PROCESS INSTRUMENTATION

CHE 426
DR. MARIA
CLOS COVERED

• CLO 1: DISCUSS THE FUNDAMENTALS OF PROCESS INSTRUMENTATION

• CLOS: SELECTION OF APPROPRIATE INSTRUMENT ACCORDING TO PROCESS REQUIREMENT

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

Mikhail Tswett invented chromatography in 1901

during his research on plant pigments.
He used the technique to separate various plant
pigments such as chlorophylls, xanthophylls and
carotenoids.

Mikhail Tswett
Russian Botanist
(1872-1919)
Chromatography: (Greek = chroma “color” and
graphein “writing” ) Tswett named this new technique
chromatography based on the fact that it separated the
components of a solution by color.
Common Types of Chromatography
Tswett’s technique is based on Liquid Chromatography.
There are now several common chromatographic
methods. These include:
Paper Chromatography
Thin Layer Chromatography (TLC)
Liquid Chromatography (LC)
High Performance Liquid Chromatography (HPLC)
Ion Chromatography
Gas Chromatography (GC)
Paper and Thin Layer Chromatography
The solvent moves up paper by capillary action,
carrying mixture components at different rates.

solvent
front

Later

solvent
 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.
Chromatography is based on a physical equilibrium
that results when a solute is transferred between the
mobile and a stationary phase.
K = distribution
A coefficient or
A A partition ratio
A A
CS
A A K =
A CM
A Where CS is the molar
A
A A
concentration of the
solute in the stationary
Cross Section of Equilibrium in a column. phase and CM is the
“A” are adsorbed to the stationary phase. molar concentration in
“A” are traveling in the mobile phase. the mobile phase.
In a mixture, each component has a different distribution coefficient,
and thus spends a different amount of time absorbed on the solid
packing phase vs being carried along with the flowing gas

Flow

Flow

Flow

Flow

More volatile materials are carried through the column more rapidly
than less volatile materials, which results in a separation.
 In a chromatography column, flowing gas or liquid
continuously replaces saturated mobile phase and results
in movement of A through the column.

Flow

Column is packed
with particulate
stationary phase.

As a material travels through the column, it assumes a

Gaussian concentration profile as it distributes between the
stationary packing phase and the flowing mobile gas or
liquid carrier phase.
If a detector is used to determine when the components elute
from the column, a series of Gaussian peaks are obtained,
one for each component in the mixture that was separated
by the column.

Note: The first two components were not completely separated.

Peaks in general tend to become shorter and wider with time.
 Gas Chromatography
 Good for volatile samples (up to about 250 oC)
 0.1-1.0 microliter of liquid or 1-10 ml vapor
 Can detect <1 ppm with certain detectors
 Can be easily automated for injection and data analysis
Both online and offline analysis
Components of a Gas Chromatograph
Gas Supply: (usually N2 or He)
Sample Injector: (syringe / septum)
Column: 1/8” or 1/4” x 6-50’ tubing packed with
small uniform size, inert support coated with
thin film of nonvolatile liquid
Detector: TCD- thermal conductivity Detector
FID - flame ionization detector
MS
ECD
.
.
Carrier gas: He (common), N2, H2
Pinlet 10-50 psig
Flow = 25-150 mL/min packed column
Flow = 1-25 mL/min open tubular column
Column: 2-50 m coiled stainless steel/glass/Teflon
Oven: 0-400 °C ~ average boiling point of sample
Accurate to <1 °C
Detectors: FID, TCD, ECD, (MS)
Mobile Phase:

Carrier gas – main purpose of the gas in GC is to move the solutes along the column, mobile
phase is often referred to as carrier gas.

Common carrier gas: include He, Ar, H2, N2

GC Detectors:
The following devices are common types of GC detectors:
1. Thermal Conductivity Detector (TCD)
2. Flame Ionization Detector (FID)
3. Nitrogen-phosphorus Detector (NPD)
4. Electron Capture Detector (ECD)
5. Mass Spectrometers (discussed later in the course)

The choice of detector will depend on the analyte and how the GC method is being
used (i.e., analytical or preparative scale)

Detector Application Sensitivity Notes

TCD everything 10’s of nanograms Not very sensitive, easy to operate, only one
gas required
FID hydrocarbons Sub-nanogram Very linear, relatively easy to operate,
required fuel gasses, not sensitive to all
NPD Nitrogen/sulfur Low-picograms Very selective, hard to operate, required fuel
gases
ECD Halogenated, nitro Low-picograms Very sensitive, radiation source, not very
linear, selective, two gases
MS Almost everything Depends on operation Sensitive, requires pump system, failry
complicated requires cleaning
1.) Thermal Conductivity Detector (TCD)

- hot-wire detector
- first universal detector developed for GC

Process
- measures a bulk property of the mobile phase leaving the column.
- measures ability to conduct heat away from a hot-wire (i.e., thermal conductivity)
- thermal conductivity changes with presence of other components in the mobile phase
- Based on principle of wheatstone bridge
Design
- based on electronic circuit known as a Wheatstone bridge.
- circuit consists of an arrangement of four resistors with a fixed current applied to them.
- thermal conductivity changes with presence of other components in the mobile phase.
- the voltage between points (+) and (-) will be zero as long as the resistances in the
different arms of the circuit are properly balanced

-one resistor in contact with mobile

phase leaving column

-another in contact with reference

stream of pure mobile phase

as solute emerge from column:

change in thermal conductivity  change in amount of heat removed from resistor  change in resistor’s temperature
and resistance  change in voltage difference between points (+) and (-).
Considerations
- mobile phase must have very different thermal conductivity then solutes being
separated.
- most compounds separated in GC have thermal conductivity of about 1-4X10-5.
- H2 and He are carrier gases with significantly different thermal conductivity values.
- H2 reacts with metal oxides present on the resistors, so not used

advantages:
- truly universal detector
‚ applicable to the detection of any compound in GC
- non-destructive
‚ useful for detecting compounds from preparative-scale columns
‚ useful in combination with other types of GC detectors

disadvantage:
- detect mobile phase impurities
- sensitive to changes in flow-rates
- limit of detection
‚ ~ 10-7 M
2.) Flame Ionization Detector (FID)
- most common type of GC detector

- “universal” detector capable of measuring the presence of almost any organic and
many
inorganic compound

Process
- measures the production of ions when
a solute is burned in a flame.

- ions are collected at an electrode to

create a current
2.) Flame Ionization Detector (FID)
advantages:

- universal detector for organics

‚ doesn’t respond to common inorganic compounds

- mobile phase impurities not detected

- carrier gases not detected

- limit of detection: FID is 1000x better than TCD

- linear and dynamic range better than TCD

disadvantage:

- destructive detector
Nitrogen-Phosphorus Detector (NPD)

- used for detecting nitrogen- or phosphorus containing compounds

- also known as alkali flame ionization detector or thermionic detector

Process
- same basic principal as FID
Alkali Bead

- measures production of ions when a solute

is burned in a flame

- ions are collected at an electrode to

create a current

- contains a small amount of alkali metal

vapor in the flame

- enhances the formation of ions from

nitrogen- and phosphorus- containing compounds
3.) Nitrogen-Phosphorus Detector (NPD)

advantages:
- useful for environmental testing
‚ detection of organophosphate pesticides

- useful for drug analysis

‚ determination of amine-containing or basic drugs

- Like FID, does not detect common mobile phase impurities or carrier gases

- limit of detection: NPD is 500x better than FID in detecting nitrogen- and
phosphorus- containing compounds

- NPD more sensitive to other heterocompounds, such as sulfur-, halogen-, and arsenic- containing molecules

disadvantage:
- destructive detector

- NPD is less sensitive to organic compounds compared to FID

4.) Electron Capture Detector (ECD)

- radiation-based detector
- selective for compounds containing electronegative atoms, such as halogens

Process
- based on the capture of electrons by
electronegative atoms in a molecule

- electrons are produced by ionization of the

carrier gas with a radioactive source
‚ 3H or 63Ni

- in absence of solute, steady stream of

these electrons is produced

- electrons go to collector electrode where

they produce a current

- compounds with electronegative atoms

capture electrons, reducing current
 HIGH PERFORMANCE LIQUID
CHROMATOGRAPHY (HPLC)

• HPLC IS A FORM OF LIQUID CHROMATOGRAPHY USED TO SEPARATE COMPOUNDS

THAT ARE DISSOLVED IN SOLUTION. HPLC INSTRUMENTS CONSIST OF A RESERVOIR
OF MOBILE PHASE, A PUMP, AN INJECTOR, A SEPARATION COLUMN, AND A
DETECTOR.

• COMPOUNDS ARE SEPARATED BY INJECTING A SAMPLE MIXTURE ONTO THE COLUMN.

THE DIFFERENT COMPONENT IN THE MIXTURE PASS THROUGH THE COLUMN AND
DIFFERENTIATES DUE TO DIFFERENCES IN THEIR PARTITION BEHAVIOR BETWEEN THE
MOBILE PHASE AND THE STATIONARY PHASE. THE MOBILE PHASE MUST BE DEGASSED
TO ELIMINATE THE FORMATION OF AIR BUBBLES.
HPLC SYSTEM
PICTURE OF HPLC INSTRUMENT
PICTURE OF AN HPLC COLUMN
 SEVERAL COLUMN TYPES
(CAN BE CLASSIFIED AS )

• NORMAL PHASE

• REVERSE PHASE

• SIZE EXCLUSION

• ION EXCHANGE
 TYPES OF DETECTORS
• ABSORBANCE (UV WITH • EVAPORATIVE LIGHT
FILTERS, UV WITH SCATTERING DETECTOR
MONOCHROMATORS) (ELSD)

• IR ABSORBANCE • ELECTROCHEMICAL

• FLUORESCENCE • MASS-SPECTROMETRIC

• REFRACTIVE-INDEX • PHOTO-DIODE ARRAY

 PROBE BASED ANALYZER
• ASSIGNMENT 3