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MODULE 1
1. VISCOSITY MEASUREMENT
General definition of viscosity: It is the resistance of a fluid (liquid or gas) to a change in shape,
or movement of neighboring portions relative to one another. Viscosity denotes opposition to
flow.

Viscosity is a measure of the flow characteristics of a

fluid. Imagine a plane of area A in a fluid shown in
the figure. It is moving with a velocity of V + dV. A
parallel plane in the fluid at a distance by dy from the
first plane is moving with a velocity of V so that the
relative velocity is dV. The change in velocity, dV, is
due to the shear stress τ caused by forces at the faces
exerted by adjacent solid surfaces or fluid.

Absolute or Dynamic Viscosity:

The shear stress divided by the rate of shear strain is constant for a given fluid at a fixed
temperature. This constant is called the dynamic, or absolute, viscosity and often simply the
viscosity.
𝑆ℎ𝑒𝑎𝑟 𝑠𝑡𝑟𝑒𝑠𝑠
Dynamic viscosity μ = 𝑉𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑔𝑟𝑎𝑑𝑖𝑒𝑛𝑡
= τ/(dV/dy)
= (F/A)/(dV/dy)
F = shearing force on area A; N
The SI unit for dynamic or absolute viscosity is Ns/m2. Before the introduction of SI unit, the
most commonly used unit for absolute or dynamic viscosity was poise
The value of viscosity decreases for liquids and increases for gases with increase in temperature.
The value of viscosity increases for liquids and decreases for gases with decrease in temperature
Kinetic viscosity:
Kinematic viscosity is the absolute viscosity of a fluid divided by its mass density. (Mass
density is the mass of a substance divided by its volume.) The dimensions of kinematic viscosity
are area divided by time; the unit in the SI system is meter squared per second(m2/s). The unit of
kinematic viscosity in the centimeter-gram-second (CGS) system, called the stokes in Britain and
the stoke in the U.S.
𝑑𝑦𝑛𝑎𝑚𝑖𝑐 𝑣𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦 μ
Kinematic viscosity ν = 𝑑𝑒𝑛𝑠𝑖𝑡𝑦
= ρ
Relative viscosity: It refers to the ratio of the viscosity of a polymer solution to the viscosity of
the solvent.
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1.1 Capillary viscometer:

In the capillary tube method,

the viscosity of a liquid is
calculated by measuring the
pressure difference for a given
length of the capillary tube.
This type of viscometer is
based on laminar flow through
a circular pipe.
It has a circular tube attached
horizontally to a vessel filled
with a liquid whose viscosity
has to be measured. Suitable
head (h f ) is provided to the
liquid so that it can flow freely
through the capillary tube of a certain length (L) into a collection tank as shown in figure. The
flow rate (Q) of the liquid having specific weight w l can be measured through the volume flow
rate in the tank.
The Hagen-Poiseuille equation for laminar flow can be applied to calculate the viscosity
(µ) of the liquid

1.2 Saybolt viscometer:

The Saybolt viscometer has a vertical

cylindrical chamber filled with liquid
whose viscosity is to be measured
(Figure). It is surrounded by a
constant temperature bath and a
capillary tube (length 12mm and
diameter 1.75mm) is attached
vertically at the bottom of the
chamber. For measurement of
viscosity, the stopper at the bottom of
the tube is removed and time for
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60ml of liquid to flow is noted which is named as Saybolt seconds.

For calculation purpose of kinematic viscosity (ν), the simplified expression is obtained
as below;

1.3 Redwood viscometer:

A Redwood viscometer works on

the same principle of Saybolt
viscometer. Here, the stopper is
replaced with an orifice and
Redwood seconds is defined for
collection of 50ml of liquid to
flow out of the orifice. Similar
expressions can be written for
Redwood viscometers. In
general, both the viscometers are
used to compare the viscosities
of different liquids. So, the value
of viscosity of the liquid may be
obtained by comparison with the
value of time for the liquid of
known viscosity.

1.4 Applications of Viscometer

Viscosity meters used mainly in the following sectors:

● Mineral oil industry (oils, hydrocarbon liquids).

● Food industry (sugar solutions, honey, beer, milk, gelatin, fruit juices).
● Chemical industry (polymer solutions, solvents, resin solutions, latex dispersions, and
adhesive solutions).
● Cosmetic/pharmaceutical industry (glycerin, emulsions, suspensions, solutions, extracts).
● Petroleum industry (crude, machine oil, petroleum).
● Related to fuels (petroleum, diesel oil).
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2. DENSITY AND SPECIFIC GRAVITY MEASUREMENT

Density:
Density is the most fundamental of all the physical properties. By measuring the density
of a process stream, one can determine its concentration, composition, and calorific values (in
the case of fuels). The density measurement is helpful for converting the mass flow rate and
volume flow rates vice versa.

Definition: The mass per unit volume of substance under fixed conditions.
ρ = 𝑚/𝑉
Where
Ρ = density of a substance
M = mass of a substance in kg
3
V = volume of the substance in 𝑚
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Most common units of density are kilogram/𝑚 (kg/𝑚 ) or gram/liter (g/l) or gram/milliliter
(g/ml).
The volume of the most of the substances changes with temperature, the density depends
on the temperature and pressure of a substance. Temperature and density are inversely
proportional.
In industrial application the density of substance is not always specified in the above
mentioned units, and the specific gravity is used widely.

Specific gravity (SG) or Relative density:

Definition: It is an abstract number expressing the ratio of the density of one substance to
density of another reference substance, both obtained at same temperature and pressure.

For solid and liquid the water is the reference number and for gases, air is the reference
SG (for liquid or solid) = Density of liquid (solid)/ density of water
SG (for gas) = Density of gas/Density of air
Purpose of Density measurement:
● To determine the mass and volume of products
● To access the quality of products
● To ascertain the value of of the products
● To determine the concentration or composition of a process stream
● To determine the calorific value of fuels
● To determine the volumetric flow measurements into mass flow information.

2.1 Hydrometer:
Principle of operation
Buoyancy principle: According to the Archimedes principle, when a body is immersed in
fluid, it loses weight equal to the weight of the liquid which is displaced.
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Construction:
Almost all hydrometers are made from high
grade glass tubing. The volume of fixed
mass is converted to linear distance by a
sealed bulb shaped glass tube containing a
long stem measurement scale, as shown in
the figure. The bulb is ballasted with a lead
shot and pitch, the mass of which is
dependent on the density range of the liquid
to be measured. The scale may be graduated
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in density units such as (kg/𝑚 ).

Working:
The constant - weight body element of the hydrometer is immersed in fluids with
differing densities, and will displace different volumes of fluid. The degree of stem scale
submersion is an indication of fluid density. Readings are made at the point where the stem
emerges from the liquid.
The accuracy of the measurement is a function of surface tension, turbulence, and sample
contamination.
2.2 Density measurement using LVDT
It is used for continuous monitoring of the density of a liquid.

Construction:
Uses a float weighed by a
chain to sink to a
predetermined depth in the
liquid under test flowing
through a glass chamber as
shown in figure. The float
carries the movable core of
LVDT. The windings of the
LVDT are wound around the
outside of the chamber (the
chamber is made of glass,
which is an insulating material,
does not interfere with the
transformer action)
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Working:
Under normal circumstances, the float is adjusted, so that the core of the LVDT is at null
position and thus the output voltage is zero. If the density of the liquid increases, float and core
level rises and vice versa, this causes a differential voltage across the output of the secondary
windings of LVDT. The magnitude of the voltage is proportional to the rise of the core from the
null position. The differential output voltage indicates the density. The more this density differs
from the normal, the greater is the magnitude of the output voltage. The phase of the output
voltage indicates whether the density is greater or lower than the normal.

2.3 Differential pressure method of density measurement :

A) Bubbler-reference column method
This method uses hydrostatic principle - 𝑃 = ρ𝑔ℎ

For a constant depth of the liquid, the force exerted by the liquid is proportional to
density. Air is pumped into two bubbler tubes which are immersed to equal depth in the test
liquid and reference liquid of known density. The pressure of air to each bubbler tube is
regulated so that it is a little higher than the column of liquids in which the tubes are immersed,
thus allowing air bubbles to be released slowly.
The pressure exerted by the two liquid columns are then compared, the pressure
difference is directly proportional to the density, so the manometer scale is calibrated in terms of
units of density being measured or liquid under test.
The hydrostatic balance for the system shown in figure is given by,
ρh = ρ𝑚ℎ𝑚 + ρ𝑟ℎ

Ρ= ( ρ𝑚ℎ𝑚
ℎ )
+ ρ𝑟
3
ρ𝑚 = density of manometric liquid ; kg/𝑚
3
ρ𝑟 = density of reference liquid ; kg/𝑚
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B) Single vessel air bubbler system

Figure shows the single-vessel air bubbler
system, it dispenses away the use of reference
liquid. Two bubbler tubes with a fixed distance
between their open ends are immersed in the
test liquid. Differential pressure is developed
on account of two factors:

1) Differential height which is known, and

2) Liquid specific gravity that determines
the liquid density. The indicated differential
pressure is a measure of the liquid density
2.4 Force Balance Method:

The liquid whose density is to be

measured flows through a tube loop of
the meter. The tube loop is suspended
from a pivoted beam carrying a weight
as shown in figure. The system is
balanced when the tube is full of sample
liquid. If a liquid of different density
from the sample liquid is passed, it
deflects the beam. The beam is
connected to a force balance system
which keeps the tube loop in balance
with the weight. This force in this
system is measured on an indicator
calibrated directly in terms of density.

3. pH Measurement
Many industrial processes require that the acidity or alkalinity of solution be measured
and controlled if the process is to produce effectively and efficiently. The degree of acidity or
alkalinity of aqueous solution is determined by the relative concentration of hydrogen and
hydroxyl ions in the solution.
When the hydrogen ion predominates the solution is acidic. Where the hydroxyl ions are
in the majority the solution is alkaline. Since the product of hydrogen ion and hydroxyl-ion
concentration in any such solution has a constant value, measurement of hydrogen ion
concentration indicates not only the acidity of a solution but its effective alkalinity as well.
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Definition: pH refers to potential of hydrogen ions concentration. Sorenson has defined pH of a

solution as the logarithm of the reciprocal of the hydrogen ions or hydronium ions concentration
[H3O+].
pH = -log10 (H+). Hydrogen ion concentration is measured on a scale called pH scale
The pH scale:

pH (potential hydrogen) is an easier way to measure the hydrogen ion concentration in a

solution, or how many hydrogen ions are present in a given liter.

Sorenson’s scale:
➔ Sørensen’s scale assigns a pH of 1 to 14, with 1 being the most acidic, 14 being the most
basic, and 7 being neutral (neither acidic or basic).
➔ The pH scale works in powers of ten, so each jump in number is a multiple of ten in
concentration. For example a pH of 1 is 10 times more acidic than pH 2.
➔ The value 7 at which the hydrogen and hydroxyl ion concentrations are about equal at
room temperature is referred to as the neutral point, or neutrality
Principle of pH measurement:
pH in a test solution is made by measuring the potential developed in an electrochemical
cell, consists of a measuring electrode and a reference electrode, both are immersed in the
solution under investigation, and connected to a measuring instrument, which measures the
electromotive force (emf) between these two electrodes are generated. The measuring electrode
is pH sensitive and its potential is proportional to the pH of the solution. The reference electrode
would always develop a constant electrical potential, against which the potential of the
measuring electrode.
Electrodes for pH measurements:
pH electrodes, which are analytical sensors, are used to measure the potential of
hydrogen (pH), or the negative logarithm of the hydrogen ion activity, in a solution.
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Reference Electrodes
A reference electrode is an electrode which has a stable electrode potential. These electrodes are
used to find out the potential of other electrodes. Reference electrodes are of two types. Primary
reference electrode and secondary reference electrode.

● Primary → SHE (Standard Hydrogen Electrode)

● Secondary → Calomel electrode, glass electrode,quinhydrone electrode
3.1 Standard Hydrogen electrode (SHE) or Hydrogen electrode:
It is the primary electrode to which all electrochemical measurements are referred.
However, owing to the experimental difficulties associated with it, other electrodes are
commonly employed for routine pH measurements. The performance of all other electrodes is
always evaluated in terms of the hydrogen electrode. The electrode can be represented as,

Pt/H2 (g), (1 atm)/ HCL (1M)

Construction:-
• It is a primary reference electrode.
• A small Pt plate coated with Pt black
is connected to a Pt wire which is sealed
in a glass jacket.
• Glass jacket having an inlet for
Hydrogen gas (1 atm pressure) at the top
and a number of small holes at the
bottom for the escape of Hydrogen gas.
• It is dipped in 1M HCl solution at
298K.
Working:- The electrode is immersed in
the solution under investigation and
electrolytic hydrogen gas at 1 atm
pressure is bubbled through the solution
and over the electrode, in such a way
that the electrode surface and the adjacent solution gets saturated with the gas at all times. The
potential set-up at the hydrogen electrode by a given activity of hydrogen ions is governed by the
Nernst equation:

SHE is a reversible electrode which can act as cathode or anode, depending on the potential of
the electrode to which it is coupled. The electrode potential of hydrogen electrodes is fixed as
zero volt. At the cathode, 2H+ + 2e−→H2(g) (reduction). At the anode, H2(g)→2H+ + 2e−
(oxidation)
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Since the hydrogen electrode is essentially a redox system and as such is affected by the
presence of oxidizing and reducing agents, it is therefore subject to a number of limitations in its
practical application by the difficulty in preparing and maintaining the electrode.
3.2 Calomel Electrode
Saturated calomel electrode is a secondary reference electrode. This is an example of metal-
metal insoluble metal salt electrode and solution of its common ion.
Construction:
• It consists of a glass tube in the bottom of which is
a layer of Hg.
• Over the Hg layer,there is a layer of solid
mercurous chloride. (Hg2Cl2)
• The remaining portion is filled with
normal,desinormal or saturated KCl
• A Pt wire is dipped into the Hg- layer and is used
for making electrical contact.
• The side tube is used for making contact with a salt
bridge.
Pt /Hg/𝐻𝑔2𝐶𝑙2/KCL/glass/Test H+solution
Working:
It can act as an anode or cathode depending on the
electrode potential of the coupled electrode.
• If it can act as anode,
2Hg+ 2Cl– →𝐻𝑔2𝐶𝑙2+2e-
Here the electrode potential of the coupled electrode is greater than the calomel electrode.
• If it can act as cathode, 𝐻𝑔2𝐶𝑙2+ 2e-→ 2Hg + 2Cl–
Here the electrode potential of the coupled electrode is less than that of calomel electrode.
• Depending up on the concentration of the KCl solution used, various values of electrode
potentials are reported.
Application:
● 1. Used for determination of electrode potential.
● 2. Used to find out pH of an unknown solution.
Limitations:
● 1. Toxic nature of mercury
● 2. cannot be used above 500c because the mercurous chloride breakdowns yielding an
unstable
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3.3 Glass electrode:

It is an iron selective secondary reference electrode for

measurement of pH

Construction:
● It is made up of a special type of glass with
relatively low melting point and high electrical
conductivity.
● Long glass tube with a thin glass bulb filled with
0.1M HCl.
● A Pt wire or silver wire coated with a layer of
AgCl is inserted into it to make electrical contact.
● Electrode representation is:
Ag/AgCl/0.1MHCl/glass/Test H+solution
or
Pt /AgCl/0.1MHCl/glass/Test H+solution

Working:
The H+ ion concentration inside the electrode is constant. When the electrode is immersed into a
test solution, the outer surface of the glass bulb comes in contact with the test solution. Glass
membrane acts as ion selective resin, equilibrium is set up between Na+ of glass and H+ ions.
Glass membrane - Na+ + H+→Glass membrane - H+ + Na+

Determination of pH by using glass electrode

Principle:
The H+ ion concentration inside the electrode is constant. When this electrode is dipped in to a
solution of unknown H+,it becomes sensitive to the outside concentration in the solution.
The potential difference is developed across the membrane. By measuring that potential
difference, we can find out pH.
Procedure
● Unknown solution is taken in beaker,
● Glass electrodes are dipped in it.
● It is connected to a saturated calomel electrode.
● emf of the cell is measured
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Advantage
● 1. It is simple and easily used.
● 2. Used in pH range 0 -12.
● 3. The results are accurate.
● 4. Can be used in presence of strong oxidizing and reducing agents.

Limitations
● 1. As the glass electrode has very high electrical resistance, an electronic potentiometer
must be used to find EMF.
● 2. Due to highly absorptive nature a lot of work is required.
3.4 Combined pH electrode (Combination electrode):
It consists of a pH-sensitive glass
electrode and the reference
electrodes are built together. The
internal reference electrode in the
glass electrode is identical with
the external reference electrode.
Both reference electrodes are the
Ag/AgCl type. The inner solutions
in the two parts of the electrode
are identical and they both are
symmetrical electrode chains. The
two Ag/AgCl reference electrodes are protected against light by means of ruby-red glass, which
absorbs light. The temperature range is from −10°C to +100°C as they have Ag/AgCl reference
electrodes. The measuring error due to small temperature differences of the buffer solutions and
the sample are negligible.
The gel format electrolyte utilizes a wick or diffusion style junction, allowing the sample
to diffuse in and the reference gel to diffuse out, causing a shift in potential. Some samples also
react with the silver ion in the gel, which forms a precipitate. Both of these processes can cause
clogging of the junction, as manifested in slower and less accurate response over time. To
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overcome this problem by providing a special micro-pore junction, consists of several small
pores in the actual body of the electrode which can be wiped clean each time the electrode is
rinsed. There is direct contact between the sample and the gel, thus resulting in faster readings.
The electrodes should never be stored dry. The preferred choice for storing is KCl
solution of any concentration between 2.0 M to 3.8 M or buffer solution with pH4. Soak the
electrode in KCl solution after cleaning and prior to use or calibration, if it is necessary to clean
the probe with acid, caustic, solvent or other cleaning solution. This will re-condition the bulb
and reference, extending the probe life and improving calibration accuracy. These are commonly
used with portable pH meters.
3.5 Digital pH meter:

Operational amplifiers with FETinput stage are available in the integrated form. They can
be directly coupled to the electrode to amplify signals from the pH cell. Digital display offers
better resolution and readings without any ambiguity. Figure shows the block diagram of the
digital pH meter. It consist of following main parts:
Input Circuit: The input circuit is a FET input operational amplifier, which offers a very high
input impedance. It incorporates asymmetry control for electrode zeroing, followed by a
unipolarity circuit which provides a positive output voltage, irrespective of the polarity of the
input voltage. The buffer amplifier provides further gain, so that the pH value can be displayed
directly on an analog meter if desired. It also incorporates temperature compensation control.
A-D Converter: The analog-to-digital converter consists of a switch, an integrator, comparator
and highly stabilized voltage reference. A-D conversion is achieved using dual slope technique.
Integrator uses an operational amplifier having a capacitor in the feedback circuit. The A-D
converter converts the analog signal to digital form the input circuit section, which is
proportional to the measured pH value.
Control and Display Circuit: This part consists of reset, transfer polarity control, 20 kHz clock,
bidirectional counters, latches, decoder driver and display devices. It would display a pH of 7
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corresponding to zero signal from the neutral solution. As such the bidirectional counters are
used to have both forward and reverse counting. The control circuit mainly does two functions,
resetting the counter and counter starts count forward & reverse if the pH is greater than 7 and
less than 7 respectively