Analytical Instruments

10/31/2018
ANALYTICAL
INSTRUMENTATION
RAJESH KUMAR, ASSITANT PROFESSOR, EED
Gas Chromatography
Chromatography is a method used to separate and/or analyze complex mixture.
It involves a sample being vaporized and injected onto the head of the chromatographic column.
The sample is transported through the column by the flow of inert, gaseous mobile phase. The
column itself contains a liquid stationary phase which is adsorbed onto the surface of an inert
solid.
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How Does Chromatography Work

In all chromatographic separations, the sample is transported in a mobile phase. The mobile
phase can be a gas, a liquid, or a supercritical fluid.
The mobile phase is then forced through a stationary phase held in a column or on a solid
surface. The stationary phase needs to be something that does not react with the mobile phase
or the sample.
The sample then has the opportunity to interact with the stationary phase as it moves past it.
Samples that interact greatly, then appear to move more slowly. Samples that interact weakly,
then appear to move more quickly. Because of this difference in rates, the samples can then be
separated into their components.
GC Theory
An inert gas such as helium is passed through the column as a carrier gas and is the moving
phase. A sample is injected into a port which is much hotter than the column and is vaporized.
The gaseous sample mixes with the helium gas and begins to travel with the carrier gas through
the column. As the different compounds in the sample have varying solubility in the column
liquid and as these compounds cool a bit, they are deposited on the column support. However, the
column is still hot enough to vaporize the compounds and they will do so but at different rates
since they have different boiling points. The process is repeated many, many times along the
column. Eventually the components of the injected sample are separated and come off of the
column at different times (called "retention times").
There is a detector at the end of the column which signals the change in the nature of the gas
flowing out of the column. Recall that helium is the carrier gas and will have a specific thermal
conductivity, for example. Other compounds have their own thermal conductivities. The elution
of a compound other than helium will cause a change in conductivity and that change is converted
to an electrical signal. The detector, in turn, sends a signal to a strip chart recorder or to a
computer. Detectors come in several varieties, for example, thermal detectors, flame-ionization
and electron capture detectors.
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GC Instrumentation
Carrier gas
- He (common), N2, H2, Argon
Sample injection port
- micro syringe
 Columns
 Detectors
◦ Thermal conductivity (TCD)
◦ Flame photometric (FPD)
◦ Electron capture detector(ECD)
◦ Flame Ionization detector (FID)
Carrier gas
The cylinder/ gas tank is fitted with a pressure controller to control the pressure of gas, a pressure
gauge that indicates the pressure, a molecular sieve to transfer filtered dry gas and a flow
regulator to ensure a constant rate of flow of mobile phase to the column.
It should meet the following criteria:
Should be chemically inert
Should be cheap and readily available
Should be of high quality and not cause any fire accidents
Should give best possible results
Should be suitable for the sample to be analyzed and for the detector
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Column unit
Columns are of different shapes and sizes that includes: “U” tube type or coiled helix type.
They are mainly made of copper, stainless steel, aluminium, Glass, nylon and other synthetic
plastics.
Support material:-
it’s main function is to provide mechanical support to the liquid phase. An ideal support should
have a large surface area, chemically inert, should get uniformly wet with liquid phase, should be
thermostable.
Commonly used solid phases are: diatomaceous earth or kieselguhr, glass beads, porous
polymers, sand,etc.
Liquid phase:-
It should have the following requirements:
It should be non-volatile
Should have high decomposition temperature
Should be chemically inert
Should posses low vapour pressure at column temperature
Should be chemically and structurally similar to that of the solute i.e., polar for polar solute.
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Types of columns
There are two general types of columns:
1. Packed columns:- In GLC, they are densely packed with finely divided, inert, solid support
material
( diatomaceous earth) coated with liquid stationary phase.
In GSC, the columns are packed with adsorbents or porous polymers.
Length- 1.5 - 10m
internal diameter- 2 - 4mm.
2. Capillary columns-
length ranges from 10-100m
inner diameter is usually 0.1-0.5mm.
Capillary columns
It is mainly of two types:
Wall-coated columns - consist of a capillary tube whose walls are coated with
liquid stationary phase.
Support-coated columns- the inner wall of the capillary is lined with a thin
layer of support material such as diatomaceous earth, onto which the stationary
phase has been adsorbed. It is also known as PLOT (porous-layer open tubular
columns).
SCOT columns are generally less efficient than WCOT columns. Both types of
capillary column are more efficient than packed columns.
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Thermostatically controlled oven

Temperature maintenance in a column is highly essential for
efficient separation.
Detectors
There are many detectors which can be used in gas chromatography. Different detectors will give
different types of selectivity.
The eluted solute particles along with the carrier gas exit from the column and enter the detector.
 The detector then produces electrical signals proportional to the concentration of the
components of solute.
 The signals are amplified and recorded as peaks at intervals on the chromatograph.
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Thermal conductivity detector

Senses the changes in the thermal conductivity of the column effluent with reference to a flow of
carrier gas.
It is based upon the alteration of the thermal conductivity of the carrier gas in the presence of an
organic compound. The platinum wires are heated electrically and assume equilibrium conditions
of temperature and resistance when carrier gas alone passes over them. They are mounted in a
whetstone bridge arrangement and when a compound emerges, the thermal conductivity of the
gas surrounding wire alters, and hence the temperature and resistance of the wire change with a
concomitant out of balance signal which is amplified and recorded.
• Advantages :-
Simple and inexpensive
Durable and posses long life
Accurate results
Non-selective, hence known as universal detectors
• Disadvantages:-
Low sensitivity
Affected by fluctuations in temperature and flow rate.
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Flame Ionization Detector (FID)

This employs hydrogen flame that is maintained in a small cylindrical jet made up of platinum or
quartz.
Effluent from the column with helium or nitrogen as carrier gas are fed into the hydrogen
flame, gets ignited and undergoes pyrolysis to produce ions.
For detection of these ions, two electrodes are used that provide a potential difference.
The ions produced are repelled by the positive electrode which hit the collector plate. The
current produced in doing so is amplified and fed to an appropriate recorder.
Flame photometric detector

It is a selective detector that is responsive to compounds containing sulphur or
phosphorous
The detection principle is the formation of excited sulphur (S2*) and excited
hydrogen phosphorous oxide species (HPO*) in a reducing flame.
A photomultiplier tube measures the characteristic chemiluminescent emission
from these species. The optical filter can be changed to allow the photomultiplier
to view light of 394 nm for sulphur measurement or 526 nm for phosphorus.
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Electron capture detector

Molecules of compounds, which posses affinity for electrons, differ in their electron absorbing
capacities. This difference is utilized in this detector for identification of the compounds.
Working- A foil made up of a radioactive metal like Ni63 (β- emitter) is placed inside a Teflon
coated cell which also contains a cathode and an anode.
In the absence of organic species, the produced electrons migrate towards positive electrode
and produce a certain constant standing current.
When a sample/eluent is present it captures the electrons, elutes from column, there is a drop in
this constant current.
The potential across two electrodes is adjusted to collect all the ions and a steady saturation
current, is therefore, recorded.
pH Measurement
pH is a method of measurement of hydrogen ion concentration.
pH is a negative logarithmic measurement of the number of moles of hydrogen ions (H+) per litre
of solution.
In pure water, hydrogen ion concentration is 10-7 moles per liter under standard conditions
(25°C), giving it a pH of 7.
The pH scale ranges between 0 and 14. Any acid fully ionizing in water gives a pH of 0.
Acidity describes higher concentration of hydrogen ions and reads below pH 7. Alkali or base
fully ionized in water reads pH 14.0. Alkalinity ranges between 7 and 14, excluding 7 as it depicts
pure water as a neutral solution.
As pH is measured on a logarithmic scale, one unit increase of pH corresponds to a decrease in
concentration by a factor of 10. For example, the concentration of hydrogen ions for pH 3 is 10
times greater than that of pH 4.
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The pH value is expressed as
Why is pH measured
Measurement of pH of a solution is necessary to judge whether the liquid is acidic, alkaline or
neutral.
The application areas are food, beverage industry, aquarium, agriculture and gardening and colour
photography, etc.
The measurement of pH of liquid is necessary in many condensate systems as a check on
corrosion, in pharmaceuticals and drug production for maximum yield
In food manufacture to reduce the spoilage and improves the taste and in innumerable chemical
processes
The continuous monitoring of blood pH is essential for the proper treatment of the patients
suffering from metabolic and respiratory problems,
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Measurement of pH
When very precise and accurate pH measurement is not required, litmus papers that change color
on coming in contact with solutions of certain pH values are used. But continuous and process
measurement demands more sophisticated measurement techniques.
Essentially two electrodes, measuring and reference electrodes are employed for its measurement
 Both these electrodes are dipped in the solution whose pH is to be measured
 These two electrodes form two half-cells and the total potential generated is the difference
between these two electrodes separately produced in each one of them.
Measuring Electrodes
Measuring electrodes of specific make (thin ion selective glass) having buffer solution of
constant H+ ion concentration and silver wire inside the glass bulb is dipped in the unknown
solution where a potential is generated across the glass bulb.
It forms one of the two half-cells. The measurement electrode’s purpose is to generate the
voltage used to measure the solution’s pH.
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Reference Electrodes
The reference electrode provides continuity to the electric circuit as one half-cell is unable to
measure the potential generated.
The reference electrodes are commonly of two types i)Calomel(Mercury–Mercurous Chloride)
and ii) Silver–Silver Chloride electrode.
The two sets of silver wires coming out from both the measuring electrode and reference
electrode complete the circuit measuring the potential generaed.
The reference electrode consists of a chemical solution of neutral (7)pH buffer solution (usually
potassium chloride) allowing exchange of ions with the process solution through a porous
separator.
The reference electrode’s purpose is to provide the stable, zero- voltage connection to the liquid
solution so that a complete circuit can be made to measure the glass electrode’s voltage and the
electrical connection is maintained through a salt bridge.
Viscosity
Viscosity is the measure of the internal friction of a fluid.
 This friction becomes apparent when a layer of fluid is made to move in relation to another layer.
The greater the friction, the greater the amount of force required to cause this movement, which is
called shear.
 Shearing occurs whenever the fluid is physically moved or distributed, as in pouring, spreading,
spraying, mixing, etc. Highly viscous fluids, therefore, require more force to move than less
viscous materials.
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We generally measures two types of viscosity :

1. Absolute/ Dynamic Viscosity (ƞ)
2. Kinematic Viscosity (ν)
Dynamic (or Absolute) Viscosity:
η= F/ [A×(u/h)]
η= τ /(u/h) N-s/m²
Kinematic Viscosity :
It is defined as the ratio of absolute viscosity to the density of fluid.
ν= η/ρ m²/s ; ρ= density of fluid
Isaac Newton defined viscosity by considering the model represented in the figure below.
Two parallel planes of fluid of equal area A are separated by a distance dx and are moving in the
same direction at different velocities V1 and V2.
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Newton assumed that the force required to maintain this difference in speed was
proportional to the difference in speed through the liquid, or the velocity
gradient. To express this, Newton wrote:
• where Ƞ is a constant for a given material and is called its viscosity.
The velocity gradient, dv/dx , is a measure of the change in speed at which the
intermediate layers move with respect to each other. It describes the shearing the
liquid experiences and is thus called shear rate.
• The term F/A indicates the force per unit area required to produce the shearing
action. It is referred to as shear stress.
• So, mathematically Viscosity can be defines as
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Why should I measure Viscosity?

• From viscosity measurement, we can obtain much useful behavioral and predictive information
for various products.
• A frequent reason for the measurement of rheological properties can be found in the area of
quality control, where raw materials must be consistent from batch to batch.
• For this purpose, flow behavior is an indirect measure of product consistency and quality.
Newtonian fluids
• This type of flow behavior Newton assumed
for all fluids is called Newtonian.
• It is, however, only one of several types of
flow behavior you may encounter.
• Graph A shows that the relationship between
shear stress and shear rate is a straight line.
• Graph B shows that the fluid's viscosity
remains constant as the shear rate is varied.
• Typical Newtonian fluids include water and
thin motor oils.
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Non Newtonian fluids

• A non-Newtonian fluid is broadly defined as one for which the relationship is not a
constant.
• It means that there is non-linear relationship between shear rate & shear stress.
• In other words, when the shear rate is varied, the shear stress doesn't vary in the same proportion
(or even necessarily in the same direction).
• E.g. Soap Solutions & cosmetics, Food such as butter, jam, cheese, soup, yogurt, natural
substances such as lava, gums, etc.
Capillary Viscometer
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Rotational Viscometer
• Though gravity is available everywhere for free, it is sometimes not strong enough as a driving
force.
• For highly viscous fluids a measurement based on gravity would take far too long.
• Therefore, rotational viscometers use a motor drive. Unlike capillary viscometers, rotational
viscometers provide dynamic or shear viscosity results.
• A rotational viscometer consists of a sample-filled cup and a measuring bob that is immersed
into the sample.
There are two main principles in use:
• The Couette Principle
• The Searle Principle
The Couette Principle

If the bob stands still and the drive rotates the sample cup, this is the Couette principle (named
after M. M. A. Couette, 1858 to 1943). Although this construction avoids problems with turbulent
flow, it is rarely used in commercially available instruments. This is probably due to problems
with the insulation and tightness of the rotating sample cup.
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The Searle Principle

In most industrially available viscometers the motor drives the measuring bob and the sample cup stands still. The
viscosity is proportional to the motor torque that is required for turning the measuring bob against the fluid’s viscous
forces. This is called the Searle principle (named after G. F. C. Searle, 1864 to 1954).
When employing the Searle principle, the bob's rotational speed in low-viscosity samples should not be too high.
Otherwise turbulent flow could occur due to centrifugal forces or the effects of inertia.
The motor turns a measuring bob or spindle in
a container filled with sample fluid. While the
driving speed is preset, the torque required for
turning the measuring bob against the fluid’s
viscous forces is measured.
Density
Density is a characteristic property of a substance. Density is the most fundamental of all the physical
properties. It applies to substance in any of the three states namely solid, liquid, or gas.
The density of a substance is the relationship between the mass of the substance and how much space it
takes up (volume).
Density ρ of a material is defined as the mass per unit volume. Units of density are pounds kilogram
per cubic meter (kg/m3).
Density is the measure of the “compactness” of a material
All substances have density including liquids, solids, and gases
Specific weight γ is defined as the weight per unit volume of a material newton per cubic meter
(N/m3). Specific gravity (SG) of a liquid or solid is defined as the density of the material divided by
the density of water or the specific weight of the material divided by the specific weight of water at a
specified temperature.
The relation between density and specific weight is given by γ=ρg
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By measuring the density of a process stream, one can determine its concentration, composition,
or in the case of fuels, one can identify its calorific value. Density measurement is also necessary
to convert volumetric flow into mass flow.
Hydrometers
Hydrometers are the simplest device for
measuring the specific weight or density of a
liquid. The device consists of a graduated glass
tube, with a weight at one end, which causes
the device to float in an upright position. The
device sinks in a liquid until an equilibrium
point between its weight and buoyancy is
reached. The specific weight or density can
then be read directly from the graduations on
the tube. Such a device is shown in
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Thermo hydrometer
Thermo hydrometer is a combination of hydrometer and thermometer, so that both the specific
weight/density and temperature can be recorded and the specific weight/density corrected from
lookup tables for temperature variations to improve the accuracy of the readings.
Induction hydrometers
Induction hydrometers are used to convert the
specific weight or density of a liquid into an
electrical signal. In this case, a fixed volume of
liquid set by the overflow tube is used in the
type of setup shown in Figure, the
displacement device, or hydrometer, has a soft
iron or similar metal core attached. The core is
positioned in a coil which forms part of a
bridge circuit. As the density/specific weight of
the liquid changes, the buoyant force on the
displacement device changes. This movement
can be measured by the coil and converted into
a density reading.
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Vibration sensors
Vibration sensors are an alternate method of
measuring the density of a fluid. Fluid is
passed through a U tube which has a flexible
mount so that it can vibrate when driven from
an outside source. The amplitude of the
vibration decreases as the specific weight or
density of the fluid increases, so that by
measuring the vibration amplitude the specific
weight/density can be calculated.
Differential bubblers
Differential bubblers can be used to measure
liquid density or specific weight. Figure shows
the setup using a bubbler system. Two air
supplies are used to supply two tubes whose
ends are at different depths in a liquid, the
difference in air pressures between the two air
supplies is directly related to the density of the
liquid by the following equation:
where Δp is the difference in the pressures and

Δh the difference in the height of the bottoms
of the two tubes
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Refractive index
The refractive index or index of refraction of a substance is a measure of the speed of light in that
substance. It is expressed as a ratio of the speed of light in vacuum relative to that in the
considered medium.
A simplified, mathematical description of refractive index is:
n = velocity of light in a vacuum / velocity of light in
medium
Hence, the refractive index of water is 1.33, meaning that
light travels 1.33 times as fast in a vacuum than it does in
water.
Why Refractive index is Important

• The refractive index of a material medium is an important optical parameter
since it exhibits the optical properties of the material.
• Its values are often required to interpret various types of spectroscopic data.
• It is used to calculate the focusing power of lenses, and the dispersive power of
prisms.
• The refractive index coefficients are important parameters in the design of a
solid state laser.
• The adulteration problem is increasing day by day and hence simple,
automatic and accurate measurement of the refractive index of materials is of
great importance these days.
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Refraction is the bending of light when the light passes from one medium to another
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10/31/2018

How Does Chromatography Work

Thermostatically controlled oven

Thermal conductivity detector

Flame Ionization Detector (FID)

Flame photometric detector

Electron capture detector

The pH value is expressed as

We generally measures two types of viscosity :

• where Ƞ is a constant for a given material and is called its viscosity.

Why should I measure Viscosity?

Non Newtonian fluids

The Couette Principle

The Searle Principle

where Δp is the difference in the pressures and

Why Refractive index is Important

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