Instrumentation of Raman

spectroscopy, EDS and Gas

chromatography
Muhammad Farooq
Typical Raman Spectrum
Instrumentation of Raman Spectroscopy
• Laser Source (Argon ion, Krypton ion, He-Neon ion , Diode)
• Sample cell
• A suitable spectrometer
• A monitoring device
• Stoke scattering usually observed
• 4000-2500 cm-1 (X-H bond) , 2500-2000 cm-1(-N=C=O)
• Both quantitative and qualitative analysis can be carried out
• Sometimes peaks are fairly close together
Energy dispersive X ray Spectroscopy
• Used for elemental analysis of a
compound as small as in cubic micronn
• Sometimes in combined form SEM
• Electrons are bombarded on sample
surface cause excitation of a surface
electron and X rays are emitted
Schematics of EDS or EDX
• Electron beam source with cathode in
conjunction with a magnetic lens
• X ray detector to convert X ray energy to
voltage signal
• Pulse processor to pass voltage signals to
the analyzer
• Analyzer processes the data and generate
spectra
cont…

• Many elements exhibit multiple peaks and some peaks of various

elements overlap too so more focus is needed on the other peaks
• Intensities or areas of the various peaks of the specific spectrum give
information about the concentration of that specific element.
• Because an electron beam can be accurately controlled, one can
collect a spectrum from a point or particle of the size of only a cubic
micrometer. Similarly, one can cover a line or an area generating an X-
ray map that depicts the elemental composition of a given surface.
Limitations
• An EDS system detects the presence of an element up to 0.1%
concentration.
• EDS cannot detect elements below carbon in the periodic table.
• EDS has only limited detection capabilities for elements below
sodium in the periodic table
Gas Chromatography
• Gas chromatography (GC) is a characterization technique that separates a
complex mixture of substances according to volatility by interaction with a
stationary phase.
• Gas chromatography is a very useful technique for polymer analysis,
particularly for following determination of residual monomer, residual
odors, volatiles, additives, nature of contamination, and identification of
comonomers after pyrolysis
• Even at trace concentration, any substance with a volatilization temperature
below 320 0C and a molecular weight below 600 g/mole can be analyzed by
gas chromatography.
• HT GC and PTV increases M.Wt analysis to 1500g/mole
Gas Chromatography Instrumentation
The gas chromatograph comprises
1. An injector
2. Gases control unit
3. Column
4. Detector and
5. Data analysis unit.
 Injectors
Split/Splitless:
• The split/splitless injector is a device of a chromatograph that injects
a liquid sample, vaporizes the sample in the injector, mixes the
sample with the carrier gas, and directs the sample into the column.
• In the split operation mode, only a fraction of the vaporized sample is
sent to the column (according to a predefined split ratio), while in the
splitless operation the majority of the sample is sent to the column.
• The splitless operation mode is used for diluted samples (trace
analysis), while the split operation mode is used for concentrated
samples.
Cool on column
• The cool on-column injector is a device of a chromatograph that allows the
injection of the sample into the column. Sample enters directly into the column in
this case.
• Advantages include less adsorption of active compounds, less degradation of
thermal sensitive compounds, and better sensitivity for trace compounds
Programmed temperature volatilization(PTV)
• In the PTV injector, the sample is introduced in the liquid state; it is then vaporized
and transferred into the column in the gaseous state. High temperatures (up to
600 0C) are required to obtain enough vapor pressure to allow a large quantity
transfer of high molecular weight materials onto the column in a reasonably short
time.
Valve/Loop
This is used for gas analysis i.e., in pyrolysis of polymers
 Column and its requirements
• The column is the support of the stationary phase where the
separation of the sample components takes place and, for this reason,
is the heart of gas chromatography.
• Requirements of column
 Low bleed and high thermal stability
 Low superficial activity
 High selectivity
 High efficiency and resolution
 Durability and low cost
Parameters for selection of column
• Polarity – A column with low polarity separates the compounds
according to the boiling point, while the high polarity column
separates by dipole-dipole interactions.
• Diameter – As the internal diameter increases, so does the capacity,
but the resolution decreases. The typical diameter of a column is in
the range of 0.53 to 0.20 mm.
• Layer thickness – In modern chromatography columns (wall-coated
open-tubular column(WCOT)), the stationary phase is deposited over
a fused silica tube (coated with polyimide polymer for mechanical
resistance) in a thin layer.
Thickness of the stationary phase in
different scenarios
• Thick layers of stationary phase (3 to 5 microns) are preferred for gases
and extremely volatile compounds (volatiles near to room temperature).
• Intermediate layers of stationary phase (1 to 3 microns) are preferred for
volatile compounds that elute at temperatures up to 200 ◦C.
• Thin layers of stationary phase (0.25 to 1.00 microns) are preferred for
compounds that elute at temperatures in the range of 200 to 300 ◦C.
• Extremely thin layers of stationary phase (0.10 to 0.25 microns) are
preferred for high molecular weight compounds that elute at
temperatures above 300 ◦C.
• Length – As the length increases and the diameter decreases, the
efficiency of column increases (as the number of equivalent
theoretical distillation plates increases). Typical column lengths are
15, 30, 50, 60, and 105 m. Columns of 30 m are universally used in GC
analysis, while columns of 50, 60, and 105m are used for the
evaluation of very complex samples and low boiling point samples.