Analysis of Hydrocarbons

ANALYTICAL
INSTRUMENTS
ASSIGNMENT – II
NAME: Akash Raja K

REG NO: 113220061004
YEAR & SEM :4TH &7TH
ROLL NO: 4
Analysis of Hydrocarbons
• Flame ionization detectors
• gas chromatographs
• by use of lasers.
Flame ionization detectors

Flame ionization detectors work according to the principle of ions released in the
combustion of the sample species. Here, the assumption is that the sample
compounds will ionize inside a flame, while the carrier gas will not ionize. A
permanent flame (usually driven by hydrogen gas that produces insignificant ions
in combustion) serves to ionize any gas molecule that leaves the column of the
chromatograph and that is not carrier gas. The common carrier gases used with
the FID sensors are helium and nitrogen, which also produce negligible ions in a
flame. The sample molecules that encounter the flame ionize, making the flame
more conductive of electricity than it was with only hydrogen and carrier gas.
This conductivity causes the detector circuit to respond with a measurable
electrical signal.
Detector Construction
The FID is constructed of a small volume chamber into which the gas
chromatograph's capillary column in directly plumbed.
Usually the small diameter capillary is fitted directly into the bottom of the
detector's flame jet. The gaseous eluents from the column are mixed with
separately plumbed in hydrogen and air and all are burned on the jet's tip. After
the fuel (H2) and oxidant (O2 in air) are begun, the flame is lit using a electronic
ignitor, actually an electrically heated filament that is turned on only to light the
flame.
The charged particles created in that combustion process create a current

between the detector's electrodes. One electrode is actually the metallic jet
itself, another is close by and above the jet. The gaseous products leave the
detector chamber via the exhaust. The detector housing is heated so that gases
produced by the combustion (mainly water) do not condense in the detector
before leaving the detector chimney.
Makeup Gases
The total volume of gas in the FID that yields the most sensitive and widest
linear response is not the same volume of gas when the column effluent flow (~
1 mL/min) and hydrogen and air flows
are flowing; these gases' total flow
into the detector is too small. Another
way to say this is that the optimum
column flow to maintain the best
chromatography and the best fuel and
oxidant flows for the best flame
conditions--all added together--don't
create the best gas flow for the FID
detector's design. This means that to
maintain the best analytical
conditions, additional gas must be
constantly flowed into the detector. This gas makes up the additional needed gas
flow and so is termed makeup gas. Since the makeup gas needs to be inert so
that its addition doesn't upset the fuel and oxidant balance and since it needs to
be added in relatively large amounts (~30+ ml/min in some detector designs),
nitrogen is usually the gas of choice. Helium would work also but is a
nonrenewable resource and more expensive. All gas flows are controlled by
adjustable gas regulators.
Ignition and Shut Down
The process of lighting the FID goes like this: fuel is turned on at a
predetermined flow rate (controlled by the H2 tank's pressure regulator); air on;
ignitor is lit and the flame ignited. After the flame is confirmed burning,
makeup gas flow is turned on. The flame stabilizes within an hour or less and
then is routinely left on continuously to maintain the lowest signal background
and therefore produce the lowest detection limits. Some labs with high sample
throughputs keep FID flames burning continuously, only shutting the fame off
when gas tanks need be replaced. GC column carrier is also obviously keep
constantly flowing.
Turning off the flame involves first shutting off the fuel flow which
extinguishing the flame, then the oxidant and makeup gas flows are closed.
Limitations
Molecules that contained only carbon and hydrogen respond best in this detector
but the presence of "heteroatoms" in a molecule, such as oxygen, decreases the
detector's response. For instance, the FID's methane response (CH4) is fabulous but
formaldehyde's (CH2O) is quite poor. Therefore, highly oxygenated molecules or
sulfides might best be detected using another detector instead of the FID. Sulfides
determination by the flame photometric detector and aldehydes and ketones
analyzed with the photoionization detector are alternatives to the use of the FID for
those molecules.
Gas Chromatography
Gas chromatography (GC) is an analytical technique used to separate and detect
the chemical components of a sample mixture to determine their presence or
absence and/or quantities. These chemical components are usually organic
molecules or gases. For GC to be successful in their analysis, these components
need to be volatile, usually with a molecular weight below 1250 Da, and thermally
stable so they don’t degrade in the GC system. GC is a widely used technique
across most industries, including for:
• Quality control in the manufacture of many products from cars,1 to

chemicals and petrochemicals, to pharmaceuticals2
• Research purposes from the analysis of meteorites3 to natural products
• Safety and monitoring from environmental samples, microplastics and
food and wine, to forensics.
Working
As the name implies, GC uses a carrier gas in the separation, this plays the part of
the mobile phase (Figure 1 (1)). The carrier gas transports the sample molecules
through the GC system, ideally without reacting with the sample or damaging the
instrument components.
• The sample is first introduced into the gas chromatograph (GC), either with
a syringe or transferred from an autosampler (Figure 1 (2)) that may also
extract the chemical components from solid or liquid sample matrices. The
sample is injected into the GC inlet (Figure 1 (3)) through a septum which
enables the injection of the sample mixture without losing the mobile phase.
• Connected to the inlet is the analytical column (Figure 1 (4)), a long (10 –
150 m), narrow (0.1 – 0.53 mm internal diameter) fused silica or metal tube
which contains the stationary phase coated on the inside walls.
• The analytical column is held in the column oven which is heated during the
analysis to elute the less volatile components.
• The outlet of the column is inserted into the detector (Figure 1 (5)) which
responds to the chemical components eluting from the column to produce a
signal.
• The signal is recorded by the acquisition software on a computer to produce
a chromatogram (Figure 1 (6)).
Limitations
GC is a widely used technique across most industries. It is used for routine analysis
through to research, analysing a few to many hundreds (or thousands with GC x
GC) of compounds in many different matrices, from solids to gases. It is a robust
technique and is easily hyphenated to other techniques including mass
spectrometry.
GC is limited to analysing volatile compounds from helium/hydrogen up to

molecular weights of around 1250 u. Thermally labile compounds can degrade in a
hot GC, therefore cold injection techniques and low temperatures should be used to
minimize this. More polar analytes can become stuck or lost in the GC, therefore
the system should be deactivated and well-maintained or these analytes
derivatized.
Common problems with gas chromatography
The most common problem in GC is leaks. The mobile phase is a gas and flows
throughout the system, therefore the correct installation of parts and consumables
is important along with regular leak checking.
Activity is another issue for more polar analytes, especially those at trace levels.
Silanol groups on the glass liners and column, and also a build-up of dirt in the
system can cause tailing peaks, irreversible adsorption or catalytic breakdown. The
inlet is the area that causes most problems as it is here the sample is injected,
vaporized and transferred into the GC column. Therefore, regular inlet
maintenance along with using the correct consumables, for example a deactivated
inlet liner, is important to keep the instrument trouble-free.
Measurements of hydrocarbons using laser-induced breakdown
spectroscopy
Methods of quickly and rapidly measuring gas composition in combustion

systems are of great practical interest. Optical methods such as Raman
spectroscopy are quite useful in understanding fluid mixing, optimizing
combustion, and minimizing emissions. However, many existing optical methods
are limited by the need for some knowledge of the reaction progress, as they
measure mole fractions of molecular reactant or product species.
Other methods measure condensed-phase (spray) concentrations before

combustion, or flame emission directly, to infer composition. Here we describe the
use of laser-induced breakdown spectroscopy (LIBS) for direct measurement of
atomic species over a wide range of mixture fractions of C3H8, CH4, and CO2 in
air.
Atomic emission from a laser-induced plasma is observed and ratios of elemental

lines present in the spectra are used to infer composition in reactants and in flames.
The method has spatial resolution on the order of 1 mm, and equivalence ratio can
be determined from the spectra obtained from a single shot of the laser, avoiding
time averaging of signals. In this paper we demonstrate that LIBS can be used to
obtain quantitative equivalence ratio measurements for propane and methane in air.
The C/(N+O) atomic ratio is used to quantify mixture fraction of C3H8 in air, and
data from individual breakdown events have a standard deviation of 3% of the
mean for mixtures of 0, 1, and 2% propane in air.
The strength of the C, O, and N lines in the spectral window 700–800 nm is

investigated for binary mixtures of C3H8, CH4, and CO2 in air. The dependence of
the atomic emission on the concentration of carbon and hydrogen is investigated in
the present paper, as well as the influence of experimental parameters such as the
laser power and the temporal gating of the detector.
In this context, an intriguing question arises, ‘What happens to diamond growth if
electronic excitations are triggered with UV laser irradiation in the gas phase?’ UV
photochemistry has long been exploited as a means of gaining chemical control in
molecular reactions motivated by suppressing side product channels to obtain the
desired deposit. However, there have been few successes in practical material
synthesis because the photochemical effects have been believed to be too small.
However, selectivity among various competing chemical processes in material
synthesis is attractive because it enables a better understanding of the reacting
channels, leading to process control and improvements.
In this work, instead of simply relying on UV laser photolysis, we introduced UV
laser irradiation into a conventional combustion diamond CVD process,
demonstrating that the flame chemistry was altered such that it favored diamond
growth and suppressed nondiamond carbon accumulation. Optical emission
spectroscopy (OES) and laser-induced fluorescence (LIF) demonstrated that UV
laser irradiation of the combustion flame promoted the generation of reactive
species that are critical to diamond growth, leading to enhanced diamond growth.
The growth rate and the film quality were significantly enhanced. Cross-sections of
the microstructures of the diamond films revealed fast lateral grain size evolution
rates as well as significantly shortened nucleation times with UV laser irradiation,
suggesting that secondary nucleation, which is closely related to the accumulation
of amorphous graphitic carbon, was significantly suppressed.
A narrow amorphous carbon transition zone, averaging 4 nm in thickness, was
identified at the film–substrate interface using transmission electron microscopy
(TEM), confirming the suppression effect of UV laser irradiation on nondiamond
carbon formation. Compared with our previous results obtained with IR laser
vibrational excitation, the UV laser irradiation acted in a nonthermal fashion, in
which reactive species for diamond growth were directly produced through
photolysis.
The systematic investigation of how the energy coupling path, either through
vibrational or electronic excitation, affects the diamond growth process provides a
clear guideline for fully exploring the advantages of laser chemistry in material
synthesis.
Conclusion
The influence of UV-laser-induced photolysis on diamond growth was investigated.

OES and LIF of the flame indicated that UV-laser-induced photolysis produced large
amounts of reactive radicals in the flame, contributing directly to the promotion of
diamond growth. Investigation of the nucleation process suggested that UV laser
irradiation modified diamond growth such that it favored diamond formation and
suppressed nondiamond carbon accumulation, leading to an enhanced diamond
deposition rate and improved diamond quality.
The diamond growth observed under UV laser irradiation was compared with that
assisted by IR vibrational excitations. The results suggest that both energy coupling
paths facilitated diamond growth to some extent, although the working mechanisms
were completely distinct. The discovery of the advantages of laser photochemistry
in diamond growth is of great significance for vastly improving the synthesis of a
broad range of technically important materials.

Analysis of Hydrocarbons

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Analysis of Hydrocarbons

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ANALYTICAL

NAME: Akash Raja K

Flame ionization detectors

The charged particles created in that combustion process create a current

• Quality control in the manufacture of many products from cars,1 to

GC is limited to analysing volatile compounds from helium/hydrogen up to

Common problems with gas chromatography

Methods of quickly and rapidly measuring gas composition in combustion

Other methods measure condensed-phase (spray) concentrations before

Atomic emission from a laser-induced plasma is observed and ratios of elemental

The strength of the C, O, and N lines in the spectral window 700–800 nm is

The influence of UV-laser-induced photolysis on diamond growth was investigated.

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