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CHEMICAL COMPOSITION ANALYZERS

Notarte, Melanie; Diaz, Jose Paulo; Ida, Carlo; Uao, Franc Ernest B.

I. CHROMATOGRAPHIC ANALYZERS
a. Gas Chromatography - provides a quantitative analysis of volatile and semi-volatile organic compounds found in a variety of
matrices (gases, liquids and solids) in foods, medical materials, plastics, environmental samples and occupational monitoring
samples. Carrier gases are He (common), N2, H2, Argon (must be chemically inert).
It is a process of separating component(s) from the given crude drug by using a gaseous mobile phase.
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.
Two major types
Gas-solid chromatography
(stationary phase: solid)
Gas-liquid chromatography
(stationary phase: immobilized liquid)
provides a quantitative analysis of volatile and semi-volatile organic compounds found in a variety of matrices (gases, liquids and
solids) in foods, medical materials, plastics, environmental samples and occupational monitoring samples.

1. The eluant (carrier gas) is introduced from a gas cylinder outside the machine. It's called
the carrier because that's exactly what it doescarry the sample we're studying through
the machine. In gas chromatography, the carrier gas is the mobile phase.

2. The rate of flow of the carrier is carefully controlled to give the clearest separation of the
components in the sample.

3. The carrier enters the machine through an inlet port/splitter.

4. The sample being measured is injected into the carrier gas using a syringe and instantly
vaporizes (turns into gas form).

5. The gases that make up the sample separate out as they move along the column , which is
the stationary phase. The column is a very thin (capillary) tube, sometimes as much as
3060m (100-200ft) long, coiled and entirely contained inside an oven that keeps it at a
high enough temperature to ensure that the sample remains in gas form. The temperature of the oven can be carefully controlled.

6. As the sample separates out and its constituent gases travel along the column at different speeds, a detector senses and records them. Various
different detectors can be used, including flame ionization detectors, thermal conductivity detectors, and mass spectrometers (usually
separate machines).

7. The data analyzer/recorder attached to the machine draws a chromatogram (chart) with peaks corresponding to the relative amounts of the
different chemicals in the sample.

Detectors for GC:

1. Flame ionization detectors (FID) - a scientific instrument that measures the concentration of organic species in a gas stream. It
is frequently used as a detector in gas chromatography. It operates by the principle that by change in conductivity of the flame as
the compound is burnt. The change in conductivity of the flame does not arise by simple ionization of the compound , it is partial
or complete stripping of the compound to give charged hydrogen-deficient polymers or aggregates of carbon of low ionization
potential.
2. Flame photometric detectors (FPD) - allows sensitive and selective measurements of volatile sulphur and phosphorus
compounds. The detection principle is the formation of excited sulphur (S 2*) and excited hydrogen phosphorous oxide species
(HPO*) in a reducing flame.
3. Thermal conductivity detectors (TCD) - also known as a Katharometer, are a bulk property detector and a chemical specific
detector commonly used in gas chromatography. This detector senses changes in the thermal conductivity of the column effluent
and compares it to a reference 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.
4. Electron Capture detector (ECD) - The ECD ionizes the carrier gas by means of a radioactive source. The potential across two
electrodes is adjusted to collect all the ions and a steady saturation current, is therefore, recorded.

b. High performance liquid chromatography is basically a highly improved form of column chromatography. Instead of a solvent
being allowed to drip through a column under gravity, it is forced through under high pressures of up to 400 atmospheres. That
makes it much faster.
It also allows you to use a very much smaller particle size for the column packing material which gives a much greater surface area for
interactions between the stationary phase and the molecules flowing past it. This allows a much better separation of the components of the
mixture.
The sample mixture to be separated and analyzed is introduced, in a discrete small volume (typically microliters), into the stream of mobile
phase percolating through the column. The components of the sample move through the column at different velocities, which are a function
of specific physical interactions with the adsorbent (also called stationary phase). The velocity of each component depends on its chemical
nature, on the nature of the stationary phase (column) and on the composition of the mobile phase. The time at which a specific analyte
elutes (emerges from the column) is called its retention time. The retention time measured under particular conditions is an identifying
characteristic of a given analyte.

The time taken for a particular compound to travel through the column to the detector is known as its retention time.

The detector
The amount of light absorbed will depend on the amount of a particular compound that is passing through the beam at the time.

c. Ion Chromatography (IC) is an analytical technique that separates ions and polar molecules based on their charge. Each species
interacts slightly differently with the stationary phase (a resin-filled column), and thus has a different retention time. Once
separated, each species can then be quantified individually as it leaves the system.

IC is used for water chemistry analysis. Ion chromatographs are able to measure concentrations of major anions, such as fluoride,
chloride, nitrate, nitrite, and sulfate, as well as major cations such as lithium, sodium, ammonium, potassium, calcium, and
magnesium in the parts-per-billion (ppb) range. Concentrations of organic acids can also be measured through ion
chromatography.

Ion chromatography, a form of liquid chromatography, measures


concentrations of ionic species by separating them based on their
interaction with a resin. Ionic species separate differently depending on
species type and size. Sample solutions pass through a pressurized
chromatographic column where ions are absorbed by column
constituents. As an ion extraction liquid, known as eluent, runs through
the column, the absorbed ions begin separating from the column. The
retention time of different species determines the ionic concentrations in
the sample.
II. INFRARED ANALYZERS

Infrared Waves
Discovered by William Herschel in 1800
Infrared (IR) light is electromagnetic radiation with longer wavelengths than those of visible light, extending from the nominal
red edge of the visible spectrum at 0.74 micrometers (m) to 1 mm. This range of wavelengths corresponds to a frequency range
of approximately 300 GHz to 400 THz, and includes most of the thermal radiation emitted by objects near room temperature.
Infrared light is emitted or absorbed by molecules when they change their rotational-vibrational movements.
Infrared radiation is popularly known as "heat radiation," but light and electromagnetic waves of any frequency will heat
surfaces that absorb them. Infrared light from the Sun only accounts for 49% of the heating of the Earth, with the rest being
caused by visible light that is absorbed then re-radiated at longer wavelengths.
The concept of emissivity is important in understanding the infrared emissions of objects. This is a property of a surface which
describes how its thermal emissions deviate from the ideal of a black body. To further explain, two objects at the same physical
temperature will not "appear" the same temperature in an infrared image if they have differing emissivities.

Applications of IR waves
Communication
-common example is remote control
Thermal imaging
-look at human body heat emissions (medical purposes and security cameras)
Spectroscopy
Astronomy
Biological and medical science

Note: Night vision is different from thermal imaging


Night vision is seeing objects at night using infrared devices, which is basically increasing the visibility in the dark without using a visible light
source. These infrared devices increase the amount of available light in the night thereby increasing visibility.

Thermal imaging is a process by which thermal images are captured and the images are totally dependent on the amount of heat (infrared radiation)
emitted by a body

Non-dispersive Infrared Analyzer

A nondispersive infrared sensor (or NDIR sensor) is a simple spectroscopic sensor often used as a gas detector. It is nondispersive in the sense
of optical dispersion since the infrared energy is allowed to pass through the atmospheric sampling chamber without deformation.

2 types of detector for NDIR


1. Two gas-filled cells separated by a diaphragm
A chopped light system is normally used in which one side of the
detector sees the source through the analyzing beam and the other side
sees through the reference beam, alternating at a frequency of a few
hertz.

2. Two thermophiles or two bolometers

III. UV AND VISIBLE-RADIATION ANALYZER


Beer-Lambert Law
- states that the absorbance of a solution is directly proportional to the concentration of the absorbing species in the solution and
the path length
Colorimetry
- a technique "used to determine the concentration of colored compounds in solution
- a technique used to test the concentration of a solution by measuring its absorbance of a specific wavelength of light

UV/Vis Spectroscopy used to determine the concentration of absorber in a solution

o UV/Vis Spectrophotometer
- Measures the intensity of light passing through a sample and compares it to the intensity of light before it passes through the
sample

Spectrochemical Analysis
- depend upon the measurement of the wavelength and the intensity of electromagnetic radiation
Emission Spectroscopy
- atoms are excited from ground state to higher energy levels by means of electrical discharges or flames
- when excited atoms return to lower energy states, they emit light of characteristic frequencies

IV. PARAMAGNETIC METHOD AND MASS SPECTROSCOPY

Principle

Oxygen and nitric oxide are paramagnetic

because the electrons in the outer shell of the molecule are unpaired
thus attracted into a magnetic field

Most other gases (e.g. nitrogen) are weakly diamagnetic and thus are repelled from a magnetic field.

Advantage Disadvantage

Rapid Frequent calibration required


Interfered by water vapour

What is a paramagnetic analyzer?

The determination of oxygen (O2) is important in many processes. Methods for measuring oxygen contents are either physical or chemical.
Physical methods use the paramagnetic property of oxygen or thermal conductivity as the basis for quantitative determinations.

Most gases are slightly diamagnetic and repelled out of a magnetic field. Oxygen is different; it is a paramagnetic gas, which means that it is attracted
by a magnetic field. There are a number of oxygen analyzers which use the unique paramagnetic properties of oxygen.
Paramagnetism is strongly temperature-dependent. Cold oxygen molecules
are attracted by a strong magnetic field and when they are heated they leave
the magnetic field. This gives rise to a current which generates a measure of
the oxygen content.

Diagram of a paramagnetic analyzer

Differences between the types of magnetism

Diamagnetism refers to materials that are not affected by a magnetic field.

Paramagnetism refers to materials like aluminum or platinum which become


magnetized in a magnetic field but their magnetism disappears when the field
is removed.

Ferromagnetism refers to materials (such as iron and nickel) that can retain their magnetic properties when the magnetic field is removed.

In Paramagnetic materials, the electron orbits do not cancel out, but the electron fields dont reinforce each other as much as those in
ferromagnetic materials. They therefore have permanent dipole moments that try to line up with the magnetic field, but are prevented from remaining
aligned by random thermal motion. When a paramagnetic material is placed in a strong magnetic field, it becomes a magnet, and as long as the strong
magnetic field is present, it will attract and repel other magnets in the usual way. But when the strong magnetic field is removed, the net magnetic
alignment is lost as the dipoles relax back to their normal random motion.

Mass Spectroscopy

Mass spectrometry is an analytical tool useful for measuring the mass-to-charge ratio (m/z) of one or more molecules present in a sample. These
measurements can often be used to calculate the exact molecular weight of the sample components as well. Typically, mass spectrometers can be
used to identify unknown compounds via molecular weight determination, to quantify known compounds, and to determine structure and chemical
properties of molecules.

Mass spectrometry is based on identifying molecules based on their molecular weight and weights of fragments formed from the molecules as
measured by using electric and magnetic fields to measure masses of ions generated in the gas phase. It is a powerful analytical technique that can
used for identification and quantification of the compounds in a mixture with the help of separation techniques such as gas chromatography (GC)
and liquid chromatography(LC)

How does a mass spectrometer perform such a feat? Every mass spectrometer consists of at least these three components:
Ionization Source
Mass Analyzer
Ion Detection System

Mass Spectrometers measure the weights of molecules. This is typically done by electric and magnetic fields in a vacuum. In order to measure the
masses of the molecules, the ions must be ionized and either formed in the vacuum or transfer to the vacuum.
The ionization usually takes place in the mass spectrometer source. The source is designed for the ionization method that is going to be used. On
some instruments the ionization source can be changed for the ionization method.
The ions formed in the source are transferred to the analyzer, which is the heart of the spectrometer. The analyzer uses magnetic and electric fields to
measure the mass to charge ratio of the ion. Finally, the ions are detected. This is usually done by sending the ions into an electron multiplier or a
micro channel plate, which multiplies the current and sends it on to a computer that plots the current vs. the mass to charge ratio. One other method
of detection is by image current, which are used on FTMS analyzers. Image current detection, detects the ions going around the instrument in pattern
by the induced current on electrodes, this current measures the frequency of the pattern, which the computer uses to come up with the mass spectrum,
which is the mass to charge ratio vs. intensity graph.

1. The Ionization Source


Molecules are converted to gas-phase ions so that they can be moved about and manipulated by
external electric and magnetic fields. In our laboratory we use a technique called
nanoelectrospray ionization, which is somewhat similar to how cars are industrially painted.
This method allows for creating positively or negatively charged ions, depending on the
experimental requirements. Nanoelectrospray ionization can directly couple the outlet of a
small-scale chromatography column directly to the inlet of a mass spectrometer. The flow from
the column is passed through a needle that is 10-15 um at its tip.

2. The Mass Analyzer


Once ionized, the ions are sorted and separated according to mass-to-charge (m/z) ratios. There are a number of mass analyzers currently available,
each of which has trade-offs relating to speed of operation, resolution of separation, and other operational requirements. The specific types in use at
the Broad Institute are discussed in the next section. The mass analyzer often works in concert with the ion detection system.

3. Ion Detection System


The separated ions are then measured and sent to a data system where the m/z ratios are stored
together along with their relative abundance. A mass spectrum is simply the m/z ratios of the
ions present in a sample plotted against their intensities. Each peak in a mass spectrum shows a
component of unique m/z in the sample, and heights of the peaks connote the relative abundance
of the various components in the sample.

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