Gas-liquid chromatography (GLC), or simply gas chromatography (GC), is a common type of chromatography Chromatography is the collective term for a set of laboratory techniques for the separation of mixtures. It involves passing a mixture dissolved in a "mobile phase" through a stationary phase, which separates the analyte to be measured from other molecules in the mixture and allows it to be isolated used in organic chemistry Organic chemistry is a discipline within chemistry which involves the scientific study of the structure, properties, composition, reactions, and preparation of chemical compounds that contain carbon. These compounds may contain any number of other elements, including hydrogen, nitrogen, oxygen, the halogens as well as phosphorus, silicon and for separating In chemistry and chemical engineering, a separation process is used to transform a mixture of substances into two or more distinct products. The separated products could differ in chemical properties or some physical property, such as size, or crystal modification or other separation into different components and analyzing compounds that can be vaporized Evaporation is the slow vaporization of a liquid and the reverse of condensation. A type of phase transition, it is the process by which molecules in a liquid state spontaneously become gaseous (e.g. water vapor). Generally, evaporation can be seen by the gradual disappearance of a liquid from a substance when exposed to a significant volume of without decomposition Chemical decomposition or analysis is the separation of a chemical compound into elements or smaller compounds. It is sometimes defined as the opposite of a chemical synthesis. Chemical decomposition is often an undesired chemical reaction. The stability that a chemical compound ordinarily has is eventually limited when exposed to extreme. Typical uses of GC include testing the purity of a particular substance, or separating the different components of a mixture (the relative amounts of such components can also be determined). In some situations, GC may help in identifying a compound. In microscale chemistry, GC can be used to prepare pure compounds from a mixture.^[1]

In gas chromatography, the moving phase (or "mobile phase") is a carrier gas In physics, a gas is a state of matter, consisting of a collection of particles without a definite shape or volume that are in more or less random motion, usually an inert In chemistry, the term inert is used to describe something that is not chemically active. The noble gases were described as being inert because they did not react with the other elements or themselves. It is now understood that the reason that inert gases are completely inert to basic chemical reactions is that their outer valence shell is gas such as helium Helium is the chemical element with atomic number 2, and is represented by the symbol He. It is a colorless, odorless, tasteless, non-toxic, inert monatomic gas that heads the noble gas group in the periodic table. Its boiling and melting points are the lowest among the elements and it exists only as a gas except in extreme conditions or an unreactive Reactivity refers to the rate at which a chemical substance tends to undergo a chemical reaction in time. In pure compounds, reactivity is regulated by the physical properties of the sample. For instance, grinding a sample to a higher specific surface area increases its reactivity. In impure compounds, the reactivity is also affected by the gas such as nitrogen Nitrogen is a chemical element that has the symbol N and atomic number 7 and atomic mass 14.00674 u. Elemental nitrogen is a colorless, odorless, tasteless and mostly inert diatomic gas at standard conditions, constituting 78% by volume of Earth's atmosphere. The stationary phase is a microscopic layer of liquid Liquid is one of the principal states of matter. A liquid is a fluid that has the particles loose and can freely form a distinct surface at the boundaries of its bulk material. The surface is a free surface where the liquid is not constrained by a container or polymer A polymer is a large molecule (macromolecule) composed of repeating structural units typically connected by covalent chemical bonds. While polymer in popular usage suggests plastic, the term actually refers to a large class of natural and synthetic materials with a variety of properties on an inert solid A solid object is in the states of matter characterized by resistance to deformation and changes of volume. In other words, it has high values both of Young's modulus and of shear modulus; this contrasts e.g. with a liquid, which has a low shear modulus. At the microscopic scale, a solid has these properties : support, inside a piece of glass Glass generally refers to hard, brittle, transparent material, such as those used for windows, many bottles, or eyewear. Examples of such materials include, but are not limited to, soda-lime glass, borosilicate glass, acrylic glass, sugar glass, isinglass , or aluminium oxynitride. In the technical sense, glass is an inorganic product of fusion or metal In chemistry, a metal is an element, compound, or alloy characterized by high electrical conductivity. In a metal, atoms readily lose electrons to form positive ions (cations); those ions are surrounded by delocalized electrons, which are responsible for the conductivity. The thus produced solid is held by electrostatic interactions between the tubing called a column. The instrument used to perform gas chromatography is called a gas chromatograph (or "aerograph", "gas separator").

The gaseous compounds being analyzed interact with the walls of the column, which is coated with different stationary phases. This causes each compound to elute Elution is a term used in analytical chemistry to describe the emergence of chemicals from the column of a chromatograph. As they elute, the chemicals typically flow into a detector. Predicting and controlling the order of elution is a key aspect of column chromatographic methods at a different time, known as the retention time of the compound. The comparison of retention times is what gives GC its analytical usefulness.

Gas chromatography is in principle similar to column chromatography (as well as other forms of chromatography, such as HPLC High-performance liquid chromatography is a form of column chromatography used frequently in biochemistry and analytical chemistry to separate, identify, and quantify compounds. HPLC utilizes a column that holds chromatographic packing material (stationary phase), a pump that moves the mobile phase(s) through the column, and a detector that shows, TLC Thin layer chromatography is a chromatography technique used to separate mixtures. Thin layer chromatography is performed on a sheet of glass, plastic, or aluminum foil, which is coated with a thin layer of adsorbent material, usually silica gel, aluminium oxide, or cellulose. This layer of adsorbent is known as the stationary phase), but has several notable differences. Firstly, the process of separating the compounds in a mixture is carried out between a liquid stationary phase and a gas moving phase, whereas in column chromatography the stationary phase is a solid and the moving phase is a liquid. (Hence the full name of the procedure is "Gas-liquid chromatography", referring to the mobile and stationary phases, respectively.) Secondly, the column through which the gas phase passes is located in an oven An oven is an enclosed compartment for heating, baking or drying. It is most commonly used in cooking and pottery. Ovens used in pottery are also known as kilns. An oven used for heating or for industrial processes is called a furnace or industrial oven where the temperature In physics, temperature is a physical property of a system that underlies the common notions of hot and cold; something that feels hotter generally has the higher temperature. Temperature is one of the principal parameters of thermodynamics. If no heat flow occurs between two objects, the objects have the same temperature; otherwise heat flows of the gas can be controlled, whereas column chromatography (typically) has no such temperature control. Thirdly, the concentration In chemistry, concentration is the measure of how much of a given substance there is mixed with another substance. This can apply to any sort of chemical mixture, but most frequently the concept is limited to homogeneous solutions, where it refers to the amount of solute in the solvent of a compound in the gas phase is solely a function The mathematical concept of a function expresses dependence between two quantities, one of which is known and the other which is produced. A function associates a single output to each input element drawn from a fixed set, such as the real numbers , although different inputs may have the same output of the vapor pressure Vapor pressure , is the pressure of a vapor in equilibrium with its non-vapor phases. All liquids and solids have a tendency to evaporate to a gaseous form, and all gases have a tendency to condense back into their original form (either liquid or solid). At any given temperature, for a particular substance, there is a pressure at which the gas of of the gas.^[1]

Gas chromatography is also similar to fractional distillation Fractional distillation is the separation of a mixture into its component parts, or fractions, such as in separating chemical compounds by their boiling point by heating them to a temperature at which several fractions of the compound will evaporate. It is a special type of distillation. Generally the component parts boil at less than 25 °C from, since both processes separate the components of a mixture primarily based on boiling point The boiling point of an element or a substance is the temperature at which the vapor pressure of the liquid equals the environmental pressure surrounding the liquid. A liquid in a vacuum environment has a lower boiling point than when the liquid is at atmospheric pressure. A liquid in a high pressure environment has a higher boiling point than (or vapor pressure) differences. However, fractional distillation is typically used to separate components of a mixture on a large scale, whereas GC can be used on a much smaller scale (i.e. microscale).^[1]

Gas chromatography is also sometimes known as vapor-phase chromatography (VPC), or gas-liquid partition chromatography (GLPC). These alternative names, as well as their respective abbreviations, are frequently found in scientific literature Scientific literature comprises scientific publications that report original empirical and theoretical work in the natural and social sciences, and within a scientific field is often abbreviated as the literature. Academic publishing is the process of placing the results of one's research into the literature. Scientific research on original work. Strictly speaking, GLPC is the most correct terminology, and is thus preferred by many authors.^[1]

History

Chromatography Chromatography is the collective term for a set of laboratory techniques for the separation of mixtures. It involves passing a mixture dissolved in a "mobile phase" through a stationary phase, which separates the analyte to be measured from other molecules in the mixture and allows it to be isolated dates to 1903 in the work of the Russian Russia (pronounced /ˈrʌʃə/ ; Russian: Россия, pronounced [rʌˈsʲijə]), officially known as both Russia and the Russian Federation(Russian: Российская Федерация​ (help·info), Rossiyskaya Federatsiya), is a country in northern Eurasia (Europe and Asia together). It is a semi-presidential republic, comprising 83 scientist, Mikhail Semenovich Tswett. German Germany (pronounced /ˈdʒɜrməni/ ), officially the Federal Republic of Germany (German: Bundesrepublik Deutschland, pronounced [ˈbʊndəsʁepuˌbliːk ˈdɔʏtʃlant] ( listen)), is a country in Central Europe. It is bordered to the north by the North Sea, Denmark, and the Baltic Sea; to the east by Poland and the Czech Republic; to the south graduate student Fritz Prior developed solid state gas chromatography in 1947. Archer John Porter Martin, who was awarded the Nobel Prize The Nobel Prize is a Swedish prize, established in the 1895 will of Swedish chemist and inventor Alfred Nobel; it was first awarded in Physics, Chemistry, Physiology or Medicine, Literature, and Peace in 1901. An associated prize, The Sveriges Riksbank Prize in Economic Sciences in Memory of Alfred Nobel, was instituted by Sweden's central bank in for his work in developing liquid-liquid (1941) and paper (1944) chromatography, laid the foundation for the development of gas chromatography and later produced liquid-gas chromatography (1950).

GC analysis

A gas chromatograph is a chemical analysis instrument for separating chemicals A chemical substance is a material with a specific chemical composition.[citation needed] It is a concept that became firmly established in the late eighteenth century after work by the chemist Joseph Proust on the composition of some pure chemical compounds such as basic copper carbonate. He deduced that, "All samples of a compound have the in a complex sample. A gas chromatograph uses a flow-through narrow tube known as the column, through which different chemical constituents of a sample pass in a gas stream (carrier gas, mobile phase) at different rates depending on their various chemical and physical properties and their interaction with a specific column filling, called the stationary phase. As the chemicals exit the end of the column, they are detected and identified electronically Electronics is a branch of science and technology that deals with the flow of electrons through nonmetallic conductors, mainly semiconductors such as silicon. It is distinct from electrical science and technology, which deal with the flow of electrons and other charge carriers through metal conductors such as copper. This distinction started. The function of the stationary phase in the column is to separate different components, causing each one to exit the column at a different time (retention time). Other parameters that can be used to alter the order or time of retention are the carrier gas flow rate, and the temperature.

In a GC analysis, a known volume of gaseous or liquid analyte An analyte is a substance or chemical constituent that is determined in an analytical procedure, such as a titration. For instance, in an immunoassay, the analyte may be the ligand or the binder, while in blood glucose testing, the analyte is glucose. In medicine, analyte often refers to the type of test being run on a patient, as the test is is injected into the "entrance" (head) of the column, usually using a microsyringe A syringe is a simple piston pump consisting of a plunger that fits tightly in a tube. The plunger can be pulled and pushed along inside a cylindrical tube , allowing the syringe to take in and expel a liquid or gas through an orifice at the open end of the tube. The open end of the syringe may be fitted with a hypodermic needle, a nozzle, or (or, solid phase microextraction fibers, or a gas source switching system). As the carrier gas sweeps the analyte molecules through the column, this motion is inhibited by the adsorption Adsorption is the accumulation of atoms or molecules on the surface of a material. This process creates a film of the adsorbate on the adsorbent's surface. It is different from absorption, in which a substance diffuses into a liquid or solid to form a solution. The term sorption encompasses both processes, while desorption is the reverse process of the analyte molecules In chemistry, a molecule is defined as a sufficiently stable, electrically neutral group of at least two atoms in a definite arrangement held together by very strong chemical bonds. Molecules are distinguished from polyatomic ions in this strict sense. In organic chemistry and biochemistry, the term molecule is used less strictly and also is either onto the column walls or onto packing materials in the column. The rate at which the molecules progress along the column depends on the strength of adsorption Adsorption is the accumulation of atoms or molecules on the surface of a material. This process creates a film of the adsorbate on the adsorbent's surface. It is different from absorption, in which a substance diffuses into a liquid or solid to form a solution. The term sorption encompasses both processes, while desorption is the reverse process, which in turn depends on the type of molecule and on the stationary phase materials. Since each type of molecule has a different rate of progression, the various components of the analyte mixture are separated as they progress along the column and reach the end of the column at different times (retention time). A detector is used to monitor the outlet stream from the column; thus, the time at which each component reaches the outlet and the amount of that component can be determined. Generally, substances are identified (qualitatively) by the order in which they emerge (elute) from the column and by the retention time of the analyte in the column.

Physical components

Autosamplers

The autosampler provides the means to introduce a sample automatically into the inlets. Manual insertion of the sample is possible but is no longer common. Automatic insertion provides better reproducibility and time-optimization.

Different kinds of autosamplers exist. Autosamplers can be classified in relation to sample capacity (auto-injectors vs. autosamplers, where auto-injectors can work a small number of samples), to robotic technologies (XYZ robot vs. rotating/SCARA-robot – the most common), or to analysis:

• Liquid
• Static head-space by syringe technology
• Dynamic head-space by transfer-line technology
• Solid phase microextraction (SPME)

Traditionally autosampler manufacturers are different from GC manufacturers and currently no GC manufacturer offers a complete range of autosamplers. Historically, the countries most active in autosampler technology development are the United States, Italy, and Switzerland.

Inlets

The column inlet (or injector) provides the means to introduce a sample into a continuous flow of carrier gas. The inlet is a piece of hardware attached to the column head.

Common inlet types are:

• S/SL (Split/Splitless) injector; a sample is introduced into a heated small chamber via a syringe through a septum - the heat facilitates volatilization Volatilisation is the process whereby a dissolved sample is vaporised. In atomic spectroscopy this is usually a two step process. The analyte is turned into small droplets in a nebuliser which are entrained in a gas flow which is in turn volatilised in a high temperature flame in the case of AAS or volatilised in a gas plasma torch in the case of of the sample and sample matrix. The carrier gas then either sweeps the entirety (splitless mode) or a portion (split mode) of the sample into the column. In split mode, a part of the sample/carrier gas mixture in the injection chamber is exhausted through the split vent. Split injection is preferred when working with samples with high analyte concentrations (>0.1%) whereas splitless injection is best suited for trace analysis with low amounts of analytes. (<0.01%)
• On-column inlet; the sample is here introduced in its entirety without heat.
• PTV injector; Temperature-programmed sample introduction was first described by Vogt in 1979. Originally Vogt developed the technique as a method for the introduction of large sample volumes (up to 250 µL) in capillary GC. Vogt introduced the sample into the liner at a controlled injection rate. The temperature of the liner was chosen slightly below the boiling point of the solvent. The low-boiling solvent was continuously evaporated and vented through the split line. Based on this technique, Poy developed the Programmed Temperature Vaporising injector; PTV. By introducing the sample at a low initial liner temperature many of the disadvantages of the classic hot injection techniques could be circumvented.
• Gas source inlet or gas switching valve; gaseous samples in collection bottles are connected to what is most commonly a six-port switching valve. The carrier gas flow is not interrupted while a sample can be expanded into a previously evacuated sample loop. Upon switching, the contents of the sample loop are inserted into the carrier gas stream.
• P/T (Purge-and-Trap) system; An inert gas is bubbled through an aqueous sample causing insoluble volatile chemicals to be purged from the matrix. The volatiles are 'trapped' on an absorbent column (known as a trap or concentrator) at ambient temperature. The trap is then heated and the volatiles are directed into the carrier gas stream. Samples requiring preconcentration or purification can be introduced via such a system, usually hooked up to the S/SL port.
• SPME (solid phase microextraction) offers a convenient, low-cost alternative to P/T systems with the versatility of a syringe and simple use of the S/SL port.

Columns

Two types of columns are used in GC:

• Packed columns are 1.5 - 10 m in length and have an internal diameter of 2 - 4 mm. The tubing is usually made of stainless steel or glass and contains a packing of finely divided, inert, solid support material (eg. diatomaceous earth Diatomaceous earth — also known as DE, TSS, diatomite, diahydro, kieselguhr, kieselgur, Celatom or celite — is a naturally occurring, soft, chalk-like sedimentary rock that is easily crumbled into a fine white to off-white powder. This powder has an abrasive feel, similar to pumice powder, and is very light, due to its high porosity. The) that is coated with a liquid or solid stationary phase. The nature of the coating material determines what type of materials will be most strongly adsorbed. Thus numerous columns are available that are designed to separate specific types of compounds.
• Capillary columns have a very small internal diameter, on the order of a few tenths of millimeters, and lengths between 25-60 meters are common. The inner column walls are coated with the active materials (WCOT columns), some columns are quasi solid filled with many parallel micropores (PLOT columns). Most capillary columns are made of fused-silica The chemical compound silicon dioxide, also known as silica , is an oxide of silicon with a chemical formula of Si with a polyimide Thermosetting polyimides are commercially available as uncured resins, stock shapes, thin sheets, laminates and machines parts. Thermoplastic polyimides are very often called pseudothermoplastic. There are two general types of polyimides. One type, so-called linear polyimides, are made by combining imides into long chains. Aromatic heterocyclic outer coating. These columns are flexible, so a very long column can be wound into a small coil.
• New developments are sought where stationary phase incompatibilities lead to geometric solutions of parallel columns within one column. Among these new developments are:
  • Internally heated microFAST columns, where two columns, an internal heating wire and a temperature sensor are combined within a common column sheath (microFAST);
  • Micropacked columns (1/16" OD) are column-in-column packed columns where the outer column space has a packing different from the inner column space, thus providing the separation behaviour of two columns in one. They can easily fit to inlets and detectors of a capillary column instrument.

The temperature-dependence of molecular adsorption and of the rate of progression along the column necessitates a careful control of the column temperature In physics, temperature is a physical property of a system that underlies the common notions of hot and cold; something that feels hotter generally has the higher temperature. Temperature is one of the principal parameters of thermodynamics. If no heat flow occurs between two objects, the objects have the same temperature; otherwise heat flows to within a few tenths of a degree for precise work. Reducing the temperature produces the greatest level of separation, but can result in very long elution times. For some cases temperature is ramped either continuously or in steps to provide the desired separation. This is referred to as a temperature program. Electronic pressure control can also be used to modify flow rate during the analysis, aiding in faster run times while keeping acceptable levels of separation.

The choice of carrier gas (mobile phase) is important, with hydrogen being the most efficient and providing the best separation. However, helium has a larger range of flowrates that are comparable to hydrogen in efficiency, with the added advantage that helium is non-flammable, and works with a greater number of detectors. Therefore, helium is the most common carrier gas used.

Detectors

A number of detectors are used in gas chromatography. The most common are the flame ionization detector A flame ionization detector is a type of gas detector used in gas chromatography. The first flame ionization detector was developed in 1957 by scientists working for the CSIRO in Melbourne, Australia (FID) and the thermal conductivity detector (TCD). Both are sensitive to a wide range of components, and both work over a wide range of concentrations. While TCDs are essentially universal and can be used to detect any component other than the carrier gas (as long as their thermal conductivities are different from that of the carrier gas, at detector temperature), FIDs are sensitive primarily to hydrocarbons, and are more sensitive to them than TCD. However, an FID cannot detect water. Both detectors are also quite robust. Since TCD is non-destructive, it can be operated in-series before an FID (destructive), thus providing complementary detection of the same analytes.

Other detectors are sensitive only to specific types of substances, or work well only in narrower ranges of concentrations. They include:

• discharge ionization detector (DID), which uses a high-voltage electric discharge to produce ions.
• electron capture detector (ECD), which uses a radioactive Beta particle Beta particles are high-energy, high-speed electrons or positrons emitted by certain types of radioactive nuclei such as potassium-40. The beta particles emitted are a form of ionizing radiation also known as beta rays. The production of beta particles is termed beta decay. They are designated by the Greek letter beta . There are two forms of beta (electron) source to measure the degree of electron capture.
• flame photometric detector (FPD)
• flame ionization detector A flame ionization detector is a type of gas detector used in gas chromatography. The first flame ionization detector was developed in 1957 by scientists working for the CSIRO in Melbourne, Australia (FID)
• Hall electrolytic conductivity detector (ElCD)
• helium ionization detector (HID)
• Nitrogen Phosphorus Detector (NPD)
• mass selective detector (MSD)
• photo-ionization detector (PID)
• pulsed discharge ionization detector (PDD)
• thermal energy(conductivity) analyzer/detector (TEA/TCD)

Some gas chromatographs are connected to a mass spectrometer Mass spectrometry is an analytical technique for the determination of the elemental composition of a sample or molecule. It is also used for elucidating the chemical structures of molecules, such as peptides and other chemical compounds. The MS principle consists of ionizing chemical compounds to generate charged molecules or molecule fragments which acts as the detector. The combination is known as GC-MS Gas chromatography-mass spectrometry is a method that combines the features of gas-liquid chromatography and mass spectrometry to identify different substances within a test sample. Applications of GC-MS include drug detection, fire investigation, environmental analysis, explosives investigation, and identification of unknown samples. GC/MS can. Some GC-MS Gas chromatography-mass spectrometry is a method that combines the features of gas-liquid chromatography and mass spectrometry to identify different substances within a test sample. Applications of GC-MS include drug detection, fire investigation, environmental analysis, explosives investigation, and identification of unknown samples. GC/MS can are connected to an NMR spectrometer Nuclear magnetic resonance spectroscopy, most commonly known as NMR spectroscopy, is the name given to a technique which exploits the magnetic properties of certain nuclei. This phenomenon and its origins are detailed in a separate section on nuclear magnetic resonance. The most important applications for the organic chemist are proton NMR and which acts as a back up detector. This combination is known as GC-MS-NMR. Some GC-MS-NMR are connected to an infrared spectrophotometer Infrared spectroscopy is the subset of spectroscopy that deals with the infrared region of the electromagnetic spectrum. It covers a range of techniques, the most common being a form of absorption spectroscopy. As with all spectroscopic techniques, it can be used to identify compounds or investigate sample composition. Infrared spectroscopy which acts as a back up detector. This combination is known as GC-MS-NMR-IR. It must, however, be stressed this is very rare as most analyses needed can be concluded via purely GC-MS.

Methods

The method is the collection of conditions in which the GC operates for a given analysis. Method development is the process of determining what conditions are adequate and/or ideal for the analysis required.

Conditions which can be varied to accommodate a required analysis include inlet temperature, detector temperature, column temperature and temperature program, carrier gas and carrier gas flow rates, the column's stationary phase, diameter and length, inlet type and flow rates, sample size and injection technique. Depending on the detector(s) (see below) installed on the GC, there may be a number of detector conditions that can also be varied. Some GCs also include valves which can change the route of sample and carrier flow. The timing of the opening and closing of these valves can be important to method development.

This image above shows the interior of a GeoStrata Technologies Eclipse Gas Chromatograph that runs continuously in three minute cycles. Two valves are used to switch the test gas into the sample loop. After filling the sample loop with test gas, the valves are switched again applying carrier gas pressure to the sample loop and forcing the sample through the Column for separation.

Carrier gas selection and flow rates

Typical carrier gases include helium, nitrogen, argon, hydrogen and air. Which gas to use is usually determined by the detector being used, for example, a DID requires helium as the carrier gas. When analyzing gas samples, however, the carrier is sometimes selected based on the sample's matrix, for example, when analyzing a mixture in argon, an argon carrier is preferred, because the argon in the sample does not show up on the chromatogram. Safety and availability can also influence carrier selection, for example, hydrogen is flammable, and high-purity helium can be difficult to obtain in some areas of the world. (See: Helium--occurrence and production.)

The purity of the carrier gas is also frequently determined by the detector, though the level of sensitivity needed can also play a significant role. Typically, purities of 99.995% or higher are used. Trade names for typical purities include "Zero Grade," "Ultra-High Purity (UHP) Grade," "4.5 Grade" and "5.0 Grade."

The carrier gas flow rate affects the analysis in the same way that temperature does (see above). The higher the flow rate the faster the analysis, but the lower the separation between analytes. Selecting the flow rate is therefore the same compromise between the level of separation and length of analysis as selecting the column temperature.

With GCs made before the 1990s, carrier flow rate was controlled indirectly by controlling the carrier inlet pressure, or "column head pressure." The actual flow rate was measured at the outlet of the column or the detector with an electronic flow meter, or a bubble flow meter, and could be an involved, time consuming, and frustrating process. The pressure setting was not able to be varied during the run, and thus the flow was essentially constant during the analysis. The relation between flow rate and inlet pressure is calculated with Poiseuille's equation for compressible fluids.

Many modern GCs, however, electronically measure the flow rate, and electronically control the carrier gas pressure to set the flow rate. Consequently, carrier pressures and flow rates can be adjusted during the run, creating pressure/flow programs similar to temperature programs.

Inlet types and flow rates

The choice of inlet type and injection technique depends on if the sample is in liquid, gas, adsorbed, or solid form, and on whether a solvent matrix is present that has to be vaporized. Dissolved samples can be introduced directly onto the column via a COC injector, if the conditions are well known; if a solvent matrix has to be vaporized and partially removed, a S/SL injector is used (most common injection technique); gaseous samples (e.g., air cylinders) are usually injected using a gas switching valve system; adsorbed samples (e.g., on adsorbent tubes) are introduced using either an external (on-line or off-line) desorption apparatus such as a purge-and-trap system, or are desorbed in the S/SL injector (SPME applications).

Sample size and injection technique

Sample injection

The real chromatographic analysis starts with the introduction of the sample onto the column. The development of capillary gas chromatography resulted in many practical problems with the injection technique. The technique of on-column injection, often used with packed columns, is usually not possible with capillary columns. The injection system, in the capillary gas chromatograph, should fulfil the following two requirements:

1. The amount injected should not overload the column.
2. The width of the injected plug should be small compared to the spreading due to the chromatographic process. Failure to comply with this requirement will reduce the separation capability of the column. As a general rule, the volume injected, V_inj, and the volume of the detector cell, V_det, should be about 1/10 of the volume occupied by the portion of sample containing the molecules of interest (analytes) when they exit the column.

Some general requirements, which a good injection technique should fulfill, are:

• It should be possible to obtain the column’s optimum separation efficiency.
• It should allow accurate and reproducible injections of small amounts of representative samples.
• It should induce no change in sample composition. It should not exhibit discrimination based on differences in boiling point, polarity, concentration or thermal/catalytic stability.
• It should be applicable for trace analysis as well as for undiluted samples.

Column selection

Column temperature and temperature program

The column(s) in a GC are contained in an oven, the temperature of which is precisely controlled electronically. (When discussing the "temperature of the column," an analyst is technically referring to the temperature of the column oven. The distinction, however, is not important and will not subsequently be made in this article.)

The rate at which a sample passes through the column is directly proportional to the temperature of the column. The higher the column temperature, the faster the sample moves through the column. However, the faster a sample moves through the column, the less it interacts with the stationary phase, and the less the analytes are separated.

In general, the column temperature is selected to compromise between the length of the analysis and the level of separation.

A method which holds the column at the same temperature for the entire analysis is called "isothermal." Most methods, however, increase the column temperature during the analysis, the initial temperature, rate of temperature increase (the temperature "ramp") and final temperature is called the "temperature program."

A temperature program allows analytes that elute early in the analysis to separate adequately, while shortening the time it takes for late-eluting analytes to pass through the column.

Data reduction and analysis

Qualitative analysis:

Generally chromatographic data is presented as a graph of detector response (y-axis) against retention time (x-axis), which is called a chromatogram. This provides a spectrum of peaks for a sample representing the analytes present in a sample eluting from the column at different times. Retention time can be used to identify analytes if the method conditions are constant. Also, the pattern of peaks will be constant for a sample under constant conditions and can identify complex mixtures of analytes. In most modern applications however the GC is connected to a mass spectrometer or similar detector that is capable of identifying the analytes represented by the peaks.

Quantitive analysis:

The area under a peak is proportional to the amount of analyte present in the chromatogram. By calculating the area of the peak using the mathematical function of integration, the concentration of an analyte in the original sample can be determined. Concentration can be calculated using a calibration curve created by finding the response for a series of concentrations of analyte, or by determining the relative response factor of an analyte. The relative response factor is the expected ratio of an analyte to an internal standard (or external standard) and is calculated by finding the response of a known amount of analyte and a constant amount of internal standard (a chemical added to the sample at a constant concentration, with a distinct retention time to the analyte).

In most modern GC-MS systems, computer software is used to draw and integrate peaks, and match MS spectra to library spectra.

Application

In general, substances that vaporize below ca. 300 °C (and therefore are stable up to that temperature) can be measured quantitatively. The samples are also required to be salt-free; they should not contain ions. Very minute amounts of a substance can be measured, but it is often required that the sample must be measured in comparison to a sample containing the pure, suspected substance.

Various temperature programs can be used to make the readings more meaningful; for example to differentiate between substances that behave similarly during the GC process.

Professionals working with GC analyze the content of a chemical product, for example in assuring the quality of products in the chemical industry; or measuring toxic substances in soil, air or water. GC is very accurate if used properly and can measure picomoles of a substance in a 1 ml liquid sample, or parts-per-billion concentrations in gaseous samples.

In practical courses at colleges, students sometimes get acquainted to the GC by studying the contents of Lavender oil or measuring the ethylene that is secreted by Nicotiana benthamiana plants after artificially injuring their leaves. These GC analyses hydrocarbons (C2-C40+). In a typical experiment, a packed column is used to separate the light gases, which are then detected with a TCD. The hydrocarbons are separated using a capillary column and detected with an FID. A complication with light gas analyses that include H₂ is that He, which is the most common and most sensitive inert carrier (sensitivity is proportional to molecular mass) has an almost identical thermal conductivity to hydrogen (it is the difference in thermal conductivity between two separate filaments in a Wheatstone Bridge type arrangement that shows when a component has been eluted). For this reason, dual TCD instruments are used with a separate channel for hydrogen that uses nitrogen as a carrier are common. Argon is often used when analysing gas phase chemistry reactions such as F-T synthesis so that a single carrier gas can be used rather than 2 separate ones. The sensitivity is less but this is a tradeoff for simplicity in the gas supply.

GCs in popular culture

Movies, books and TV shows tend to misrepresent the capabilities of gas chromatography and the work done with these instruments.

In the U.S. TV show CSI, for example, GCs are used to rapidly identify unknown samples. "This is gasoline bought at a Chevron station in the past two weeks," the analyst will say fifteen minutes after receiving the sample.

In fact, a typical GC analysis takes much more time; sometimes a single sample must be run more than an hour according to the chosen program; and even more time is needed to "heat out" the column so it is free from the first sample and can be used for the next. Equally, several runs are needed to confirm the results of a study - a GC analysis of a single sample may simply yield a result per chance (see statistical significance).

Also, GC does not positively identify most samples; and not all substances in a sample will necessarily be detected. All a GC truly tells you is at which relative time a component eluted from the column and that the detector was sensitive to it. To make results meaningful, analysts need to know which components at which concentrations are to be expected; and even then a small amount of a substance can hide itself behind a substance having both a higher concentration and the same relative elution time. Last but not least it is often needed to check the results of the sample against a GC analysis of a reference sample containing only the suspected substance.

A GC-MS can remove much of this ambiguity, since the mass spectrometer will identify the component's molecular weight. But this still takes time and skill to do properly.

Similarly, most GC analyses are not push-button operations. You cannot simply drop a sample vial into an auto-sampler's tray, push a button and have a computer tell you everything you need to know about the sample. According to the substances one expects to find the operating program must be carefully chosen.

A push-button operation can exist for running similar samples repeatedly, such as in a chemical production environment or for comparing 20 samples from the same experiment to calculate the mean content of the same substance. However, for the kind of investigative work portrayed in books, movies and TV shows this is clearly not the case.

See also

• Thin layer chromatography
• Analytical chemistry
• Chromatography
• Gas chromatography-mass spectrometry
• Katharometer
• Standard addition
• Unresolved Complex Mixture

References

1. ^ ^{a b c d} Pavia, Donald L., Gary M. Lampman, George S. Kritz, Randall G. Engel (2006). Introduction to Organic Laboratory Techniques (4th Ed.). Thomson Brooks/Cole. pp. 797-817. ISBN 978-0-495-28069-9.

External links

• Gas Chromatography at the Open Directory Project
• Gas Chromatography Help Site

Categories: Gas chromatography | Chromatography | Laboratory techniques | Scientific techniques | Separation processes

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