Module-1:

Modern Methods of Water Analysis

Engineering Chemistry (CHY1701)

By Dr. Kiran Kumar Tadi

Assistant Professor
Department of Chemistry
School of Advanced Sciences (SAS)
Vellore Institute of Technology, Chennai
Does Water Analysis Method Depends on the Application?

 Similarly
 Water Quality
Water quality refers to the physical, chemical, and biological
characteristics of water. It is a measure of the condition of water relative to the
requirements of one or more biotic species and or to any human need or
purpose.
It is most frequently used by reference to a set of standards against which
compliance can be assessed. The most common standards used to assess water
quality relate to health of ecosystems, safety of human contact and drinking
water.
Properties Analyzed: Total Dissolved Solids, Total Suspended Solids, PH, Chloride
(Cl-) Content, Conductivity, Sulphate content, Turbidity, Iron Content,
and Manganese content
 Water Quality

Aesthetically
Acceptable

Free from Absence of

Radioactiv
Bacteria
e elements

Safe water/
wholesome
water

Absence of Chemically
Organic Safe
Substances
 Modern methods of water analysis
oImportance of Water Analysis
Water analysis is essential to ensure its quality or to detect pollutants that should be
removed by water treatment.

However, water quality does not mean making the water suitable for human
consumption; it depends on its end use.

For example, completely different quality standards are applied in case of industrial
water compared to those applied to drink water, i.e., drinking water must be fit for human
consumption, while industrial water should be free from any contaminants that may
corrode or damage equipment.
Conventional Methods of Analysis

Chemical Analysis Spectrometry, colorimetry

Limitations
 sampling, expensive, and manpower; besides, they are
time-consuming and difficult to conduct onsite.
 Water Quality

oLimitations of Traditional Methods of Water Analysis

The traditional analysis includes

 chemical analysis

 colorimetry,

 spectrometry,

 chromatography, and atomic absorption.

Although these techniques differ in sensitivity and accuracy, most of them are

highly accurate. Nevertheless, they require sampling, expensive devices, and manpower;

besides, they are time-consuming and difficult to conduct onsite.

Modern Methods of Water Analysis

Electronic Tongue

Microfluidic-based
Lab-on-Chip
 Lab-on-a-Chip
o A lab-on-a-chip (LOC) is a device that integrates one or several laboratory functions on a
single integrated circuit (commonly called a "chip") of only millimeters to a few square
centimeters to achieve automation and high-throughput screening
o Lab-on-a-chip devices are a subset of microelectromechanical systems (MEMS) devices and
sometimes called "micro total analysis systems" (µTAS)
o LOCs may provide advantages, which are specific to their application. Typical advantages are:
a) low fluid volumes consumption (less waste, lower reagents costs, and fewer sample volumes)
b) faster analysis and response time due to short diffusion distance & high surface to volume
ratio.
c) better process control because of a faster response of the system compactness of the systems
due to the integration of much functionality and small volumes
d) lower fabrication costs, allowing cost-effective disposable chips, fabricated in mass production
e) safer platform for chemical, radioactive or biological studies because of integration of
functionality, smaller fluid volumes, and stored energies
 Lab-on-a-Chip
Microfluidics and Lab-On-A-Chip for Water Analysis

o Microfluidics and lab-on-a-chip systems are advanced technologies that may replace the traditional methods of water

analysis in the near future.

o Lab-on-a-chip technology employs microfluidics, which deals with very minute amounts of fluids in microchannels, to

perform the analysis.

o The lab-on-a-chip device is a chip that resembles electronic chips, but with micro-channels instead of electrical circuits.

o It shrinks the lab to the chip size and can perform complete analysis or even series of analysis.

Advantages of using lab-on-a-chip for water analysis:

o can reduce time and manpower in the sampling process because this technology can offer immediate, onsite results.

o In addition, this technique is much less expensive and offers higher accuracy, because of the small volumes analyzed and

the possibility of eliminating the sampling process, which reduces the human error.
 Components of Lab-on-a-Chip System
The main components of a lab-on-a-chip system for water analysis are; a liquid delivery system (injector and
fluidic transporter), mixer, reactor, separator, and power supply.
• The Injector is used to deliver precise volumes into the chip. The most common types of the injectors are
syringe pumps and robotic pipets.
• Transporters control all aspects of the flow. They can be active, which need an energy source, or passive,
which are achieved by manipulating the geometries of the channels and do not require any energy source. The
choice between the active and passive types is based on the application. There are multiple types of active
transporters, but the most preferred is electrochemical pumping systems, such as microsyringe pumps,
because they eliminate the design complexity.
• Mixers are used to mix different fluids into the channels. Similar to the transporters, the types of mixers are
divided into passive, which are achieved by design manipulation, and active, which require power.
• The Reactor is where the reaction takes place. There are three types of reactors used in lab-on-a-chip
systems: gas phase, liquid phase, and packed-bed reactors.
• Controllers are used for controlling all types of activities in the chip as well as data acquisition and signal
processing.
• Power supplies, such as batteries, are essential to run the lab-on-a-chip systems. Many research studies
focus on finding more advanced power supplies because some types of lab-on-a-chip systems require high
voltage.
Picture Ref: Y. C Lim, A. Z Kouzani, W Duan, Lab-on-a-chip: a component view, Microsyst Technol (2010) 16:1995–2015
References:
1. J. Cleary, C. Slater, D. Diamond, Analysis of phosphate in wastewater using an autonomous
microfluidics-based analyser, World Acad. Sci. Eng. Technol. 52 (2009) 196–199.
2. R. Paul Payel, “Lab on a Chip” Systems for Environmental Analysis, University of Stavanger, 2014.
 Applications in Water Analysis

o Lab-on-a-chip technology is rapidly developing and being used in different industrial and research
fields.

o Most biological lab-on-a-chip devices are commercialized, while those for water analysis are still
developing.

o However, some lab-on-a-chip applications in water analysis are already established, such as pH
testing and detection of various chemicals (e.g., nitrates and nitrites, manganese, phosphates, and
silicates).

o For example, the microfluidic pH analysis uses sulfonephthalein as the main indicator.

o It includes the absorption cell, a static mixer, as well as a syringe pump and four valves attached to
the chip to regulate the flow.
 Ion Selective Electrodes (ISEs)

Ion Selective Electrodes can be regarded as electrochemical half cells consisting of a suitable
reference electrode/ reference solution system separated from the sample by a membrane. The
nature of the membrane determines the ions to which an electrode responds. When the electrode is
placed in solution, an electric potential is developed across the membrane, the magnitude of which
depends on the concentration of the ion to which the electrode responds. Measurement of this
potential is accompanied by means of suitable reference electrode and connecting the electrodes to
a high impedence mV meter.
With limited sample preparation when used in conjunction with an appropriate analyser, ISE
represent an economical and powerful means of analysing a wide range of substances.
Principle: An ideal I.S.E. consists of a thin membrane across which only the intended ion can be
transported. The transport of ions from a high conc. to a low one through a selective binding with
some sites within the membrane creates a potential difference.
 pH Electrode (Glass Membrane Electrode)
The pH glass electrode although somewhat mechanically
fragile, resists a variety of sample media and with the
exception of hydroxide is largely free from interferences.
Moreover, pH-sensitive glass electrodes form the basis of
many successful sensors for environmentally sensitive gases.
As illustrated in the Figure, these electrodes have thin
glass membrane fused to the end of a glass or plastic body.
The main body of the electrode contains an internal reference
electrode typically Ag/AgCl and is filled with a solution that is
usually the aqueous HCl of concentration around 1.0 mol/L

The pH electrode responds to hydrogen ions as a

result of the thin ion-exchange sites on the surface of a
hydrated glass membrane. The electrode consists of a thin
layer of glass, typically about 50 μm thick.
pH sensitive glasses are manufactured primarily from SiO2 which are connected via a tetrahedral network
with oxygen atoms bridging two silicon atoms. In addition, the glasses are made to contain varying amounts of other
metal oxides, like Na2O and CaO. Oxygen atoms within the lattice that are not bound to two silicon atoms possess a
negative charge, to which cations can ion pair. In this way, ions (primarily Na+) are able to diffuse slowly in the lattice,
moving from one charge pair site to another. While the membrane resistance is very high (~100 MΩ), this movement
of cations within the glass allows a potential to be measured across it.
If glasses of this type are placed in an aqueous solution
containing H+, the glass surface in contact with solution
becomes hydrated as water enters a short distance into
the crystal lattice and causes it to swell. The “interior” of
the glass remains dry. Some of the metal ions within the
glass close to the solution boundary are able to diffuse
into the solution, and some H+ ions are able to charge
pair with oxygen near the glass surface. In this way, ion
exchange equilibrium is established between the fixed
negative sites on the glass surface and H+, with an
increasing number of charge pairs with H+ occurring as its
activity in the contacting solution increases. This
equilibrium can be expressed by
H+/−O−Si−⇔H+ + −O−Si- (1)

A difference in the H activities on either side of the glass membrane leads to a difference in the number of ion pairs
+

that exist, and an imbalance in the surface charge between the hydrated layers. This results in a membrane
potential that is pH dependent, described according to the Nernst equation
Emembrane = Einner − Eouter = 0.0592log[(Ainner)/(Aouter)]

where E and E are the surface potentials on either side of the membrane, and
inner outer AinnerAinner and AouterAouter represent the
H activities of the inner and outer solutions, respectively.
+
 Applications of Ion-Selective Electrodes
Here are two common solid-state ion-selective electrodes where the active surface consists of a polished
crystal of lanthanum fluoride (LaF3) or silver sulfide (Ag2S). The electrode is sensitive toward either of the
ions that make up the crystal. While there is seldom interest in measuring the concentration of
lanthanum, fluoride is often added to municipal water supplies to reduce tooth decay. Fluoride selective
electrodes are easy to use on a sample by sample or continuous monitoring basis to insure that the
fluoride levels of the water are in the proper range. Similarly, there is usually not much need to measure
silver ion in solution but sulfide ion is indicative of the ability to form hydrogen sulfide (H2S), a toxic, foul-
smelling gas.
CHEMFET calcium probe- another example of a simple, mass producible, low cost sensor.
Diagnosis of Cystic Fibrosis using a Potentiometric Array- an example of a clinical application,and
the use of multiple sensors in a small, flow-through array. CF can be diagnosed based on elevatedlevels of
Na+, Cl+, and K+ in sweat.