PROCESS INSTRUMENTATION

CHE 426
DR. FAHAD REHMAN
CLOS COVERED

• CLO 1: DISCUSS THE FUNDAMENTALS OF PROCESS INSTRUMENTATION

• CLO2 : SELECTION OF APPROPRIATE INSTRUMENT ACCORDING TO PROCESS REQUIREMENT

• COURSE CONTENTS
• INSTRUMENTATION FOR CONCENTRATION MEASUREMENT OF LIQUID AND GASES.
RATIONALE

• IT’S THE CORE OF WHAT IS WE DO IN INDUSTRY

• HOW WOULD WE KNOW THE PRODUCT HAS BEEN PRODUCED?
• QUALITATIVE ANALYSIS
• QUANTITATIVE ANALYSIS
• NH3, H2SO4, H2, HYDROCAROBS, PETROCHEMICALS- EACH PRODUCT PRODUCED MUST
ANALYZED QUALITATIVELY AND QUANTITATIVELY.
ANALYZERS

• THERE ARE SEVERAL TYPES OF ANALYZERS;

• GC (MS/TCD/FID), HPLC, TLC, IR (FTIR, NIR), UV-VIS SPECTROMETER FOR QUALITATIVE AND
QUANTITATIVE ANALYSIS OF MOST LIQUID AND GASEOUS PRODUCTS
• XRD FOR MATERIAL (POWDER AND PASTE) CHARACTERIZATION
• AAS FOR DETERMINATION OF HEAVY METALS IN WATER AND WASTEWATER
• CHNS ANALYZER- ELEMENTALS ANALYZER FOR COAL, BIOMASS ETC,
• GAS ANALYZER-NH3, CO2, CO, H2, SYN GAS ANALYZER
• TITRATION
• BET- SURFACE AREA ANALYSIS
• TGA-FOR THERMOGRAVEMTIRC ANALYSIS
• XPS, SEM, TEM, AFM, ICPMS AND SO MANY MORE………….
 SPECTROSCOPY

SPECTROSCOPY IS THE MEASUREMENT AND INTERPRETATION OF

ELECTROMAGNETIC RADIATION ABSORBED OR EMITTED WHEN THE
MOLECULES OR ATOMS OR IONS OF A SAMPLE MOVES FROM ONE
ENERGY STATE TO ANOTHER ENERGY STATE
 TYPES

• 1) ATOMIC SPECTROSCOPY :
THE CHANGES IN ENERGY TAKES PLACE AT ATOMIC LEVEL FOR EXAMPLE ATOMIC ABSORPTION
SPECTROSCOPY, FLAME PHOTOMETRY, OPTICAL EMISSION SPECTROSCOPY (OES)
• 2)MOLECULAR SPECTROSCOPY :
THE CHANGES IN ENERGY TAKES PLACE AT MOLECULAR LEVEL. FOR EXAMPLE UV SPECTROSCOPY,
COLORIMETRY, INFRA RED SPECTROSCOPY
 ABSORPTION SPECTROPHOTOMETRY

• ABSORPTION SPECTROPHOTOMETRY CAN BE DEFINED AS THE MEASUREMENT OF ABSORPTION

OF RADIANT ENERGY BY VARIOUS SUBSTANCES.

• IT INVOLVES THE MEASUREMENT OF ABSORPTIVE CAPACITY FOR RADIANT ENERGY IN THE

VISIBLE, UV AND IR REGIONS (FTIR, NIR) OF THE SPECTRUM.
 UV-VIS SPECTROSCOPY
• UV SPECTROSCOPY IS CONCERNED WITH THE STUDY OF ABSORPTION OF UV RADIATION WHICH
RANGES FROM 200-400NM. VISIBLE 400-800/900 NM
• VALENCE ELECTRONS ABSORB THE ENERGY THEREBY MOLECULES UNDERGOES TRANSITION
FROM GROUND STATE TO EXCITED STATE.
• THIS ABSORPTION IS CHARACTERISTIC AND DEPENDS ON THE NATURE OF ELECTRONS PRESENT.
• TYPES OF ELECTRONS
• Σ ELECTRONS: IN SATURATED COMPOUNDS
• Π ELECTRONS: IN UNSATURATED COMPOUNDS
• N ELECTRONS: IN NON BONDED ELECTRONS
 UV-VIS SPECTROSCOPY

• TO MEASURE CONCENTRATION OF SOLUTION

• QUANTITATE ANALYSIS
• SIMPLE, FAST AND INEXPENSIVE
• APPLIED TO
• WATER TREATMENT ANALYSIS – DYE REMOVAL, PHARMACEUTICAL WASTE,
PETROCHEMICALS SUCH AS PHENOLS, TOLUENE ETC.,
• BIOLOGICAL PROCESSES-ALGAL PROCESSING-GROWTH
• FOOD PROCESSING
• AND MANY MORE
 UV-VIS -WHAT CAN BE ANALYZED

• SOLUTES THAT CAN BE DISSOLVED IN SOLVENTS LIKE WATER, ETHANOL AND HEXANE

• SOLUTES THAT ABSORB UV OR VISIBLE LIGHT

• QUANTITATIVE MEASUREMENTS WITH A SINGLE SOLUTE IN THE SOLUTION OR MORE IF THEY

DO NOT INTERFERE.
WORKING PRINCIPLE

• IN UV-VIS, A BEAM WITH A WAVELENGTH VARYING

BETWEEN 180NM-1100NM PASSES THROUGH A
SOLUTION IN A CUVETTE.

• THE SAMPLE IN THE CUVETTE ABSORBS THIS UV OR

VISIBLE RADIATION.

• I₀ IS THE RADIATION COMING IN AND I IS THE

RADIATION COMING OUT
THE AMOUNT OF LIGHT THAT IS ABSORBED BY THE SOLUTION DEPENDS ON:
• THE CONCENTRATION
• THE PATH LENGTH OF THE LIGHT THROUGH THE CUVETTE
• HOW WELL THE ANALYTE LIGHT ABSORBS AT A CERTAIN WAVELENGTH
The relation of absorbance to concentration is given by lambert-Beer’s law (Beer’s Law):

A=ɛlc
Absorbance Epsilon Path Length Concentration of
analyte
Molar absorption coefficient of the
analyte for a certain wavelength
CALIBRATION CURVE
0.3

Sr. Conc . (mg/l) Absorbance 0.25 y = 19199x - 0.0024

R² = 0.9982
No. (a.u)

Absorbance (a.u)
1 10 0.1 0.2

2 20 0.2
3 30 0.3 0.15

4 40 0.4
0.1
5 50 0.5
6 60 0.6
0.05

7 70 0.7
0
0.00E+00 2.00E-06 4.00E-06 6.00E-06 8.00E-06 1.00E-05 1.20E-05 1.40E-05
Concentration (mol/dm3)
UV-VIS SPECTROPHOTOMETER
MONOBEAM SPECTROPHOTOMETER
DOUBLE BEAM SPECTROPHOTOMETER
DEVIATIONS FROM BEER-LAMBERT’S LAW
 DEVIATIONS

Dissociation of molecules
This can be explained by the fact that dichromate ions posses their maximum
absorbance at 450nm which is orange in colour .But upon dilution, it will be
dissociated to chromate ions having maximum absorbance at 410nm which is
yellow in colour.

This law is not valid in case if the absorbing material coagulated into a small
number of large units.

This law shows deviation if the absorbing material at the required wavelength
contains presence of impurities.
 DEVIATIONS
This law is not applicable in case of suspension.

INSTRUMENTAL DEVIATIONS:
Strict adherence of an absorbing system to this law is observed only
when the radiation used is monochromatic.

Stray radiation, slit width also causes deviation.

Hence, the reasons for the deviation depends on environment such as

temperature, pressure, solvent, refractive index of the sample
ADVANTAGES & DISADVANTAGES

• ANALYZE SUBSTANCES QUICKLY AND THEY ARE NOT DIFFICULT TO USE

• UV-VIS SPECTROMETERS BRING HIGH-TECH SPECTRAL ANALYSIS TO THE FOOD INDUSTRY, WHERE THEY
HELP LABORATORY TECHNICIANS STUDY FOOD PRODUCTS
• THESE DEVICES ARE USED IN FIELDS AS DIVERSE AS FORENSIC ANALYSIS, RESEARCH AND MEDICINE
• DUST OR GRIM MAY COAT THE MIRRORS IN A DOUBLE-BEAM UV-VIS SPECTROMETER, THE DEVICE'S
PERFORMANCE WILL DEGRADE
• REPAIR COSTS CAN ALSO DOUBLE BECAUSE YOU CAN'T REPLACE ONE MIRROR IF IT NEEDS FIXING.
BECAUSE THEY WORK AS A PAIR, YOU MUST REPLACE BOTH MIRRORS.
• STRAY LIGHT CAUSED BY FAULTY EQUIPMENT DESIGN AND OTHER FACTORS COULD DECREASE AN
INSTRUMENT'S LINEARITY RANGE AND REDUCE THE ABSORBENCY OF THE SUBSTANCE IT MEASURES
• ELECTRONIC COMPONENTS IN THE SPECTROMETER OR SAMPLE SOURCE MAY ALSO GENERATE NOISE THAT
DECREASES MEASUREMENT ACCURACY AND REDUCES THE DEVICE'S SENSITIVITY.
 INFRARED SPECTROSCOPY

 The primary source of infrared radiation is thermal radiation (heat).

 All object radiates in the infrared. Even an ice cube, emits infrared.

 It is the radiation produced by the motion of atoms and molecules in an object. The
higher the temperature, the more the atoms and molecules move and the more
infrared radiation they produce.
 INFRARED SPECTROSCOPY

• INFRARED RADIATION STIMULATES MOLECULAR VIBRATIONS.

• INFRARED SPECTRA ARE TRADITIONALLY DISPLAYED AS %T (PERCENT TRANSMITTANCE) VERSUS
WAVE NUMBER (4000-400 CM-1).
• FTIR SPECTROSCOPY
• NIR SPECTROSCOPY
• USEFUL IN IDENTIFYING PRESENCE OR ABSENCE OF FUNCTIONAL GROUPS.
• TO SEE IF A CHANGE IS PHYSICAL OR CHEMICAL IN NATURE
FOURIER TRANSFORM INFRA-RED (FTIR)
SPECTROSCOPY
 FTIR SPECTROSCOPY
 FT-IR stands for Fourier Transform Infrared, the preferred method of
infrared spectroscopy. In infrared spectroscopy, IR radiation is passed
through a sample. Some of the infrared radiation is absorbed by the
sample and some of it is passed through (transmitted).

 The resulting spectrum represents the molecular absorption and

transmission, creating a molecular fingerprint of the sample.

 Like a fingerprint no two unique molecular structures produce the same

infrared spectrum. This makes infrared spectroscopy useful for several
types of analysis.
 FTIR SPECTROSCOPY

According to Principle of IR, Molecular Vibration takes place as a result

of Absorption of IR radiation when –

Applied Infrared Frequency = Natural frequency of vibration

Every bond or functional groups requires different frequency

for Absorption. Hence characteristics Peak is observed for
every functional group or part of the molecule.
 FTIR/INFRARED SPECTROSCOPY

WHAT IS A VIBRATION IN A MOLECULE?

• ANY CHANGE IN SHAPE OF THE MOLECULE- STRETCHING OF BONDS, BENDING OF
BONDS, OR INTERNAL ROTATION AROUND SINGLE BONDS

WHAT VIBRATIONS CHANGE THE DIPOLE MOMENT OF A MOLECULE?

• ASYMMETRICAL STRETCHING/BENDING AND INTERNAL ROTATION CHANGE THE
DIPOLE MOMENT OF A MOLECULE. ASYMMETRICAL STRETCHING/BENDING ARE IR
ACTIVE.
 FTIR/INFRARED SPECTROSCOPY

H H H H H H

C C C

H H H H H H

Asymmetrical Symmetrical Bending or scissoring

stretching stretching

H H H H H H

C C C

H H H H H H

Rocking or in Twisting or out- Wagging or

plane bending of-plane out-of-plane
bending bending
 FTIR/INFRARED SPECTROSCOPY

• ONLY VIBRATIONS THAT CAUSE A CHANGE IN ‘POLARITY’ GIVE RISE TO

BANDS IN IR SPECTRA – WHICH OF THE VIBRATIONS FOR CO2 ARE INFRARED
ACTIVE?

Symmetric stretch
Asymmetric stretch

Bending (doubly
degenerate)
 INFRARED SPECTROSCOPY
• IN GENERAL

4000-3000 3000-2000 2000-1500 1500-1000

cm-1 cm-1 cm-1 cm-1

O-H CC C=C C-O

N-H CN C=O C-F
C-H C-Cl
deformations
 INFRARED SPECTROSCOPY

Aspirin (acetylsalicylic acid)

120

100

80
%T

60

40

20

0
4000 3500 3000 2500 2000 1500 1000 500

wavenumber/ cm-1
 INFRARED SPECTROSCOPY

• HUMAN BREATH

100

80

60
%T

40

20

0
4000 3500 3000 2500 2000 1500 1000 500
wavenumber/cm -1
INFRARED SPECTROSCOPY
 FTIR/INFRARED SPECTROSCOPY

Fourier transform infrared spectroscopy is preferred over dispersive

or filter methods of infrared spectral analysis for several reasons:
• It is a non-destructive technique.
• It provides a precise measurement method which
requires no external calibration.
• It can increase speed, collecting a scan every second.
• It can increase sensitivity.
• It has greater optical throughput.
• It is mechanically simple with only one moving part.
• SAMPLING TECHNIQUES
• 1.LIQUID SAMPLES:
• NEAT SAMPLE
• DILUTED SOLUTION
• LIQUID CELL

• 2.SOLID SAMPLES:
• NEAT SAMPLE
• CAST FILMS
• PRESSED FILMS
• KBR PELLETS

• 3.GAS SAMPLES:
• SHORT PATH CELL
• LONG PATH CELL