 ions detection.
SWCNT are very sensitive to the chemical environment because of the high
sensitivity of their band gap energies to the local dielectric or redox environment. The
authors of the work point out that a strong response of SWCNT conductance upon
Hg+2 exposure is caused by the strong redox reaction between SWCNT and Hg+2in
which mercury is reduced to HgO by SWCNT and deposited on the walls of the
nanotubes. The selectivity of the sensor can be explained by looking at the different
standard potentials of the metal ions which indicate that Hg+2 ions are the only ones
that can be thermodynamically favorable reduced by SWCNT. Fig (upper part) shows
the plausible mechanism for Hg+2 reduction on the top of SWCNT. In contrast,
Pb+2ions cannot be reduced by SWCNT and remain as Pb+2 ions in solution (Fig.
8(b.1)). Real-time current measurement obtained from the SWCNT-FET after the
introductionof Hg+2 at various concentrations ispresented in Fig. 8(b.2). The addition
of Hg+2 from 1 pM to 1 nM showed no significance effect on the source–drain current,
while drastic current increase with fast response was observed after the addition of 10
nM of Hg+2. The same strategy involving the reduction of Hg+2 through CNTs was
recently used by Lee et al. with the additional theoretical study for the prediction of
the sensor response.

a.6. SCOPE
The goal is to create chemical sensors to detect heavy metals in waste water or
any other water source by using Chemical Sensor and to provide the required quality
and safety of water from the standpoint of heavy metal contamination. SCOPE:
Studies have used ZnO to load onto supports in effort to create a hybrid adsorbent.
Kikuchi et al published an extensive analysis on the effect of ZnO loading onto
activated carbon. There have been reports of coating the surface of ZnO with humic
acid to remove phenanthrene but no mention of its applicability for heavy metal
removal was made. Other studies have reported on the use of semiconductor
nanocrystals, notably, ZnS. Amiri et al published work on the development of
CdS/ZnS core-shell nanoparticles for heavy metal removal from aqueous solutions.
Zan et al used ZnS nanocrystals for Hg(II) removal. These studies will not be
mentioned further because the focus of this discussion is dedicated to the use of ZnO
nanomaterials.

2 PROJECT PLANNING AND SCHEDULING

WBS

The Work Breakdown Structure (“WBS”) helps synthesize the project scope into a
disciplined framework. The WBS is the most important tool in the planning of a
project. Its family tree format can be based on the deliverables or products of the
project, or, as a task-based structure detailing the work to be done. Model car and
airplane builders remember the schematic included with the indecipherable assembly
directions. The WBS is this parts-explosion of the components of work tasks or
deliverable products that breaks down the “big thing,” the project.
CPM

Many, many years ago in the 1950s, at the height of the Cold War and at the
emergence of Rock and Roll, two major network analysis tools became into
being—CPM and PERT. The chaotic, political gyrations within both large
corporations and governmental agencies, and the resultant whipsawing of
projects, begged for some semblance of order. CPM and PERT provided the
salvation of disciplined order to the crisis.
The Critical Path Method (“CPM”) flowed from the mathematical engineering
labs of du Pont, to address the need to focus limited resources on competing
priorities. The invention of Program Evaluation Review Technique (“PERT”)
invented by the U.S. Navy and Booze-Allen specifically for the Polaris Missile
System, addressed the uncertainty and risks with new ventures. Interestingly,
both were computer-based for network analysis; PERT using probabilistic
time estimates with CPM using deterministic scheduling values
To start the planning process the following sequence is suggested albeit it does not
mean that it must be followed in a strict chronological order. It is supposed that prior
activities such as market study, design of the product object of the project, and
approval from Board of Directors are completed, as well as the Project Charter, and
also that a rough estimate of costs and feasibility has been performed and found
adequate. It is also assumed that the owner’s staffis doing the project management or
that a consultancy firm has been retained for that purpose.

1.1GANTT CHART
.

A Gantt chart is a bar chart commonly used in project management to track project
schedules. On the left of the chart is a list of the activities (tasks or events) and along
the top is a suitable time scale. Each activity is represented by a bar; the position and
length of the bar reflects the start date, duration and end date of the activity. This
allows you to see at a glance:

 What the various activities are

 When each activity begins and ends
 How long each activity is scheduled to last
 Where activities overlap with other activities, and by how much
 The start and end date of the whole project

Gantt Charts are a way to graphically show progress of a project. Management of

a project is made easier if it is viewed as small manageable items where the
dependencies are visually illustrated, parallel processes are discovered, the overall
processing time determined and progress tracked. The tasks of a project can be
quite complex and dependent on each other. With a project management tool, such
as a Gantt chart, all subtasks of a task can be viewed graphically

1.1.1. REASONS TO USE GANTT CHARTS

1. Gantt charts are highly visual - By providing a visual overview of

milestones and other key dates, gantt charts offer a more understandable and
memorable method of maintaining timescale-based tasks and deliverables
whether tracked on a daily, weekly, monthly or yearly basis.
2. Keeps project on track - Stakeholders throughout an organization can easily
understand where teams are in a process while grasping the ways in which
independent elements come together toward project completion. Everyone
involved in the project is therefore on the same page.
3. Communication – Gantt charts communicate status updates – all teams can
clearly see task progress and how each task relates to each other. This in itself
helps communication between teams.
4. Resource allocation – by being able to look ahead on the Gantt chart, users
can clearly see where resources need to be anticipated and allocated. The more
 closely the chart is followed, the better chance there is of keeping project costs
within budget while also better assuring on-time completion.
5. Flexibility – the ability to amend or create new Gantt charts as the project
evolves lets you react to unexpected changes in project scope or timeline
(which is almost guaranteed in every project!)
6. Efficiency – visualising resource usage during projects allows managers to
make better use of people, places and things. Team members have the ability
to leverage each other’s deadlines to maximise efficiency.
7. Time management – scheduling is one of the major benefits of Gantt charts.
By understanding the impact of project delays, teams work better together on
their task organisation. Decision makers can also look further ahead to ensure
each given project is working towards achieving the organisations strategic
objectives.
1.1.2. GANTT CHART:
1.2. PROGRAM EVALUATION AND REVIEW TECHNIQUE
(PERT CHART)
PERT Chart is acronym for (Program Evaluation and Review Technique). A PERT
chart is a project management tool used to schedule, organize, and coordinate tasks
within a project. It is basically a method to analyze the tasks involved in completing a
given project, especially the time needed to complete each task, and to identify the
minimum time needed to complete the total project.

1.2.1. WHEN TO DRAW PERT CHART

Project managers can use PERT charts to solve the following problems:

 Plan a realistic timetable for project completion.

 Identify critical path - since the path leads to the minimum time the project
requires, any delays to these tasks will impact the completion of the overall
project.
 Identify tasks that can be carried out concurrently.
 Identify tasks that need to be compressed if the overall project time needs to
be reduced.
 Identify slack time where certain tasks are not as time-critical to the overall
deadline.

1.2.2. THE BENEFITS OF PERT CHARTS

A PERT chart allows managers to evaluate the time and resources necessary to
manage a project. This evaluation includes the ability to track required assets during
any stage of production in the course of the entire project.

PERT analysis incorporates data and information from multiple departments. This
combining of information encourages department responsibility, and it identifies all
responsible parties across the organization. It also improves communication during
the project, and it allows an organization to commit to projects that are relevant to
its strategic positioning.

Finally, PERT charts are useful for what-if analyses, Understanding the possibilities

concerning the flow of project resources and milestones allows management to
achieve the most efficient and useful project path.

1.2.3. THE DISADVANTAGES OF PERT CHARTS

Disadvantage:

Complicated Charts

 PERT charts can be complicated and confusing, with hundreds or even

thousands of tasks and dependency relationships, as noted by the
University of Pittsburgh. This is especially true of very large projects.
PERT diagrams can be expensive to develop, update and maintain.

Disadvantage:

Prediction Inaccuracies
 PERT charts depend on the ability to predict precise time frames for
multitudes of tasks. Complicated projects involving many activities and
suppliers can make this prediction difficult, as explained by U.S. Legal
Definitions. Unexpected events occur, and sometimes the original
estimate of time needed for specific steps was inaccurate. PERT works
best in projects where previous experience can be relied on to
accurately make these predictions.

1.2.4. PROJECT PERT CHART

 1.3. WORK BREAKDOWN STRUCTURE:

The WBS is a method for getting a complex, multi-step project done. It's a way to
divide and conquer large projects so you can get things done faster and more
efficiently. Work breakdown structure (or WBS) is a hierarchical tree structure that
outlines your project and breaks it down into smaller, more manageable portions. In
Wrike, you can build a WBS by creating folders and subfolders, and can even go
further to divide individual tasks into subtasks. The goal of a WBS is to make a large
project more manageable. Breaking it down into smaller chunks means work can be
done simultaneously by different team members, leading to better team productivity
and easier project management overall.

1.3.1. WHY USE A WORK BREAKDOWN STRUCTURE?

There’s no doubt about it: Estimating projects can be confusing and somewhat
difficult. But creating a project estimate doesn’t have to cause you heartburn. Asking
questions, analyzing needs, and breaking your scope down into chunks can help.
Creating a work breakdown structure for any plan or set of tasks helps you get
granular about the work that needs to be done on any given project. If you estimate
your projects based on units—whether it’s weeks, days, or hours—using a work
breakdown structure will help you understand very quickly if your estimate will
exceed the intended budget or deadline.

Now that you have the complete work breakdown structure, it’s time to review why
you should use this approach to project management. Using a work breakdown
structure delivers numerous benefits, including:

 Improved planning: Large, complex projects can be difficult to wrap

your head around, let alone plan from start to finish. Using work
breakdown structure helps improve planning by making it easy to visualize
the scope of the project and break it down into more manageable
milestones. As a result, work breakdown structure allows you to set clear
timelines earlier on, make sure no work gets duplicated or overlooked, and
understand the level of output at any point in the project timeline.

 Smarter budget and resource allocation: By improving project

planning, work breakdown structure allows for smarter budget and
resource allocation. Specifically, it ensures that all budget and time
requirements get accounted for at the very beginning of a project.
Additionally, the mutually exclusive rule guarantees that no duplicate
work will take place, which eliminates wasted budget and time.
  Simplified risk identification: The visual nature of work breakdown
structure makes it easier to identify areas of risk so that you can get ahead
of problems and remedy them faster.

 Improved accountability: The clear work assignments, timelines, and

budgets identified by work breakdown structure improve accountability
among team members. That’s because everyone involved should have a
clear understanding of what they are responsible for and the time they have
to complete that work.

 Enhanced visibility: Finally, work breakdown structure provides a high

level of visibility into every project. This visibility makes it easy to
communicate expectations to stakeholders and team members and track
progress throughout the project.

A work breakdown structure is a helpful method for managing the challenges that
accompany large-scale enterprise projects and enjoying successful outcomes.
1.3.2. WBS STRUCTURE

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 2. PROCESS DETAILS AND EQUIPMENT DESCRIPTION:
2.1. Zno preparation:
Techniques for preparation of heavy metals.:
■ Chemical Precipitation
Solution precipitation relies on the precipitation of nanometer-sizedparticles within a
continuous fluid solvent. An inorganic metal salt, such aschloride, nitride and so on, is
dissolved in water. Metal cations exist in theform of metal hydrate species, for
example, Al(H2O)3+ or Fe(H2O6)3+.These hydrates are added with basic solutions,
such as NaOH or Na4OH.The hydrolyzed species condense and then washed, filtered,
dried andcalcined in order to obtain the final product.

■ Vacuum Deposition and Vaporization

In vacuum deposition process, elements, alloys or compounds are vaporized and
deposited in a vacuum ..
■ Chemical Vapor Deposition (CVD) and Chemical Vapor Condensation
(CVC)
CVD is a well known process in which a solid is deposited on a heated surface via a
chemical reaction from the vapor or gas phase.
■ Gas Condensation:
Formation of nanoparticles occurs when vapours cool down in the condensation zone
which is larger as the gas pressure is lower
■ Sol-Gel Techniques.
It involves the evolution of networks through the formation of colloidal suspension
(sol) and gelatin to form a network in continuous liquid phase (gel). Sol-gel formation
occurs in four stages.
■ Hydrolysis
■ Condensation
■ Growth of particles
■ Agglomeration of particles
EMPLOYED METHOD:
MATERIALS AND METHODOLOGY
RAW MATERIALS:
a) Zinc Acetate
b) Potassium Hydroxide
c) Methanol
d) H2O

METHOD
Firstly,prepared following solutions:
1. 5.487 gm zinc acetate dissolve in 250 ml methanol.
2. 1.9965 gm copper acetate dissolve in 100 ml methanol.
3. 2.8 gm KOH dissolve in 50 ml methanol.

REACTION

Heating the solution of zinc acetate and copper acetate.After reaching 55 degree
celsius.Take 22 ml KOH pipette out and pour into each flasks(four) and stirring till 30
mins

SETTLING
.Then after we added 100 ml water in each flasks(four) along with continuously
heating and stirring and carring temperature upto 80 degree celcius ,beyond 80 degree
celcius stop the heating and reduce the temperature automatically.Maintain the
temperature at 80 degree celcius,then continuously stirring for 1 hour at the same
temperature.

GEL FORMATION

Take four samples already prepared in previous procedure.We need

four chemicals list are given below:
1. Deionized water (50%) (Dispersing)
2. Ethanol (25%) (Dispersed)
3. Ethylene glycol (20%) (Gel formation)
4. Glycerine (5%) (Adhesion)
INITIAL CALCULATIONS AT LABORATORY SCALE

219.38 g of zinc acetate contains 65.38 g of zinc.

5.487g of zinc acetate contains 5.487 x 65.38/219.38 = 1.63g

Moles of Zn: 1.63 = 0.025 moles

65.38

Moles of O2 in ZnO = moles of Zn

=0.025 moles

mass of O2: 0.025 x 16 = 0.4 g

total theoretical yield = 1.63 + 0.4

= 4.075g of ZnO

experimental yield = 1.6214g

% yield = 39.8%

2.2. SONICATION
Sonication is the act of applying sound energy to agitate particles in a sample, for
various purposes such as the extraction of multiple compounds from plants,
microalgae and seaweeds. Ultrasonic frequencies (>20 kHz) are usually used,
leading to the process also being known as ultrasonication or ultra-sonication
 2.2.1. WORKING
Ultrasonic cleaning uses cavitation bubbles induced by high frequency pressure
(sound) waves to agitate a liquid. The agitation produces high forces on contaminants
adhering to substrates like metals, plastics, glass, rubber, and ceramics. This action
also penetrates blind holes, cracks, and recesses

2.2.2. PRINCIPLE
Sonication uses sound waves to agitate particles in a solution. It converts an electrical
signal into a physical vibration to break substances apart. These disruptions can mix
solutions, accelerate the dissolution of a solid into a liquid, such as sugar into water,
and remove dissolved gas from liquids.

2.2.3. WHY SONICATION USED FOR CLEANING?

Ultrasonic waves are used to clean the objects on hard to reach places like spiral
tubes, etc. The object is dipped in a cleaning solution and the ultrasonic waves are
sent into the solution. Due to the high frequency sound the dust or grease get
detatched from the object and the object gets cleaned
 2.3. SPIN COATING
Spincoating is a procedure used to deposit uniform thin films onto flat substrates.
Usually a small amount of coating material is applied on the center of the substrate,
which is either spinning at low speed or not spinning at all.

2.3.1. SPIN COATER

A machine used for spin coating is called a spin coater, spin processor or simply
spinner. Rotation is continued while the fluid spins off the edges of the substrate, until
the desired thickness of the film is achieved. The applied solvent is usually volatile,
and simultaneously evaporates.

2.3.2. WHY SPIN COATING?

Spin coating is one of the most common techniques for applying thin films to
substrates. ... It also has some differences due to the relatively thin films and high
uniformity required for effective device preparation, as well as the need for self-
assembly and organisation to occur during the casting process.
 2.3.3. APPLICATION OF SPIN COATING
Spin coating applications can vary greatly. The technique can be used to coat small
substrates (from a few mm square) or flat panel TVs which might be a metre or more
in diameter. It is used for coating substrates with everything from photoresists,
insulators, organic semiconductors, synthetic metals, nanomaterials, metal and metal
oxide precursors, transparent conductive oxides, and  many more materials. In short, it
is ubiquitous throughout the semiconductor and nanotechnology R&D/Industrial
sectors

2.3.4. ADVANTAGES AND DISADVANTAGES OF SPIN

COATING
The advantages of spin coating are the simplicity and relative ease with which a
process can be set up, coupled with the thin and uniform coating that can be achieved.
Due to the ability to have high spin speeds the high airflow leads to fast drying times,
which in turn results in high consistency at both macroscopic and nano length scales.
The disadvantage of spin coating is that it is an inherently batch (single substrate)
process and therefore has a relatively low throughput compared to roll-to-roll
processes. The fast drying times can also lead to lower performance for some
particular nano-technologies (small molecule OFETs for example), which require
time to self-assemble and/or crystallise. Finally, the actual material usage in a spin
coating process is typically very low (at around 10% or less), with the rest being flung
off the side and wasted. Whilst this is not usually an issue for research environments,
it is clearly wasteful for manufacturing.

2.3.5. SPECIAL REQUIREMENTS FOR SPIN COATING

NANOPARTICLES
In many areas of organic electronics and nanotechnology, the casting and drying
stages of an ink are an integral part of the technology, and is where all the "action"
happens. It is sometimes refereed to as "the science of paint drying" and in all of the
examples below, part or all of the key process happens during the drying of the ink.
Control of this process is critical.

a) π-π stacking/crystallisation of a small molecule or polymers

b) self-assembly of a block-copolymer
c) phase separation of a polymer-fullerene blend
d) aggregation/assembly of nanoparticles and colloids

In short, this means that when spin coating nanoparticles for OE/nano applications,
the properties of the film don't just depend upon its physical characteristics (thickness,
uniformity) but also very strongly upon the processing (drying time and conditions).
This compares with many more general spin coating processes such as applying a
photoresist where the end result is oadly independent of the exact application route.
For this reason there are a wider variety of techniques that are often used in organic
electronics and nanotech - especially in a research environment..

SPIN COATING DURATION

For most standard spin coating techniques the objective is to keep the substrate
spinning until the film is fully dry. As such this will mainly depend upon the boiling
point and vapour pressure of the solvent that is used but also on the ambient
conditions (temperature and humidity) that the spin coating is performed in. For most
solvents (such as the list below) a spin coating duration of 30 seconds is usually more
than adequate and is therefore recommended as a starting point for most processes.

2.4. CYCLIC VOLTAMMETRY

Cyclic Voltammetry (CV) is an electrochemical technique which measures the
current that develops in an electrochemical cell under conditions where voltage is in
excess of that predicted by the Nernst equation. CV is performed by cycling the
potential of a working electrode, and measuring the resulting current.

2.4.1. CHARACTERISTICS OF VOLTAMMETRY

The common characteristic of all voltammetric techniques is that they involve:
a) the application of a potential (E) to an electrode
b) the monitoring of the resulting current (i) flowing through the electrochemical
cell.
c) In many cases, the applied potential is varied or the current is monitored over
a period of time (t).
d) Thus, all voltammetric techniques can be described as some function of E, i,
and t.
A voltammetric cell consists of the three micro electrodes. They are
a) THE WORKING ELECTRODE

A reference electrode is an electrode  which has a stable and well-known  electrode

potential.The high stability of the electrode potential is usually reached by employing
a redox system with constant (buffered or saturation concentrations of each
participant of the redox reaction.

B) THE AUXILIARY ELECTRODE(COUNTER):

Counter electrode is a sink of electron which facilitate the movement of electron from
working electrode (source of electron) to counter electrode. The actual role is measuring the
current of working electrode
C) THE REFERENCE ELECTRODE
-The reference electrode should provide a reversible half-reaction with Nernstian
behaviour. Its only role is to act as reference in measuring and controlling the working
electrode’s potential.
The most commonly used reference electrodes for aqueous solutions are the calomel
electrode
.

2.4.2. APPLICATIONS
Cyclic Voltammetry can be used to study qualitative information about
electrochemical processes under various conditions, such as the presence of
intermediates in oxidation-reduction reactions, the reversibility of a reaction.
CV can also be used to determine the electron stoichiometry of a system, the
diffusion coefficient of an analyte, and the formal reduction potential, which
can be used as an identification tool. In addition, because concentration is
proportional to current in a reversible, Nernstian system, concentration of an
unknown solution can be determined by generating a calibration curve of
current vs. concentration.

2.5. FET SENSING:

2.5.1. FET:
A bipolar transistor has terminals labeled base, collector, and emitter. ... For a field-
effect transistor, the terminals are labeled gate, source, and drain, and a voltage at the
gate can control a current between source and drain. The image represents a typical
bipolar transistor in a circuit.
The field-effect transistor (FET) is an electronic device which uses an electric field to
control the flow of current. FETs are devices with three terminals: source, gate, and
drain. ...FETs are also known as unipolar transistors since they involve single-carrier-
type operation.

2.5.2. TERMINALS OF FET (SOURCE, GATE, DRAIN)

Source means the source of electrons and drain symbolizes the sink, or the lower
potential region for electrons. In a NFET, source is usually grounded and drain is
connected to a source voltage. This means that the current flows from s drain to
source but electrons flow from source to drain.
FET is three terminal semiconductor devices, with source, drain and gate terminals.
The charge carries are electrons or holes, which flow from the source to drain though
an active channel. This flow of electrons from source to drain is controlled by voltage
applied across the gate and source terminals.
The FET controls the flow of electrons (or electron holes) from the source to drain by
affecting the size and shape of a 'conductive channel' created and influenced by
voltage (or lack of voltage) applied across the gate and source terminals. The gate
terminal is always reverse bias.
Since the gate source junction is a reverse biased silicon diode, only a very small
reverse current flows through it. Ideally gate current is zero. As a result, all the free
electrons from the source go to the drain i.e. ... FET takes larger changes in input
voltage to produce changes in output current.
2.5.3. WORKING PRINCIPLE OF ISFET
The working principle of an ISFET pH electrode is a change of normal field effect
transistor and they are used in many amplifier circuits. In the ISFET normally the
input is used as metal gates, which are replaced by the ion-sensitive membrane. Hence
the ISFET gather in one device the sensing surface and a single amplifier gives the
high current, low impedance output and it allows the use of connecting cables without
unnecessary shielding. The following diagram shows the illustration of ISFET pH
electrode.
The ion sensitive field effect transistors are the novel integrated devices in the micro
electrochemical lab on chip systems. These are the common type of chemically
sensitive field effect transistors, and the structure is same as the general metal oxide
semiconductor field effect transistor. The sensitive area represents a transistor gate
and incorporates the means of transduction from an ion concentration to a voltage. In
the case of ISFET the metal oxide and the metal gates are of general MOSFET are
replaced by the simple solution with the reference electrodes deep in the solutions and
the insulating layers are for detecting the specific analyte. The nature of the insulating
layers is defined as the functionality and sensitivity if the ISFET sensor.
2.5.4. WHAT IS AN ISFET?
The abbreviation of the ISFET is Ion Sensitive Field Effect Transistor. It is a field
effect transistor, used for the measuring the concentration of ion solutions. The ion
concentration like H+ is changed as pH then there is a change in current through the
transistor consequently. Here the gate electrode is the solution and the voltage
between the oxide surface and the substrate are due to the ion sheath.
2.5.5. FABRICATION STEPS FOR ISFET
The following step by step process shows the fabrication of the ISFET
ISFET is fabricated with the help of the CMOS technology and without any post
processing steps
All the fabrication is done in the in house in the micro fabrication Lab
The material should be 4inch p-type silicon wafer
In the ISFET the gate terminal is prepared with the material of SiO2, Si3N4, both
COMS computable materials.
There are six masking steps which are a creation of n-well, n and p source drains,
gate, contact and material.
The design of Si3N4 and SiO2 is through the buffer oxide etch solutions

The following fabrication steps show the standard MOSFET process and up to the
time of the deposition of silicon nitride as an ion sensing film. The performance of the
deposition of the silicon nitride is with the help of the plasma enhanced chemical
vapor deposition method. The thickness of the film is measured with the ellipsometer.
After the nitride deposition, the process is continued to contact form by using the
contact mask. A ChemFET is a chemically-sensitive field-effect transistor, that is a
field-effect transistor used as a sensor for measuring chemical concentrations in
solution.[1] When the target analyte concentration changes, the current through the
transistor will change accordingly.[2] Here, the analyte solution separates the source
and gate electrodes.[3] A concentration gradient between the solution and the gate
electrode arises due to a semi-permeable membrane on the FET surface containing
receptor moieties that preferentially bind the target analyte.[3] This concentration
gradient of charged analyte ions creates a chemical potential between the source and
gate, which is in turn measured by the FET.
The schematic view of a ChemFET. Source, drain, and gate are the three electrodes
used in a FET system. The electron flow takes place in a channel between the drain
and source. The gate potential controls the current between the source and drain
electrodes.

A ChemFET's source and drain are constructed as for an ISFET, with the gate
electrode separated from the source electrode by a solution.[4] The gate electrode's
interface with the solution is a semi-permeable membrane containing the receptors,
and a gap to allow the substance under test to come in contact with the sensitive
receptor moieties.[5] A ChemFET's threshold voltage depends on the concentration
gradient between the analyte in solution and the analyte in contact with its receptor-
embedded semi-permeable barrier.[5]
ChemFETs can be utilized in either liquid or gas phase to detect target analyte,
requiring reversible binding of analyte with a receptor located in the gate electrode
membrane.[8][3]There is a wide range of applications of ChemFETs, including most
notably anion or cation selective sensing.[5] More work has been done with cation-
sensing ChemFETs than anion-sensing ChemFETs.[5] Anion-sensing is more
complicated than cation-sensing in ChemFETs due to many factors, including the
size, shape, geometry, polarity, and pH of the species of interest.
 3. MATERIAL AND ENERGY BALANCES:
3.1. Material Balances:
As per the reaction, the amount of raw materials and the products along with the
solvent is calculated for a basis of 1000 mol of ZnO nanoparticles.
The Material balances calculations are done around the reactor that is our only
process equipment and quantities can be seen from the following tables:
Table 1.1.

Components   Inlet Outlet Inlet Outlet

  mol mol gm Gm
1509.434 509.434 331139.6 111759.6
Zinc Acetate
2113.208 1113.208 118550.9 1.8536
Alcholic Potash
436847.5 436847.5 13996595 13996595
Methanol
0 1000 0 99424
Zinc Hydroxide
0 1000 0 81380
Zinc Oxide
 0 2025.96 0 198848
Potassium Acetate
836211.2 836211.2 15051801 15051801
Water

For Gel Formation:

The amount of substances that are required are:

Ethylene Glycol            
for 8 ml of ZnO paste = 2 ml of ethylene glycol
for 1 ml of ZnO paste = 0.25 ml of ethylene glycol
for 401529.5 ml of ZnO paste = 100382.4 ml of ethylene glycol
        = 100.3824 liters of ethylene glycol 

2 Methoxy
Ethanol            
for 8 ml of ZnO paste = 2 ml of 2 methoxy ethanol
for 1 ml of ZnO paste = 0.25 ml of 2 methoxy ethanol
for 401529.5 ml of ZnO paste = 100382.4 ml of 2 methoxy ethanol
        = 100.3824 liters of methoxy ethanol

Glycerol
:              
for 8 ml of ZnO paste = 2 ml of glycerol
for 1 ml of ZnO paste = 0.25 ml of glycerol
for 401529.5 ml of ZnO paste = 100382.4 ml of glycerol
        = 100.3824 liters of glycerol

For DI Water            
for 8 ml of ZnO paste = 4 ml of DI water
for 1 ml of ZnO paste = 0.5 ml of DI water
for 401529.5 ml of ZnO paste = 200764.8 ml of DI water
        = 200.7648 liters of DI water

For amount of utility water required for heat transfer:

        
Q = m cp delta t
217665585.9 = m 4.2 15
777377092.3 gm = m  
777377092.
Volume= = 3 cm3  
777377.092
Water required for heating = 3 liter  
777.377092
  = 3 m3  

3.2. ENERGY BALANCES:

The heat requirement for this batch process was calculated and the heat
requirements for the production of 1000 mol of ZnO is shown in form of a table.
First finding the heat of reaction from 55 oC to 25 oC reference:
From 55 to 25              
  Q = n cp ΔT    
KOH Q = 2113.207548 65.87 -30 -4175909.4 J
Zinc Acetate Q = 1509.433962 153.6 -30 -6955471.7 J
Zinc Hydroxide Q = 0 72.27 -30 0 J
Potassium Acetate Q = 0 109.38 -30 0 J
Methanol Q = 436847.5193   -30 -671.90287 J
        Q1 Q total= -116494660 J

Now finding the requirement from 25 oC to 80 oC:

 From 25 to 80:              
               
1113.20754 4032983.9
KOH Q = 8 65.87 55 7 J
509.433962 4303698.1
Zinc Acetate Q = 2 153.6 55 1 J
Zinc Hydroxide Q = 1000 72.27 55 3974850 J
2025.96026 12187974.
Potassium Acetate Q = 5 109.38 55 4 J
436847.519 1299.5436
Methanol Q = 3 0 55 2 J
Q 21766558
        Q2 total= 6 J

Now the total reaction heat becomes:

Qrxn = Q2 - Q1
334160246.
Qrxn = 1 Joules  

4. REACTOR AND STORAGE TANK SIZES:

For Basis of 1000 mol of ZnO              

There would 1501.5015 mol of ZnAcetate would be
be 02 required.  
and for this we 3003.0030 mol of KOH would be
need 03 required.  
   
mass of Zinc 329399 329.399
Acetate = .4 g 4 Kg  
168468 168.468
mass of KOH = .5 g 5 kg  
   
Volume of Methanol
required:  
4. g of zinc acetate 235 ml of  
 4 Methanol
fo 329399.3 g of Zinc 175929 ml of
r 99 Acetate = 22 Methanol  
m3 of
17592.9 Liters 17.592 methano
  = 2 Methanol or 92 l
Volume of water required:  
ml
4. wat
4 g of zinc acetate = 200 er  
fo 329399.3 g of Zinc 149727 ml of
r 99 Acetate = 00 water  
Liters of 14.972 m3 of
          14972.7 water or 7 water

32565.6
Total Volume of reactor = 2 Liters        
8141.40
for safety volume = 6 Liters  
40707.0
Total Reactor Volume = 3 Liters  
40.7070
Total Reactor Volume = 3 m3  
   
21.9911
Total volume of Methanol Tank = 5 m3  
Total volume of Water 18.7158
tank = 7 m3  
   
Inside diameter of Methanol Tank = 5 m  
Radius = 2.5 m  
1.11999
height of tank = 8 m or 1.2 m
   
Inside diameter of Methanol Tank = 5 m  
Radius = 2.5 m  
0.95318
height of tank   = 9 m or 1 m

5. HAZARDS AND ENVIRONMENTAL ANALYSIS OF CHEMICALS

AND REAGENTS USED FOR THE PREPARATION OF ZNO NANO
PARTICLES USED IN ELECTROCHEMICAL AND FET SENSORS
 5.1. INTRODUCTION:
Heavy metal ions are non-biodegradable and contaminate most of the natural
resources occurring in the environment including water. Some of the heavy
metals including Lead (Pb), Mercury (Hg), Arsenic (As), Chromium (Cr)
and Cadmium (Cd) are considered to be highly toxic and hazardous to human health
even at trace levels. This leads to the requirement of fast, accurate and reliable
techniques for the detection of heavy metal ions. This review presents
various electrochemical detection techniques for heavy metal ions those are user
friendly, low cost, provides on-site and real time monitoring as compared to other
spectroscopic and optical techniques. The categorization of different electrochemical
techniques is done on the basis of different types of detection signals generated due to
presence of heavy metal ions in the solution matrix like current,
potential, conductivity, electrochemical impedance, and electrochemiluminescence.
Also, the recent trends in electrochemical detection of heavy metal ions with various
types of sensing platforms including metals, metal films, metal
oxides, nanomaterials, carbon nano tubes, polymers, microspheres and biomaterials
have been evoked.

5.2. HAZARDS OF ZNO

Zinc oxide is on the hazardous substance list because it s regulated by OSHA and
cited by ACGIH, DOT, DEP, EPA.

5.2.1. ECOTOXICITY:The product contains a substance which is very

toxic to aquatic organisms and which may cause long term adverse effects
in the aquatic environment.
The product is not readily biodegradable.

5.2.2. INHALATION: May cause irritation to the respiratory system.

5.2.3. SKIN CONTACT: Irritating to the skin.
5.2.4. EYE CONTACT: Irritating to eyes.
5.2.5. AQUATIC: Very toxic to aquatic organism.
4.3.6. WORKPLACE EXPOSURE LIMITS
5.3. OSHA: The legal airborne permissible exposure limit (PEL) is 5 mg/m3
(for Zinc Oxide fume), 15 mg/m3 (for total dust), and 5 mg/m3 (for
respirable dust) averaged over an 8-hour workshift.
5.4. NIOSH: The recommended airborne exposure limit is 5 mg/m3 (for Zinc
Oxide fume and dust) averaged over a 10-hour workshift, 10 mg/m3 as a
short-term exposure limit (for Zinc Oxide fume), and 15 mg/m3 (for Zinc
Oxide dust), not to be exceeded at any time.
5.5. ACGIH: The recommended airborne exposure limit is 2 mg/m3
averaged over an 8-hour workshift and 10 mg/m3 as a STEL (short-term
exposure limit) for the respirable fraction.
5.6. HEALTH HAZARD INFORMATION
Acute Health Effects; The following acute (short-term) health effects may occur
immediately or shortly after exposure to Zinc Oxide: * Exposure to Zinc Oxide can
cause “metal fume fever.” This is a flu-like illness with symptoms of metallic taste in
the mouth, headache, fever and chills, aches, chest tightness and cough. The
symptoms may be delayed for several hours after exposure and usually last for a day
or two.

5.6.1. CHRONIC HEALTH EFFECTS: The following chronic (long-

term) health effects can occur at some time after exposure to Zinc Oxide
and can last for months or years.
5.6.2. CANCER HAZARD: According to the information presently
available to the New Jersey Department of Health and Senior Services,
Zinc Oxide has not been tested for its ability to cause cancer in animals.
5.6.3. REPRODUCTIVE HAZARD: * Zinc Oxide may damage the
developing fetus.
5.6.4. OTHER LONG-TERM EFFECTS: * Zinc Oxide has not been
tested for other chronic (long-term) health effects.

5.7. WORKPLACE CONTROLS AND PRACTICES

Special controls should be in place for highly toxic chemicals or when significant
skin, eye, or breathing exposures are possible.
In addition, the following control is recommended:
* Where possible, automatically transfer Zinc Oxide from drums or other storage
containers to process containers. Good WORK PRACTICES can help to reduce
hazardous exposures. The following work practices are recommended:
* Workers whose clothing has been contaminated by Zinc Oxide should change into
clean clothing promptly.
* Do not take contaminated work clothes home. Family members could be exposed.
* Contaminated work clothes should be laundered by individuals who have been
informed of the hazards of exposure to Zinc Oxide.
* Eye wash fountains should be provided in the immediate work area for emergency
use.
* If there is the possibility of skin exposure, emergency shower facilities should be
provided.
* On skin contact with Zinc Oxide, immediately wash or shower to remove the
chemical. At the end of the workshift, wash any areas of the body that may have
contacted Zinc Oxide, whether or not known skin contact has occurred.
* Do not eat, smoke, or drink where Zinc Oxide is handled, processed, or stored,
since the chemical can be swallowed. Wash hands carefully before eating, drinking,
applying cosmetics, smoking, or using the toilet.
* Use a vacuum or a wet method to reduce dust during clean-up. DO NOT DRY
SWEEP.
PERSONAL PROTECTIVE EQUIPMENT
Clothing:* Avoid skin contact with Zinc Oxide. Wear protective gloves and clothing.
Safety equipment suppliers/manufacturers can provide recommendations on the most
protective glove/clothing material for your operation. * All protective clothing (suits,
gloves, footwear, headgear) should be clean, available each day, and put on before
work.
Eye Protection: * Wear eye protection with side shields or goggles.
Respiratory Protection

5.8. IMPROPER USE OF RESPIRATORS IS DANGEROUS. Such

equipment should only be used if the employer has a written program that
takes into account workplace conditions, requirements for worker training,
respirator fit testing, and medical exams, as described in the OSHA
Respiratory Protection Standardin some studies investigating the toxicity
of zinc oxide nanoparticles in different biological systems such as bacteria
and mammalian cells. In mammalian cells, the toxic effects of ZnO
nanoparticles such as membrane injury, inflammatory response, DNA
damage have been demonstrated.
5.9. HAZARDS OF METHANOL: As a volatile, strongly polar alcohol
methanol has numerous biological environmentalphysical and chemical
hazards. Methanol is a major industrial chemical and solvent and haslong
been connected with ethanol as a denaturant With the numerous proposed
large scale uses of methanol, especially as a fuel, the hazards are receiving
more serious attention. Methanol shares with its homologues this acute
narcotic action but is anomalous in that it also exerts characteristic chronic
toxic effects, probably due to the slowness with which it is eliminated
from the body and the toxicity of the products of its metabolic oxidation,
formaldehyde and formic acid. there is a definite hazard associated with
the now extensive industrial use of methanol. The danger is increased by
the tendency to confuse
methanol with ethanol and use it as a beverage. The danger from its use in
industry was first noted by McFarlan in 1856 (McCord, 1931), and
numerous cases of industrial poisoning have been reported since then. It
was early shown that exposure of rats, mice, dogs, and cats to methanol
vapour may cause death. McCord concluded that continued exposure to a
vapour concentration of 1,000 p.p.m. or exposure to conditions where 31
ml. Results obtained in experiments with animals have been used to
estimate safety limits of exposure to methanol for man. It has been noted
that McCord suggested that conditions where 31 ml. of methanol may be
absorbed in 41 hours (18 g./24 hours) are dangerous. It May be fatal or
cause blindness if swallowed.
 5.9.1. HAZARD STATEMENTS:
H225 Highly flammable liquid and vapour.
H301+H311+H331 Toxic if swallowed, in contact with skin or if inhaled.
H370 Causes damage to organs (eye, heart, brain, liver, central
nervous system).
Precautionary Statements
P210 Keep away from heat, hot surfaces, sparks, open flames
and other ignition sources. No smoking.
P241 Use explosion-proof
electrical/ventilating/lighting/tooling/equipment.
P260 Do not breathe mist/vapours/spray.
P280 Wear protective gloves/protective clothing/eye
protection/face protection.
P301+P310 IF SWALLOWED: Immediately call a POISON
CENTER/doctor/….
P303+P361+P353 IF ON SKIN (or hair): take off immediately all
contaminated clothing. Rinse skin with water/shower.
P304+P340 IF INHALED: Remove person to fresh air and keep
comfortable for breathing.
P403+P235 Store in a well-ventilated place. Keep cool.
P501 Dispose of contents/container to ...

5.10. HAZARDS OF KOH:

identification:
HAZARD STATEMENTS (GHS-US): H302 - Harmful if swallowed
H314 - Causes severe skin burns and eye damage
H402 - Harmful to aquatic life
PRECAUTIONARY STATEMENTS (GHS-US): P260 - Do not breathe dust.
P264 - Wash exposed skin thoroughly after handling.
P270 - Do not eat, drink or smoke when using this product.
P273 - Avoid release to the environment.
P280 - Wear protective gloves, protective clothing, eye protection, face protection.
P301+P330+P331 - IF SWALLOWED: Rinse mouth. Do
not induce vomiting.

Personal protective equipment:

Corrosionproof clothing. Protective goggles. Dust formation: dust mask. Gloves.
FIRST-AID MEASURES
DESCRIPTION OF FIRST AID MEASURES
FIRST-AIDMEASURESGENERAL :
Check the vital functions. Unconscious: maintain adequate airway and respiration.
Respiratory arrest: artificial respiration or oxygen.
Cardiac arrest: perform resuscitation. Victim conscious with labored breathing: half-
seated. Victim in shock: on his back with legs slightly raised.
Vomiting: prevent asphyxia/aspiration pneumonia. Prevent cooling by covering the
victim (no warming up). Keep watching the victim. Give psychological aid. Keep the
victim calm, avoid physical strain.
Depending on the victim's condition: doctor/hospital. First-aid measures after
Inhalation : Remove the victim into fresh air. Doctor: administration of corticoid
spray. Respiratory problems: consult a doctor/medical service.
First-aid measures after skin contact : Wash immediately with lots of water (15
minutes)/shower.Do not apply (chemical) neutralizing agents. Remove clothing while
washing. Do not remove clothing if it sticks to the skin. Cover wounds with sterile
bandage. Consult a doctor/medical service. If burned surface > 10%: take
victim to hospital.

First-aid measures after eye contact : Rinse immediately with plenty of water for
15 minutes. Cover eyes aseptically. Do not apply neutralizing agents. Take victim to
an ophthalmologist.
First-aid measures after ingestion : Rinse mouth with water. Immediately after
ingestion: give lots of water to drink. Do not induce vomiting. Do not give activated
charcoal. Immediately consult a doctor/medical service. Call Poison Information
Centre (www.big.be/antigif.htm). Ingestion of large quantities: immediately to
hospital. Take the container/vomit to the doctor/hospital. Do not give chemical
antidote.

5.11. Hazards of Zinc Acetate: Statements: Harmful if swallowed \Causes

serious eye damage\
Precautionary Statements:
Prevention:Wash face, hands and any exposed skin thoroughly after handling Do not
eat, drink or smoke when using this product
Wear protective gloves/protective clothing/eye protection/face protection.
Eyes
IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses,
if present and easy to do. Continue rinsing
Immediately call a POISON CENTER or doctor/physician
Ingestion
IF SWALLOWED: Call a POISON CENTER or doctor/physician if you feel unwell
Rinse mouth
Disposal
Dispose of contents/container to an approved waste disposal plant
Hazards not otherwise classified (HNOC)
Toxic to aquatic life with long lasting effects.
First-aid measures
General Advice If symptoms persist, call a physician.
Eye Contact Rinse immediately with plenty of water, also under the eyelids, for at
least 15 minutes. Get
medical attention.
Skin Contact Wash off immediately with plenty of water for at least 15 minutes. If
skin irritation persists,
call a physician.
Inhalation Move to fresh air. If not breathing, give artificial respiration. Get medical
attention if
symptoms occur.
Ingestion Clean mouth with water and drink afterwards plenty of water. Get medical
attention if
symptoms occur.
Most important symptoms and
effects
None reasonably foreseeable. Causes severe eye damage.

Personal Precautions Ensure adequate ventilation. Use personal protective

equipment. Avoid dust formation.
Environmental Precautions Do not flush into surface water or sanitary sewer
system. Should not be released into the
environment. Do not allow material to contaminate ground water system.
Hazard Statements of Potassium Acetate: May form combustible dust
concentrations in air
Precautionary Statements
Storage
Store in a well-ventilated place. Keep container tightly closed.
First-aid measures
Eye Contact Rinse immediately with plenty of water, also under the eyelids, for at
least 15 minutes. Get
medical attention.
Skin Contact Wash off immediately with plenty of water for at least 15 minutes. Get
medical attention
immediately if symptoms occur.
Inhalation Move to fresh air. If breathing is difficult, give oxygen. Get medical
attention immediately if
symptoms occur.
Ingestion Do not induce vomiting. Obtain medical attention.
Most important symptoms and
effects
No information available.
Handling Wear personal protective equipment. Ensure adequate ventilation. Avoid
contact with skin,
eyes and clothing. Avoid ingestion and inhalation. Avoid dust formation. Protect from
moisture.
Storage Keep containers tightly closed in a dry, cool and well-ventilated place.
Exposure controls / personal protection
Exposure Guidelines This product does not contain any hazardous materials with
occupational exposure
limitsestablished by the region specific regulatory bodies.
Stability and reactivity
Engineering Measures None under normal use conditions.
Personal Protective Equipment
Eye/face Protection Wear appropriate protective eyeglasses or chemical safety
goggles as described by
OSHA's eye and face protection regulations in 29 CFR 1910.133 or European
Standard
EN166.
Skin and body protection Wear appropriate protective gloves and clothing to
prevent skin exposure.
Respiratory Protection No protective equipment is needed under normal use
conditions.
Hygiene Measures Handle in accordance with good industrial hygiene and safety
practice.

6. MATERIALS OF CONSTRUCTION:
When it comes to building a process plant, there are many material of construction
options for you to consider.  For some plants, the application itself can dictate what
MOCs are needed.  Previous experience, continuity and plant standards can also play
a crucial role in this decision. 
Common building materials used for process plants include carbon steel, stainless
steel, steel alloys, graphite, glass, titanium, plastic, Monel, and many more.  For this
discussion let’s focus on materials of construction that are used for highly corrosive
and abrasive media.  

6.1. Selection Variables

There are several variables that should influence your decision when selecting the best
material of construction for your plant.  The three major ones are:

 Corrosion resistance – What chemicals are you processing? You’ll need to be

conscious of selecting materials that comply with the chemical composition of
your process to ensure it will perform to your expectations.
 Cost – What is your budget? Capital expenditures need to be taken into
consideration to ensure you don’t exceed the financial limits for the project. 
 Expected operating life – How long do you plan to keep your system in
operation? Whether it’s a continuous or batch process, how frequently it is run,
and how many years of service you hope to get out of it are all questions that
need to be accounted for when you are determining what type of system
components to employ. 

There are other minor variables such as compatibility of material of construction with
existing plant installations, plant operating conditions, ease of maintenance, and
cleaning requirements to name a few.  While these are less critical, they are still
important to keep in mind as you establish the criteria for your plant. 

6.2. Corrosion Resistant MOC Options

When looking at materials of construction for highly corrosive media your options are
more limited. Depending on your operating conditions and the actual media being
processed in your plant you will most probably end up with a combination of
materials, including:

 Hastelloy C-276 –A nickel-molybdenum-chromium superalloy that contains

tungsten to give it excellent corrosion resistance in a wide range of severe
environments.
 Inconel 600 - Typically used in high temperature applications, this material
forms a thick oxide layer when heated to protect the surface from chemical
attack. 
 Titanium – This alloy combines high strength with low density to provide
good corrosion resistance across a range of temperatures and is advantageous in
applications that benefit from weight savings (e.g. aerospace structures)
 Tantalum – Offers outstanding resistance to aqueous solutions and metal melts
with a high melting point, superconductivity, and biocompatibility.
 Monel 400 – A nickel-copper alloy that is resistant to sea water/salt solutions
and steam at high temperatures as well as caustic solutions.
 Plastics (PFA, PP, FRP, TEFZEL) – A variety of plastic polymers can be used
to provide extended service in hostile environments, offering excellent mechanical
stress resistance as well as stability at a wide range of temperatures.

 Glass – Available as Borosilicate 3.3 glass (i.e. QVF SUPRA-Line) and glass-
lined steel. We’ll dive into this more in the next sections.

6.3. MATERIAL COSTS

An indication of the cost of some commonly used metals is given in Table. The actual
cost of metals and alloys will fluctuate quite widely, depending on movements in the
world metal exchanges.

The quantity of a material used will depend on the material density and strength
(design stress) and these must be taken into account when comparing material costs.
Moore (1970) compares costs by calculating a cost rating factor defined by the
equation:

His calculated cost ratings, relative to the rating for mild steel (low carbon), are
shown in Table . Materials with a relatively high design stress, such as stainless
and low alloy steels, can be used more efficiently than carbon steel.
The relative cost of equipment made from different materials will depend on the
cost of fabrication, as well as the basic cost of the material. Unless a particular
material requires special fabrication techniques, the relative cost of the finished
equipment will be lower than the relative bare material cost. For example; the
purchased cost of a stainless-steel storage tank will be 2 to 3 times the cost of the
same tank in carbon steel, whereas the relative cost of the metals is between 5 to
8.
 6.4. SELECTION FOR CORROSION RESISTANCE

In order to select the correct material of construction, the process environment to

which the material will be exposed must be clearly defined. Additional to the main
corrosive chemicals present, the following factors must be considered:
1. Temperature affects corrosion rate and mechanical properties.
2. Pressure.
3. pH.
4. Presence of trace impurities stress corrosion.
5. The amount of aeration differential oxidation cells.
6. Stream velocity and agitation erosion-corrosion.
7. Heat-transfer rates differential temperatures.

The conditions that may arise during abnormal operation, such as at start-up and
shutdown, must be considered, in addition to normal, steady state, operation.

Hence the selected material of construction is Austintin chromium nickel corrosion

resistant stainless steel .

7. COST ANALYSIS:

INTRODUCTION

Fixed Cost: Costs that do not vary with production rate. These are the bills
that have to be paid whatever the quantity produced. [1] For example:
Maintenance (labor and materials), Operating labor, Laboratory costs, capital
 charges.

Variable Cost: Costs that are dependent on the amount of product

produced. [1] For example: Raw materials, miscellaneous operating materials,
utilities (services). Shipping and packaging etc.

7.1. COSTING FOR STORAGE TANKS:

Costing for the tanks were done by the method prescribed by Coulson Richardson's
Chemical Engineering Vol.6 Chemical Engineering Design 4th Edition.
A/c to this method data were taken from table 6.2
For Methanol Storage Tank: S-101
atmos. Press. Carbon
S = 22 m3   Vertical Process Tank steel
Ce = CS^n  
for C = 2400 from table6.2  
n = 0.6 from table6.2  
15334.3
ce = 3 cost in 2004  
39217.8
cost in 2020= 9 $  
                     

For Water Storage Tank: S-102

S = 19 m3              
atmos. Press. Carbon
Ce = CS^n Vertical Process Tank steel
for C = 2400 from table6.2  
n = 0.6 from table6.2  
ce = 14043.11 cost in 2004  
cost in 2020= 35915.57 $              

For Utility Water Storage Tank: S-103

S = 980 m3            
Ce = CS^n Cone Roof Stainless Steel
for C = 2300 from table 6.2  
N = 1.1 from table 6.2  
Ce = 4887949 cost in 2004  
1250103
cost in 2020= 9 $            

1257617
Total Storage Tank Costs: 2 $

7.2. COST FOR REACTOR:

The cost analysis for reactor is also done in the same way from the above
mentioned book:
For reactor R-101:

R-101              
Agitated Reactor costing  
S = 40 m3 glass lined Carbon Steel
C = 31000 from table 6.2  
N = 0.45  
163037.
Ce = 9 cost in 2004  
416973.
cost in 2020 = 1 $  
   
416973.
  Total Reactor Cost: 1 $      

7.3. COST OF RAW MATERIALS:

 This particular costing was done by present prices and rates of the chemicals used
in the above mentioned process.

For Zinc Acetate:        

kg of Zinc Acetate
1 dihydrate = 255 $
kg of Zinc Acetate 83996.8
329.3994 dihydrate = 5 $

For Potassium Hydroxide:      

Kg of Potassium
1 Hydroxide = 34.48 $
Kg of Potassium 5808.79
168.4685 Hydroxide = 3 $

For Methanol:        
1 liter of Methanol = 6.6043 $
116188.
17592.92 liter of Methanol = 9 $

For Glycerine:        
1 liter of glycerin = 6.6043 $
662.955
100.3824 liter of glycerin = 4 $

For ethylene Glycol:      

1 liter of Ethylene Glycol = 11.37 $
1141.34
100.3824 liter of Ethylene Glycol = 8 $

For 2 methoxy ethanol:      

1 liter of 2 methoxy ethanol = 195.19 $
19593.6
100.3824 liter of 2 methoxy ethanol = 4 $

For DI water:        
1 liter of DI Water = 6.3492 $
1274.69
200.7648 liter of DI Water = 6 $

228667.
Total Raw Material Cost: 2 $
 7.4. COST OF SERVICES:
Sonication: 40,000$
Spin Coating: 30,000$
Cyclic Voltammetry: 30,000$
Characterization:10,000$

7.5. TOTAL COSTING:

Fixed Costs: 12,993,145 $
Variable Costs: 228,667.2 $ + 110,000 $ = 338,667.2 $
Total Cost for the Research Project: 13331812 $
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3. ZnO safety data sheet
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Dept.of Mech.Engrg., Univ.of Minnesota Passenger Car MeetingDetroit Plaza,
DetroitSeptember 26-30,1977, 770792
5. A study of the conditions under which methanol may exert a toxic hazard in industry
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G. Leaf and l. J. Zatman
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Methanol
Version number: GHS 3.0
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Revision: 2016-08-10
8. Potassium hydroxide
Safety Data Sheet
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Date of Issue: 10/09/2004 revision date: 02/06/2018 supersedes: 02/06/2018 version:
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Creation Date 26-Sep-2009 Revision Date 11-Apr-2019 Revision Number 4
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