Laser-induced breakdown spectroscopy

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Schematic of a LIBS system - Courtesy of US Army Research Laboratory Laser-induced breakdown spectroscopy (LIBS) is a type of atomic emission spectroscopy which uses a highly energetic laser pulse as the excitation source. The laser is focused to form a plasma, which atomizes and excites samples. In principle, LIBS can analyse any matter regardless of its physical state, be it solid, liquid or gas. Because all elements emit light of characteristic frequencies when excited to sufficiently high temperatures, LIBS can (in principle) detect all elements, limited only by the power of the laser as well as the sensitivity and wavelength range of the spectrograph & detector. In practice, detection limits are a function of a) the plasma excitation temperature, b) the light collection window, and c) the line strength of the viewed transition. LIBS makes use of optical emission spectrometry and is to this extent very similar to arc/spark emission spectroscopy. LIBS operates by focusing the laser onto a small area at the surface of the specimen; when the laser is discharged it ablates a very small amount of material, in the range of nanograms to picograms, which generates a plasma plume with temperatures in excess of 100,000 K. During data collection, typically after local thermodynamic equilibrium is established, plasma temperatures range from 5,000±20,000 K. At the high temperatures during the early plasma, the ablated material dissociates (breaks down) into excited ionic and atomic species. During this time, the plasma emits a continuum of radiation which does not contain any useful information about the species present, but within a very small timeframe the plasma expands at supersonic velocities and cools. At this point the characteristic atomic emission lines of the elements can be observed. The delay between the emission of continuum radiation and characteristic radiation is in the order of 10 µs, this is why it is necessary to temporally gate the detector.

LIBS can often be referred to as its alternative name: laser-induced plasma spectroscopy (LIPS). Unfortunately the term LIPS has alternative meanings that are outside the field of analytical spectroscopy, therefore the term LIBS is preferred. LIBS is technically very similar to a number of other laser-based analytical techniques, sharing much of the same hardware. These techniques are the vibrational spectroscopic technique of Raman spectroscopy, and the fluorescence spectroscopic technique of laserinduced fluorescence (LIF). In fact devices are now being manufactured which combine these techniques in a single instrument, allowing the atomic, molecular and structural characterisation of a specimen as well as giving a deeper insight into physical properties.

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1 Design 2 Advantages 3 Disadvantages 4 Recent developments 5 See also 6 References 7 Further reading

[edit] Design
A typical LIBS system consists of a neodymium doped yttrium aluminium garnet (Nd:YAG) solid-state laser and a spectrometer with a wide spectral range and a high sensitivity, fast response rate, time gated detector. This is coupled to a computer which can rapidly process and interpret the acquired data. As such LIBS is one of the most experimentally simple spectroscopic analytical techniques, making it one of the cheapest to purchase and to operate. The Nd:YAG laser generates energy in the near infrared region of the electromagnetic spectrum, with a wavelength of 1064 nm. The pulse duration is in the region of 10 ns generating a power density which can exceed 1 GW·cmí2 at the focal point. Other lasers have been used for LIBS, mainly the Excimer (Excited dimer) type that generates energy in the visible and ultraviolet regions. The spectrometer consists of either a monochromator (scanning) or a polychromator (non-scanning) and a photomultiplier or CCD detector respectively. The most common monochromator is the Czerny-Turner type whilst the most common polychromator is the Echelle type. However, even the Czerny-Turner type can be (and is often) used to disperse the radiation onto a CCD effectively making it a polychromator. The

polychromator spectrometer is the type most commonly used in LIBS as it allows simultaneous acquisition of the entire wavelength range of interest. The spectrometer collects electromagnetic radiation over the widest wavelength range possible, maximising the number of emission lines detected for each particular element. Spectrometer response is typically from 1100 nm (near infrared) to 170 nm (deep ultraviolet), the approximate response range of a CCD detector. All elements have emission lines within this wavelength range. The energy resolution of the spectrometer can also affect the quality of the LIBS measurement, since high resolution systems can separate spectral emission lines in close juxtaposition, reducing interference and increasing selectivity. This feature is particularly important in specimens which have a complex matrix, containing a large number of different elements. Accompanying the spectrometer and detector is a delay generator which accurately gates the detector's response time, allowing temporal resolution of the spectrum.

[edit] Advantages
Because such a small amount of material is consumed during the LIBS process the technique is considered essentially non-destructive or minimally-destructive, and with an average power density of less than one watt radiated onto the specimen there is almost no specimen heating surrounding the ablation site. Due to the nature of this technique sample preparation is typically minimised to homogenisation or is often unnecessary where heterogeneity is to be investigated or where a specimen is known to be sufficiently homogeneous, this reduces the possibility of contamination during chemical preparation steps. One of the major advantages of the LIBS technique is its ability to depth profile a specimen by repeatedly discharging the laser in the same position, effectively going deeper into the specimen with each shot. This can also be applied to the removal of surface contamination, where the laser is discharged a number of times prior to the analysing shot. LIBS is also a very rapid technique giving results within seconds, making it particularly useful for high volume analyses or on-line industrial monitoring. LIBS is an entirely optical technique, therefore it requires only optical access to the specimen. This is of major significance as fibre optics can be employed for remote analyses. And being an optical technique it is non-invasive, non-contact and can even be used as a stand-off analytical technique when coupled to appropriate telescopic apparatus. These attributes have significance for use in areas from hazardous environments to space exploration. Additionally LIBS systems can easily be coupled to an optical microscope for micro-sampling adding a new dimension of analytical flexibility. With specialised optics or a mechanically positioned specimen stage the laser can be scanned over the surface of the specimen allowing spatially resolved chemical analysis and the creation of 'elemental maps'. This is very significant as chemical imaging is becoming more important in all branches of science and technology. Portable LIBS systems are more sensitive, faster and can detect a wider range of elements (particularly the light elements) than competing techniques such as portable x-ray

Industrial applications of LIBS are e. And LIBS does not use ionizing radiation to excite the sample. Hydrogen as an impurity in solids). If the orthogonal laser pulse is delayed with respect to the perpendicular one. The accuracy of LIBS measurements is typically better than 10% and precision is often better than 5%. LIBS is one of several analytical techniques that can be deployed in the field as opposed to pure laboratory techniques e. The detection limits for LIBS vary from one element to the next depending on the specimen type and the experimental apparatus used. In orthogonal configuration a laser pulse is fired parallel to the sample surface either before or after the perpendicular pulse hits the specimen. The Mars Science Laboratory mission will bring ChemCam. onto Mars in 2012. low power. Recent developments in LIBS have seen the introduction of double-pulsed laser systems. [edit] Recent developments Recent interest in LIBS has focused on the miniaturization of the components and the development of compact. analysis of inclusions in steel. Double-pulsed systems are also proving useful in conducting analysis in liquids. It is subject to variation in the laser spark and resultant plasma which often limits reproducibility. The laser plasma ignited in the surrounding medium above the surface by a first pulse causes (by its shock wave) an area of reduced pressure above the specimen into which the actual plasma from the sample can expand. In perpendicular configuration the laser is fired twice on the same spot on the specimen with a pulse separation in the order of one to a couple of tens of microseconds. For double-pulse LIBS one distinguishes between orthogonal and perpendicular configuration. Depending on pulse separation. Recent research on LIBS is focusing on compact and (man-)portable systems. Even so detection limits of 1 to 30 ppm by mass are not uncommon. resulting in a reheating of the laser plasma leading to signal enhancement.fluorescence. It also significantly reduces the matrix effects. the detection of material mix-ups. a LIBS instrument. ESA as well as the military. but can range from >100 ppm to <1 ppm.g. [edit] Disadvantages LIBS. analysis of slags in . like all other analytical techniques is not without limitations. as the initial laser pulse forms a cavity bubble in which the second pulse acts on the evaporated material. This direction has been pushed along by interest from groups such as NASA. This has similar positive effects on sensitivity like LIBS performed at reduced pressures. the effects are similar as in the perpendicular configuration.g.g. spark OES. the second pulse is more or less absorbed by the plasma plume caused by the previous pulse. portable systems. Both double-pulse LIBS as well as LIBS at reduced pressures are aimed at increasing the sensitivity of LIBS and the reduction of errors caused by the differential volatility of elements (e. which is both penetrating and potentially carcinogenic.

and J. 20(6).secondary metallurgy and high-speed identification of scrap pieces for material specific recycling tasks. B.. Winefordner. 1275±1278 . L. Israel Schechter. Spectrochimica Acta Part B 56 (6): 637±649. Spectroscopy 2000. Lee Y. "Steel analysis with laser-induced breakdown spectrometry in the vacuum ultraviolet" Appl.. 385. K. 552-556. 2006) ISBN 0521852749 B.B. Noll. Smith. Winefordner. Gornushkin. Winefordner.. Amponsah-Manager. Handbook of Laser-Induced Breakdown Spectroscopy (London: John Wiley & Sons.W. Amponsah-Manager.W. (2001). 762-769. N.. 2004. Sturm V.1081/ASR-120028868.B. ³Microchip Laser Ablation of Metals: Investigation of the Ablation Process in View of its Application to Laser Induced Breakdown Spectroscopy´ JAAS 2005. Noll R. B. Peter L. ³Microchip Laser Induced Breakdown Spectroscopy: Preliminary Feasibility Investigation´ Applied Spectroscopy 2004. 37. and J. [edit] See also y y y y y Spectroscopy Atomic spectroscopy Raman spectroscopy Laser-induced fluorescence List of surface analysis methods [edit] References y y Lee W. Laser Induced Breakdown Spectroscopy (New York: Cambridge University Press. R. Miziolek. "Laser-induced breakdown spectrometry ± applications for production control and quality assurance in steel industry". Wu J. Smith I. N. 54. Y. R. Vincenzo Palleschi. Sturm. Peter. "High-speed laser-induced breakdown spectrometry for scanning microanalysis" J. Omenetto. ³Quantitation of Low-alloy Steel Samples by Powerchip Laser Induced Breakdown Spectroscopy´ JAAS 2005.. Radziemski. B. Mönch I.D.W. Smith. "Recent applications of laserinduced breakdown spectrometry: A review of material approaches". I. 58(7). Noll.D. D: Appl. Bette. doi:10. H. 2006) ISBN 0470092998 Andrzej W.. "New approach to monitoring the Al depth profile of hot-dip galvanised sheet steel online using laser-induced breakdown spectroscopy" Anal Bioanal Chem 2006. Omenetto. Noll. Balzer. Brysch A. Cremers & Leon J.1016/S0584-8547(01)00214-2. V. Kraushaar M. Phys. Omenetto. 225±233 V. Höhne. Sturm. [edit] Further reading y y y y y y y y David A.. doi:10. Lopez-Moreno.. Phys.D. M. (2004). Amponsah-Manager. N. C. Gornushkin. 544-551. 20(6). I. Gornushkin. 1281±1288 H. K. Sneddon J.Bette H.. K. and J. R. B. Applied Spectroscopy Review 39 (1): 27±97.

Spectrom. 23. 694±701 10. "Quantitative molecular analysis with molecular bands emission using laser-induced breakdown spectroscopy and chemometrics" J.y y y J. . . . Anal. .C.J. M.wikipedia. . . At.R. . .1039/b714219f . J.. Lyon. Vadillo. issue 2. . p. . R. 2008. Laserna. .org/wiki/Laser-induced_breakdown_spectroscopy" Categories: Scientific techniques | Spectroscopy Hidden categories: Articles lacking in-text citations from December 2010 | All articles lacking in-text citations Personal tools y Log in / create account Namespaces y y Article Discussion Variants Views y y y Actions Search Read Edit View history . "Laser-induced plasma spectrometry: truly a surface analytical tool" Spectrochimica Acta Part B: Atomic Spectroscopy 2004. Doucet. vol. Faustino." LEA S500" 2008. P. 147-161 F. 59.M. Sabsabi. 1 (Russian) [hide]v · d · eSpectroscopy Atomic spectroscopy · Emission spectroscopy · Electron spin resonance · Fluorescence spectroscopy · Gamma spectroscopy · Infrared spectroscopy · Laser-induced breakdown spectroscopy · Mössbauer spectroscopy · Nuclear magnetic resonance spectroscopy · Raman spectroscopy · Resonance enhanced multiphoton ionization · Rotational spectroscopy · Terahertz spectroscopy · Ultraviolet-visible spectroscopy · Vibrational spectroscopy · X-ray spectroscopy Retrieved from "http://en.J.

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LIBS Plasma plume The plasma is emitted into >2 steradians.For analysis of a wide range of samples. a filter is rarely required.wikipedia. Echelle spectrographs are typically used. The tighter the Laser-Induced Breakdown Spectroscopy (LIBS) LIBS Fundamentals A short laser pulse is focused on to the surface of a sample to create the plasma.y y y Privacy policy About Wikipedia Disclaimers http://en. A laser with a good Gaussian profile allows focusing to a near diffraction-limited spot. a system based on an echelle spectrograph offers a combination of high resolution and wide wavelength coverage.It is also possible to relay the laser light to the . For LIBS. Typically energies of only tens of millijoules are required. Sometimes a blocking filter is used to remove any scatter from the incident laser however. since the incident laser light and the signal are well resolved temporally. the less laser energy is required to produce the laser-induced breakdown. An Intensified CCD (ICCD) detector attached to a spectrograph analyzes the collected plasma light. so a fast f/1 lens will collect more light.

The plasma plume expands with time and the excited species relax further. The intensity of the plasma emission is usually high enough to allow good spectra to be recorded in single scan mode. but typically the evolution of the plasma and the changes in its content occur on a microsecond timescale.The high intensity laser pulse interacting with the sample produces a plasma plume that evolves with time from the point of impact of the incident laser pulse.The exact timing and the spectral lines vary with the type of sample. a high power laser pulse is focusedon to a sample to create a plasma or laser spark. the distance from the center of the plasma and the wavelength of the incident laser light.After around 1 s from the incident laser pulse. so a slow gate ICCD is suitable.The spectral emission occurs as a result of the subsequent relaxation of the constituent excited species.The atomic spectral lines can be used to determine the elemental composition or theelemental . The laser pulse usually lasts for 5 to 20ns.The plasma created breaks down all the sample's chemical bonds and ionizes many of the constituent elements.The emission from the plasma plume is collected and analyzed by the detection system.In the LIBS technique. consequently no discrete lines can be observed. with the controller board triggering the laser and the delay generator. Typical LIBS Configuration LIBS Techniques LIBS spectroscopy can be produced from a variety of lasers but typically excimers or pulsed Nd:Yag lasers are used.A typical experimental configuration is shown below.Emission from the atoms and ions in the plasma is collected by a lens or fiber optics and analyzed by a spectrograph and gated detector. The gating requirements of LIBS are not very demanding.sample and collect the signal by fiber optics. Applications of LIBS LIBS is a useful method for determining the elemental composition of various solids. white-light radiation.The spectrum that is observed in the first 100ns is dominated by continuous.Typically the emission is collected at some distance from the sample to reduce the significance of self-absorption effects or surface effects. intense. liquidsand gases. Gate times and delays of several microseconds are typical. discrete spectral lines originating from various ionic species start to become visible.The spectra below indicate how the spectral lines evolve over time. The system can usually be operated in internal trigger mode.

The analysis is similar tothat performed by an ICP (Inductively Coupled Plasma) analyzer.1 mol l-1nitric acid At 5 s atomic emission lines start to become visible through the broadened ionic lines At 10µs the atomic spectral lines dominate and clear identification of the atomic species is possible .The great appeal of LIBS is that little or no sample preparation is required to obtain useful results and the technique is readily portable to the field.concentrations in the sample. A typical spectrum seen from a solution of potassium pertechnetate dissolved in 0.

minimum insertion delay and compact detector head. lowest propagation delay. with features like fast or slow gating. without any compromises.Andor Solutions for LIBS Andor Recommended LIBS Cameras The Andor range of iStar cameras is ideally suited for LIBS. iStar iStar Options y y iStar Gen II W type photocathode iStar Gen II WR type photocathode The iStar offers a wide range of photocathodes and sensor depending on the exact application. . Based on the Echelle grating principle. Combined with an Andor iStar. internal delay generator and 25ps step resolution making the iStar the ideal choice for LIBS. this "no moving parts" spectrograph is unique. Andor advantages such as compact detector head. wide spectral range. Gating for LIBS applications is typically in the microsecond regime so the High QE "W" and "WR" type photocathodes are ideal for LIBS applications. When coupled with a Mechelle spectrometer this would provide an ideal LIBS solution. this patented design achieves the highest bandwidth coverage while simultaneously achieving the highest spectral resolution.

Permits analysis of extremely hard materials that are difficult to digest or dissolve.1 g to 1mg) and is therefore practically non-destructive. depending on the sample homogeneity. and excitation properties of the laser. ceramics and superconductors. sample matrix. Disadvantages of LIBS y y y y y Increased cost and system complexity.typically 5-10%. Difficulty in obtaining suitable standards (semi-quantitative). e. LIBS typically samples very small amounts of material (~0.QE curves relevant to LIBS Advantages of LIBS y y y y y y y y Versatile sampling of solids. Little or no sample preparation is necessary. greater convenience and fewer opportunities for contamination to occur. Possibility of simultaneous multi-elemental analysis. Local analysis in microregions offers a spatial resolving power of ~1-100 m.g. in the case of LIBS in aerosols. Poor precision .The result is increased throughput. Large interference effects (including matrix interference and. Potential for direct detection in aerosols (a solid or liquid particle in a gaseous medium). Simple and rapid analysis (ablation and excitation processes are carried out in a single step). gases or liquids. Detection limits are generally not as good as established solution techniques. . the potential interference of particle size).

Martin was able to produce a chemical "fingerprint" of wood based on heavy metals and other trace elements. Case Study Analysis of Wood Samples from a Crime Scene Using LIBS The Laboratory of Tree-Ring Science (LTRS) in the Department of Geography. 2) The logs likely came from the same tree or from a group of trees growing in the same area. Office of the Sheriff.University of Tennessee. Dr. Texas. and it has been steadily gaining a lot of importance in the research community. New techniques such as Femto-nano Dual-Pulse LIBS has taken LIBS into its next generation. Madhavi Martin at Oak Ridge National Labs (ORNL) was asked to determine if the logs from the crime scene could have originated from the same tree or from the same location as the logs found at the gathering. strongly suggesting that:1) The wood logs come from the same type of tree species. It was subsequently shown that the chemical fingerprint was consistent for all the wood samples that were tested. Collin County. received 14 logs from Criminal Investigation Section. Chemical "fingerprints" of wood from crime scene. Oak Ridge National Laboratory. Courtesy of Dr.D. and collection of plasma light still need to be worked on. However.y Possibility of ocular damage by the high-energy laser pulses. Oak Ridge TN Through a LIBS technique using an Andor iStar and a Mechelle.999% accurate and supported a successful conviction in this case. Ph.The results were shown to be 99. Dr. LIBS is a relatively new diagnostic tool. issues such as repeatabilty of results. before LIBS becomes a standard industry tool. Madhavi Martin. and it has helped to solve a number of issues being faced in . Environmental Sciences Division.

g. Inks. spectrographs or spectral analyzers. e. http://www. Neon and other noble gases have characteristic emission colors. a plot of the response of interest as a function of wavelength or frequency. spectroscopy originated through the study of visible light dispersed according to its wavelength. Historically. Spectroscopic data is often represented by a spectrum. search Analysis of white light by dispersing it with a prism is example of spectroscopy.this technique. however more work needs to be done before a standard solution is developed. Spectroscopy From Wikipedia. Spectral measurement devices are referred to as spectrometers. Spectroscopy is the study of the interaction between matter and radiated energy. Neon lighting is a direct application of atomic spectroscopy. Spectrometry and spectrography are terms used to refer to the measurement of radiation intensity as a function of wavelength and are often used to describe experimental spectroscopic methods. by a prism. and neon lamps use electricity to excite these emissions. dyes and paints include chemical compounds selected for their spectral characteristics in order to generate specific colors and hues. Later the concept was expanded greatly to comprise any interaction with radiative energy as a function of its wavelength or frequency. Daily observations of color can be related to spectroscopy. A commonly encountered molecular spectrum is that . There is a huge potential for LIBS in the industry and military.andor. the free encyclopedia Jump to: navigation.

identify and quantify chemicals. Spectroscopy is also used in astronomy and remote sensing.4 Nuclei 3 Other types 4 Applications 5 Scientists of note 6 See also 7 References 8 External links [edit] Theory One of the central concepts in spectroscopy is a resonance and its corresponding resonant frequency. Most research telescopes have spectrographs. Rayleigh scattering is a spectroscopic scattering phenomenon that accounts for the color of the sky.3 Type of material  2.2 Nature of the interaction o 2. and they can also be used to detect.3. A plot of amplitude vs.1 Atoms  2. and most spectral lines have a similar appearance. and this gives air polluted with nitrogen dioxide a reddish brown color.2 Molecules  2. Resonances were first characterized in mechanical systems such as pendulums. The measured spectra are used to determine the chemical composition and physical properties of astronomical objects (such as their temperature and velocity). Mechanical systems that vibrate or oscillate will experience large amplitude oscillations when they are driven at their resonant frequency. These spectra can be interpreted to derive information about the atoms and molecules. with the peak often referred to as a spectral line. Contents [hide] y y y y y y y y 1 Theory 2 Classification of methods o 2. Gaseous nitrogen dioxide has a characteristic red absorption feature.3 Crystals and extended materials  2.3.3. Spectroscopy is used in physical and analytical chemistry because atoms and molecules have unique spectra. Spectroscopic studies were central to the development of quantum mechanics and included Max Planck's explanation of blackbody radiation. excitation frequency will have a peak centered at the resonance frequency.1 Type of radiative energy o 2. Albert Einstein's explanation of the photoelectric effect and Niels Bohr's explanation of atomic structure and spectra.3. . This plot is one type of spectrum.of nitrogen dioxide.

were one of the experimental enigmas that drove the development and acceptance of quantum mechanics. [edit] Nature of the interaction Types of spectroscopy can also be distinguished by the nature of the interaction between the energy and the material. each one representing a resonance between two different quantum states. and the spectral patterns associated with them. can also be a source of radiative energy and both electrons and neutrons are commonly used. each with numerous implementations of specific spectroscopic techniques. its kinetic energy determines its wavelength. near infrared. via an oscillatory source of energy such as a photon.In quantum mechanical systems. The energy (E) of a photon is related to its frequency ( ) by E = h where h is Planck's constant. Acoustic spectroscopy involves radiated pressure waves. The hydrogen spectral series in particular was first successfully explained by the RutherfordBohr quantum model of the hydrogen atom. such as an atom. Techniques that employ electromagnetic radiation are typically classified by the wavelength region of the spectrum and include microwave. but spectral lines can also overlap and appear to be a single transition if the density of energy states is high enough. In many applications. photon frequency will peak at the resonant frequency or energy. similar to acoustic waves. The explanation of these series. Particles. [edit] Type of radiative energy Types of spectroscopy are distinguished by the type of radiative energy involved in the interaction. The types of radiative energy studied include: y y y y Electromagnetic radiation was the first source of energy used for spectroscopic studies. to solid materials. The coupling of the two states is strongest when the energy of the source matches the energy difference between the two states. Mechanical methods can be employed to impart radiating energy. The various implementations and techniques can be classified in several ways. terahertz. Particles such as electrons and neutrons have a comparable relationship. and so a spectrum of the system response vs. infrared. visible and ultraviolet. between their kinetic energy and their wavelength and frequency and therefore can also excite resonant interactions. due to their de Broglie wavelength. In some cases spectral lines are well separated and distinguishable. the de Broglie relations. Spectra of atoms and molecules often consist of a series of spectral lines. These interactions include: . [edit] Classification of methods Spectroscopy is a sufficiently broad field that many sub-disciplines exist. x-ray and gamma spectroscopy. the spectrum is determined by measuring changes in the intensity or frequency of this energy. the analogous resonance is a coupling of two quantum mechanical stationary states of one system. For a particle.

Atomic absorption spectroscopy (AAS) and atomic emission spectroscopy (AES) involve visible and ultraviolet light. For optical applications. often referred to as atomic spectral lines. to examine the arrangement of atoms in proteins and solid crystals. Crystallography employs the scattering of high energy radiation. Absorption is often determined by measuring the fraction of energy transmitted through the material. such as particle collisions and energy transfer. Robert Bunsen. A comprehensive explanation of the hydrogen spectrum was an early success of quantum mechanics and . Coherent or resonance spectroscopy are techniques where the radiative energy couples two quantum states of the material in a coherent interaction that is sustained by the radiating field. absorption will decrease the transmitted portion. Emission can also be induced by other sources of energy such as a flames or sparks or electromagnetic radiation in the case of fluorescence. developer of the Bunsen burner. are due to electronic transitions of an outer shell electron to an excited state. The coherence can be disrupted by other interactions. Emission indicates that radiative energy is released by the material. Impedance spectroscopy studies the ability of a medium to impede or slow the transmittance of energy. Atoms also have distinct x-ray spectra that are attributable to the excitation of inner shell electrons to excited states. Nuclear magnetic resonance (NMR) spectroscopy is a widely used resonance method and ultrafast laser methods are also now possible in the infrared and visible spectral regions. [edit] Type of material Spectroscopic studies are designed so that the radiated energy interacts with specific types of matter. A material's blackbody spectrum is a spontaneous emission spectrum determined by its temperature. Elastic scattering and reflection spectroscopy determine how incident radiation is reflected or scattered by a material. Atoms of different elements have distinct spectra and therefore atomic spectroscopy allows for the identification and quantitation of a sample's elemental composition. and Gustav Kirchhoff discovered new elements by observing their emission spectra. [edit] Atoms Atomic spectroscopy was the first application of spectroscopy developed. and so often require high intensity radiation to be sustained. such as x-rays and electrons. These absorptions and emissions. Inelastic scattering phenomena involve an exchange of energy between the radiation and the matter that shifts the wavelength of the scattered radiation.y y y y y y Absorption occurs when energy from the radiative source is absorbed by the material. Atomic absorption lines are observed in the solar spectrum and referred to as Fraunhofer lines after their discoverer. These include Raman and Compton scattering. this is characterized by the index of refraction.

molecular vibration and electronic states.explaining the Lamb shift observed in the hydrogen spectrum led to the development of quantum electrodynamics.. though. Distinct nuclear spin states can have their energy separated by a magnetic field. Molecular spectra can be obtained due to electron spin states (electron paramagnetic resonance). For instance. [edit] Nuclei Nuclei also have distinct energy states that are widely separated and lead to gamma ray spectra. Vibrations are relative motions of the atomic nuclei and are studied by both infrared and Raman spectroscopy. and this allows for NMR spectroscopy. Studies in molecular spectroscopy led to the development of the first maser and contributed to the subsequent development of the laser. Acoustic and mechanical responses are due to collective motions as well. blackbody radiation is due to the thermal motions of atoms and molecules within a material. rotational spectroscopy and microwave spectroscopy are synonymous. can have distinct spectral transitions and the crystal arrangement also has an effect on the observed molecular spectra. broader. Modern implementations of atomic spectroscopy for studying visible and ultraviolet transitions include flame emission spectroscopy. [edit] Molecules The combination of atoms into molecules leads to the creation of unique types of energetic states and therefore unique spectra of the transitions between these states. Electronic excitations are studied using visible and ultraviolet spectroscopy as well as fluorescence spectroscopy. molecular rotations. and spark or arc emission spectroscopy. electrons or neutrons allowing for crystallographic studies. These states are numerous and therefore have a high density of states. glow discharge spectroscopy. inductively coupled plasma atomic emission spectroscopy. Techniques for studying x-ray spectra include X-ray spectroscopy and X-ray fluorescence (XRF). microwave induced plasma spectroscopy. [edit] Crystals and extended materials The combination of atoms or molecules into crystals or other extended forms leads to the creation of additional energetic states. Rotations are collective motions of the atomic nuclei and typically lead to spectra in the microwave and millimeter-wave spectral regions. Pure crystals. The regular lattice structure of crystals also scatters x-rays. [edit] Other types . This high density often makes the spectra weaker and less distinct. i.e.

but uses neutrons instead of photons. See also Mössbauer effect. Deep-level transient spectroscopy measures concentration and analyzes parameters of electrically active defects in semiconducting materials Dual polarisation interferometry measures the real and imaginary components of the complex refractive index EPR spectroscopy Force spectroscopy Fourier transform spectroscopy is an efficient method for processing spectra data obtained using interferometers.[3] for selective excitation of atomic or molecular species. Mössbauer spectroscopy probes the properties of specific isotopic nuclei in different atomic environments by analyzing the resonant absorption of gammarays. Baryon spectroscopy and meson spectroscopy are both types of hadron spectroscopy. Inelastic electron tunneling spectroscopy (IETS) uses the changes in current due to inelastic electron-vibration interaction at specific energies that can also measure optically forbidden transitions. . also called Laser-induced plasma spectrometry (LIPS) Laser spectroscopy uses tunable lasers[2] and other types of coherent emission sources.[1] Cold vapour atomic fluorescence spectroscopy Correlation spectroscopy encompasses several types of two-dimensional NMR spectroscopy. such as optical parametric oscillators. parity. Hadron spectroscopy studies the energy/mass spectrum of hadrons according to spin. Cavity ring down spectroscopy Circular Dichroism spectroscopy Coherent anti-Stokes Raman spectroscopy (CARS) is a recent technique that has high sensitivity and powerful applications for in vivo spectroscopy and imaging.Other types of spectroscopy are distinguished by specific applications or implementations: y y y y y y y y y y y y y y y y y y y y y y Auger spectroscopy is a method used to study surfaces of materials on a microscale. It is often used in connection with electron microscopy. Photoemission spectroscopy Photothermal spectroscopy measures heat evolved upon absorption of radiation. Laser-Induced Breakdown Spectroscopy (LIBS). Inelastic neutron scattering is similar to Raman spectroscopy. Raman optical activity spectroscopy exploits Raman scattering and optical activity effects to reveal detailed information on chiral centers in molecules. Neutron spin echo spectroscopy measures internal dynamics in proteins and other soft matter systems Photoacoustic spectroscopy measures the sound waves produced upon the absorption of radiation. Fourier transform infrared spectroscopy (FTIR) is a common implementation of infrared spectroscopy NMR also employs Fourier transforms. and other particle properties.

[4] Cure monitoring of composites using Optical fibers [edit] Scientists of note y y y y y y y y y y y y y y y y y y y y y y y y y y Charles Glover Barkla Nikolay Basov Nicolaas Bloembergen Niels Bohr Bertram Brockhouse Robert Bunsen Arthur Compton Robert Curl Louis de Broglie Peter Debye Richard R. Glauber John L. Vibrational circular dichroism spectroscopy X-ray photoelectron spectroscopy (XPS) [edit] Applications y y Estimate weathered wood exposure times using near infrared spectroscopy. Hall Theodor W. Ernst James Franck Roy J. Thermal infrared spectroscopy measures thermal radiation emitted from materials and surfaces and is used to determine the type of bonds present in a sample as well as their lattice environment. mineralogists. The techniques are widely used by organic chemists. and planetary scientists. Hänsch Werner Heisenberg Gerhard Herzberg Victor Francis Hess Antony Hewish Dorothy Hodgkin Pierre Janssen Alfred Kastler Gustav Kirchhoff Harold Kroto Willis Eugene Lamb Norman Lockyer .y y y y y y y Saturated spectroscopy Scanning tunneling spectroscopy Spectrophotometry Time-resolved spectroscopy is the spectroscopy of matter in situations where the properties are changing with time.

1146/annurev.2008. Evans and X.112754 Annual Review of Analytical Chemistry. doi:10. Xie. Jr.S.1. ^ C.. Wilhelm Conrad Röntgen Johannes Rydberg Martin Ryle Arthur Leonard Schawlow Kai Siegbahn Manne Siegbahn Richard Smalley Johannes Stark Charles Hard Townes Joseph von Fraunhofer Philipp Eduard Anton von Lenard Kurt Wüthrich Pieter Zeeman Ahmed Zewail [edit] See also y y y y y y y y y y Absorption cross section Applied spectroscopy 2D correlation analysis Kelvin probe force microscope Metamerism (color) Rigid rotor Scattering theory Spectral power distributions Spectroscopic notation Spectrum analysis [edit] References 1.L. Coherent Anti-Stokes Raman Scattering Microscopy: Chemical Imaging for Biology and Medicine. 1: 883±909. .031207.anchem.y y y y y y y y y y y y y y y y y y y y y y y y y Hendrik Lorentz Theodore Lyman Albert Abraham Michelson Robert Andrews Millikan Edward Morley Rudolf Mössbauer Max Planck Aleksandr Mikhailovich Prokhorov Isidor Isaac Rabi Sir Chandrasekhara Venkata Raman Norman Foster Ramsey.

2. 3.

^ W. Demtröder, Laser Spectroscopy, 3rd Ed. (Springer, 2003). ^ F. J. Duarte (Ed.),Tunable Laser Applications, 2nd Ed. (CRC, 2009) Chapter 2. 4. ^ "Using NIR Spectroscopy to Predict Weathered Wood Exposure Times".

[edit] External links
y y y y y

Spectroscopy links at the Open Directory Project Amateur spectroscopy links at the Open Directory Project MIT Spectroscopy Lab's History of Spectroscopy Timeline of Spectroscopy NIST government spectroscopy data

F. J. Duarte (Ed.), Tunable Laser Applications, Second Edition (CRC, New York, 2009)
ISBN: 1420060090

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In chemistry, spectrophotometry is the quantitative measurement of the reflection or transmission properties of a material as a function of wavelength.[1] It is more specific than the general term electromagnetic spectroscopy in that spectrophotometry deals with visible light, near-ultraviolet, and near-infrared, but does not cover time-resolved spectroscopic techniques. Spectrophotometry involves the use of a spectrophotometer. A spectrophotometer is a photometer (a device for measuring light intensity) that can measure intensity as a function of the light source wavelength. Important features of spectrophotometers are spectral bandwidth and linear range of absorption or reflectance measurement. Spectrophotometers are commonly used for the measurement of transmittance or reflectance of solutions, transparent or opaque solids, such as polished glass, or gases. However they can also be designed to measure the diffusivity on any of the listed light ranges that usually cover around 200nm - 2500nm using different controls and calibrations.[2] Within these ranges of light, calibrations are needed on the machine using standards that vary in type depending on the wavelength of the photometric determination.[3] An example of an experiment in which spectrophotometry is used is the determination of the equilibrium constant of a solution. A certain chemical reaction within a solution may occur in a forward and reverse direction where reactants form products and products break down into reactants. At some point, this chemical reaction will reach a point of balance called an equilibrium point. In order to determine the respective concentrations of reactants and products at this point, the light transmittance of the solution can be tested using spectrophotometry. The amount of light that passes through the solution is indicative of the concentration of certain chemicals that do not allow light to pass through. The use of spectrophotometers spans various scientific fields, such as physics, materials science, chemistry, biochemistry, and molecular biology.[4] They are widely used in many industries including semiconductors, laser and optical manufacturing, printing and forensic examination, as well in laboratories for the study of chemical substances. Ultimately, a spectrophotometer is able to determine, depending on the control or calibration, what substances are present in a target and exactly how much through calculations of observed wavelengths.

y y y y y

1 Design 2 UV-visible spectrophotometry 3 IR spectrophotometry 4 Spectroradiometers 5 See also


6 References

[edit] Design

Single beam spectrophotometer There are two major classes of devices: single beam and double beam. A double beam spectrophotometer compares the light intensity between two light paths, one path containing a reference sample and the other the test sample. A single beam spectrophotometer measures the relative light intensity of the beam before and after a test sample is inserted. Although comparison measurements from double beam instruments are easier and more stable, single beam instruments can have a larger dynamic range and are optically simpler and more compact. Additionally, some specialized instruments, such as spectrophotometer built onto microscopes or telescopes, are single beam instruments due to practicality. Historically, spectrophotometers use a monochromator containing a diffraction grating to produce the analytical spectrum. The grating can either be movable or fixed. If a single detector, such as a photomultiplier tube or photodiode is used, the grating can be scanned stepwise so that the detector can measure the light intensity at each wavelength (which will correspond to each "step"). Arrays of detectors, such as charge coupled devices (CCD) or photodiode arrays (PDA) can also be used. In such systems, the grating is fixed and the intensity of each wavelength of light is measured by a different detector in the array. Additionally, most modern mid-infrared spectrophotometers use a Fourier transform technique to acquire the spectral information. The technique is called Fourier Transform Infrared. When making transmission measurements, the spectrophotometer quantitatively compares the fraction of light that passes through a reference solution and a test solution. For reflectance measurements, the spectrophotometer quantitatively compares the fraction of light that reflects from the reference and test samples. Light from the source lamp is passed through a monochromator, which diffracts the light into a "rainbow" of wavelengths and outputs narrow bandwidths of this diffracted spectrum. Discrete frequencies are transmitted through the test sample. Then the photon flux density (watts per metre squared usually) of the transmitted or reflected light is measured with a photodiode, charge coupled device or other light sensor. The transmittance or reflectance

These curves can be used to test a new batch of colorant to check if it makes a match to specifications e. need the data provided through colorimetry.. 3.without/with uv filter to control better the effect of uv brighteners within the paper stock. . and some of these instruments also operate into the near-infrared region as well. ISO printing standards. Visible region 400±700 nm spectrophotometry is used extensively in colorimetry science. There are two major setups for visual spectrum spectrophotometers.value for each wavelength of the test sample is then compared with the transmission (or reflectance) values from the reference sample. textiles vendors. In short. so the absorbancies of all other substances are recorded relative to the initial "zeroed" substance. Many older spectrophotometers must be calibrated by a procedure known as "zeroing.[4] [edit] UV-visible spectrophotometry Main article: Ultraviolet-visible spectroscopy The most common spectrophotometers are used in the UV and visible regions of the spectrum. the Beer-Lambert law holds and the absorbance between samples vary with concentration linearly. Where a colorant contains fluorescence. The names are due to the geometry of the light source. Ink manufacturers. If the compound is more concentrated more light will be absorbed by the sample. printing companies. A fraction of the light is transmitted or reflected from the sample The light from the sample is imaged upon the entrance slit of the monochromator The monochromator separates the wavelengths of light and focuses each of them onto the photodetector sequentially." The absorbancy of a reference substance is set as a baseline value. observer and interior of the measurement chamber. the sequence of events in a modern spectrophotometer is as follows: 1. Scientists use this instrument to measure the amount of compounds in a sample. and many more. In the case of printing measurements two alternative settings are commonly used. and produce a spectral reflectance curve or a data stream for alternative presentations. The light source is imaged upon the sample. Traditional visible region spectrophotometers cannot detect if a colorant or the base material has fluorescence.g. This can make it difficult to manage color issues if for example one or more of the printing inks is fluorescent. They take readings in the region of every 5±20 nanometers along the visible region. within small ranges. d/8 (spherical) and 0/45. 4. The spectrophotometer then displays % absorbancy (the amount of light absorbed relative to the initial substance). 2. a bi-spectral fluorescent spectrophotometer is used.

The detector detects how much light was reflected from or transmitted through the sample. Samples for IR spectrophotometry may be smeared between two discs of potassium bromide or ground with potassium bromide and pressed into a pellet. The detector then converts how much light the sample transmitted or reflected into a number. making it incompatible as an optical medium. The light source shines onto or through the sample. but infrared measurement is also challenging because virtually everything emits IR light as thermal radiation. or quartz. One major factor is the type of photosensors that are available for different spectral regions. 2. Components: 1. are designed to measure the spectral density of illuminants in order to evaluate and categorize lighting for sales by the manufacturer. depending on the region of interest. especially at wavelengths beyond about 5 m. or for the customers to confirm the lamp they decided to purchase is within their specifications. Where aqueous solutions are to be measured. which operate almost like the visible region spectrophotometers. insoluble silver chloride is used to construct the cell. 3. [edit] IR spectrophotometry Main article: Infrared spectroscopy Spectrophotometers designed for the main infrared region are quite different because of the technical requirements of measurement in that region. plastic. Ideal optical materials are salts. they may be constructed of glass. which do not absorb strongly. [edit] See also y y y y y y Atomic Absorption Spectrophotometry Atomic emission spectroscopy Inductively coupled plasma atomic emission spectroscopy Inductively coupled plasma mass spectrometry Spectroradiometry Slope spectroscopy [edit] References . The sample transmits or reflects light. [edit] Spectroradiometers Spectroradiometers. Another complication is that quite a few materials such as glass and plastic absorb infrared light.Samples are usually prepared in cuvettes. 4.

. In each samples measures fluorescent intensity. LIF spectra were measured by a developed measuring system.Japanese Abstract. Textile Sci. The Essential Guide to Analytical Chemistry. In this research. 1976. October 5). rayon cloth as standard cloth of sample. (author abst....wikipedia. 1617 4.C1-14(2005) Figure&Table&Reference. Retrieved from http://www. Country. Spectrophotometry. D. pp. (Brooks Haderlie. & Tsai. pp. Textile Sci. This paper also describes tried the grasp of the distribution situation of the model dirt in two dimensions. D. and Technol. Textile Sci. (Original Work Published 1943). C. and Technol. George. tried fixed quantity evaluation of model dirt. ( The Application of Laser Induced Fluorescence Spectroscopy to Measurement of Purity Level in Textiles Accession number.. B.06A0129627 Title. Then we used cotton cloth. PA. This paper describes a new purity level evaluation method in textiles by the application of LIF Spectroscopy..... ^ Allen.nist. JPN) TOBA EIJI(Shinshu Univ. There are a peculiar absorption and luminescence peak in the molecule. Cooksey. Georg.1. Cooksey. B. Saunders Company: Philadelphia.Jido Seigyo Rengo Koenkai (CD-ROM) Journal Code:F0989D ISSN: VOL.PAGE. & Tsai. (2010. JPN) ISHIZAWA HIROAKI(Shinshu Univ. Graduate School. B.Laser Induced Fluorescence (LIF) method is one of the fluorometric analysis methods that are very excellent methods as the method of the quantitative analysis of the material of a small amount.. ^ Schwedt. trans.) http://sciencelinks.NO. NY: Wiley.. we used artificial sweat and artificial lipid as model dirt of sample.. October 5).nist. Chichester. JPN) Journal Title. Retrieved from http://www.cfm 2.Japan Language.The Application of Laser Induced Fluorescence Spectroscopy to Measurement of Purity Level in Textiles Author. (1997). JPN) KANAI HIROYUKI(Shinshu .TANAKA TAKEYUKI(Shinshu Univ. JPN) NISHIMATSU TOYONORI(Shinshu Univ. cupra cloth. 46-55 http://en. Pub. C.. ^ a b Rendina.48th. Textile Sci.). Experimental Methods in Modern Biochemistry W.. ^ Allen. and Technol. 3. and Technol.

is an exact The basis of all progress in modern civilization is that there are people out there who are willing to study and learn most. progress and innovation have resulted from hours and hours of tedious testing and chemical analysis. www. EDXRF replaces AA & ICP wet Gravimetric Analysis High accuracy instrumentation for gases and vapours Chemical & Material Tests Comprehensive analytical laboratory for complex.senetas-europe. non-routine testing www.alliancetechgroup. Theoretical and physical sciences have dominated human pursuits for Change. Some of the best sources of new learning are experiments. This is why it involves complicated mathematical formulae.php How To Understand Different Chemical Analysis Methods By Staff Writer Ads by Google Trace Elemental Analysis PPB-level LLD for aqueous 5-Sulfo Isophthalic Acid Isophthalic Acid always in stock. There are many different chemical analyses techniques . Chemical methods and chemical testing are continually being improved to attain the precision that is requisite. if not all the processes in nature.east/article/200605/000020060506A0129627. Analytical chemistry. the branch of science that studies the chemical composition of matter. Small scale experiments that are successful are then created in large scale set ups that can be useful to society. In some cases environments and situations have to be simulated to gain better understanding and Tapping Fibre Optics Fibre Optic security de-bunked! See just how easy data can be stolen www. Professional chemistry distribution www.

With all the different types of chemical analysis.howtodothings.selected Article . To better understand this. qualitative analysis is the study of elements present in a given solution or compound. No counterweights are used here. Examples of these are titration and gravimetry. the added material is removed by some system or technique to identify the amount of the compound to be measured.employed in laboratories that are currently being used. of urine. an example of qualitative analysis involves the identification of the elements present in a sample of water. Another common example of traditional analytical techniques is gravimetry. y y Titration is the addition of an element or a compound to a solution to reach a point of equivalence. it can be concluded that these are done for the purpose of progress and change. In this system. In the lab. to know the figures corresponding to the amount of an element in a sample. For example. on the other hand. one will tend to find instruments that are specialized for only one function. And this is performed in the reverse order to determine just how much acid there is in a solution. the elements that form the acid are known through qualitative studies. in acid Abstract . Qualitative analysis is used. Traditional analytical techniques gather the same results. The most common and well-known type of titration is acid-base titration. Quantitative Analysis. This deals with the determination of the material by weighing the amount of material prior to an experiment and after the material¶s transformation. y y Qualitative Analysis. The neutralization that results from the reaction will determine just how much of the basic substance there is. and that function is either qualitative or quantitative. Rather. But any form of chemical testing belongs to either qualitative or quantitative measurement. an acid is added to a base to determine the amount of base present. What better way to innovate than by studying matter and finding the most applicable solutions to everyday problems? http://www. And the chemical methods vary because each kind is highly centered on the equipment being used. etc. while the amount of each part of the elements present are known through quantitative research. As the term suggests. This type is concerned with the make up or the composition of the object to be studied.

.Figures/Tables Figures/Tables . c a DuPont Haskell Laboratory for Health and Environmental Sciences. 02-093.95 Bogdan Szosteka. Pasteura 1. Newark. Pages 179-192 doi:10. All rights reserved. Warsaw.selected References References . 03-195. Jowita Orska-Gawrysb. DE 19719. Poland . Issue 2. Cited By in Scopus (55) Permissions & Reprints Investigation of natural dyes occurring in historical Coptic textiles by high-performance liquid chromatography with UV±Vis and mass spectrometric detection Purchase $ 41. 1090 Elkton Rd.V.1016/S0021-9673(03)01170-1 | How to Cite or Link Using DOI Copyright © 2003 Elsevier B. Warsaw University. Poland Department of Chemistry. .selected Journal of Chromatography A Volume 1012. 19 September 2003. USA b c Institute of Nuclear Chemistry and Technology. Izabella Surowiecc and Marek Trojanowicz . Warsaw. Dorodna 16.

kaempferol. Chromatographic retention.1. rhamnetin. utilizing different scanning modes of a triple quadrupole mass spectrometer. alizarin. monochloroalizarin. . and UV±Vis properties of reference substances 3. apigenin. Mass spectrometric detection. Difficulties with the ionization by electrospray were experienced for indigotin and brominated indigotins.and indigo-types were studied. Abstract Liquid chromatography (LC) combined with ultraviolet±visible (UV±Vis) and mass spectrometric (MS) detection was utilized to study the chemical components present in extracts of natural dyes originating from fiber samples obtained from Coptic textiles from Early Christian Art Collection of National Museum in Warsaw. alizarin. and so the type of dye that was utilized to dye the textiles could be identified. and indirubin showed similar signal-to-noise ratios for UV±Vis and mass spectrometric detection. anthraquinone. Using this approach the following compounds were identified in the extracts of Coptic textiles: luteolin.2. but these were ionized by atmospheric pressure chemical ionization. UV±Vis and mass spectra of twenty selected dye compounds of flavanoid-. ionization. mass spectrometric. Art analysis Article Outline 1. revised 12 June 2003. Chemicals 2. xanthopurpurin. Analysis of authentic fiber extracts Acknowledgements References . purpurin. Experimental 2. Available online 28 August 2003. Sample preparation and experimental procedures 3. The signal-tonoise ratios obtained for luteolin. combined with the UV±Vis detection was demonstrated to be a powerful approach to detection and identification of dyes in the extracts of archeological textiles. Most of the investigated compounds could be ionized by positive and negative ion electrospray ionization. Apparatus 2.2. Chromatographic. Detection capabilities for several dye-type analytes were compared for the UV±Vis and mass spectrometric detection. Purpurin. indirubin. Introduction 2. accepted 30 June 2003. apigenin. Results and discussion 3.1.3. Author Keywords: Dyes Subject-index terms: Textiles.Received 30 December 2002. and rhamnetin were higher for the MS detection for most of the examined sample extracts.

C. monochloroalizarin.5 min. (C) daughter ion spectrum of ion m/z: 491.2 min. Identification of carminic acid in sample extract of red silk using System I: (A) UV trace at 255 nm. alizarin. m/z: 273 (A-4). Negative (A) and positive (B) electrospray ion spectra of lac dye solution.Fig. carminic acid peak at 19. 2. Proposed fragmentation pattern for xanthopurpurin (B). (B) extracted ion trace for m/z: ion 491 from the full scan ESI chromatogram. Fig.5 min (C) daughter ion spectrum of m/z: 273 obtained for peak at 35. carminic acid peak at 19. A. Fig. (B) daughter ion spectrum of m/z: 239 obtained for peak at 33. m/z: 307 (A-5). 1. 3. m/z: 255 (A-3).3 min. 4. Identification of unknowns in the extract of sample red wool: (A-1) UV trace at 255 nm. Fig. extracted ion trace for ion m/z: 239 (A-2). Chromatography .

The two are not mutually exclusive. which separates the analyte to be measured from other molecules in the mixture based on differential partitioning between the mobile and stationary phases. Subtle differences in a compound's partition coefficient result in differential retention on the stationary phase and thus changing the separation. Chromatography may be preparative or analytical. It involves passing a mixture dissolved in a "mobile phase" through a stationary phase. chroma "color" and graphein "to write") Chromatography (from Greek is the collective term for a set of laboratory techniques for the separation of mixtures. This instrument records concentrations of acrylonitrile in the air at various points throughout the chemical laboratory. Contents [hide] y y y y y y 1 History 2 Chromatography terms 3 Techniques by chromatographic bed shape o 3.1 Gas chromatography o 5. The purpose of preparative chromatography is to separate the components of a mixture for further use (and is thus a form of purification).From Wikipedia. the free encyclopedia Jump to: navigation. search Pictured is a sophisticated gas chromatography system.1 Column chromatography o 3.2 Planar chromatography  3. Analytical chromatography is done normally with smaller amounts of material and is for measuring the relative proportions of analytes in a mixture.2.2 Thin layer chromatography 4 Displacement chromatography 5 Techniques by physical state of mobile phase o 5.2.1 Paper chromatography  3.1 Supercritical fluid chromatography .2 Liquid chromatography 6 Affinity chromatography o 6.

Analytical chromatography is used to determine the existence and possibly also the concentration of analyte(s) in a sample. Since then.7 Chiral chromatography 9 See also 10 References 11 External links History Main article: History of chromatography The history of chromatography begins during the mid-19th century. primarily for the separation of plant pigments such as chlorophyll. and their work encouraged the rapid development of several types of chromatography method: paper chromatography. was used²and named² in the first decade of the 20th century. They established the principles and basic techniques of partition chromatography. the technology has advanced rapidly.4 Pyrolysis gas chromatography o 8. Chromatography. and what would become known as high performance liquid chromatography. gas chromatography.y y y y y 7 Techniques by separation mechanism o 7. allowing the separation of increasingly similar molecules.6 Countercurrent chromatography o 8. Chromatography terms y y y The analyte is the substance to be separated during chromatography. New types of chromatography developed during the 1930s and 1940s made the technique useful for many types of separation process. resulting in the different varieties of chromatography described below.3 Simulated moving-bed chromatography o 8. Researchers found that the main principles of Tsvet's chromatography could be applied in many different ways.1 Reversed-phase chromatography o 8. advances continually improved the technical performance of chromatography.1 Ion exchange chromatography o 7. Chromatography became developed substantially as a result of the work of Archer John Porter Martin and Richard Laurence Millington Synge during the 1940s and 1950s.2 Two-dimensional chromatography o 8.5 Fast protein liquid chromatography o 8. Simultaneously. A bonded phase is a stationary phase that is covalently bonded to the support particles or to the inside wall of the column tubing. . literally "color writing".2 Size-exclusion chromatography 8 Special techniques o 8.

The eluent is the solvent that will carry the analyte. The mobile phase consists of the sample being separated/analyzed and the solvent that moves the sample through the column. Chromatography is a physical method of separation in which the components to be separated are distributed between two phases. or a supercritical fluid (supercritical-fluid chromatography. An immobilized phase is a stationary phase which is immobilized on the support particles. mass spectrometer or a variety of other detectors) corresponding to the response created by the analytes exiting the system. one of which is stationary (stationary phase) while the other (the mobile phase) moves in a definite direction. In the case of an optimal system the signal is proportional to the concentration of the specific analyte separated. The eluate is the mobile phase leaving the column. y y y y y y y A chromatograph is equipment that enables a sophisticated separation e.y A chromatogram is the visual output of the chromatograph. gas chromatographic or liquid chromatographic separation.g. It may be a liquid (LC and CEC). a gas (GC). In the case of an optimal separation. Plotted on the x-axis is the retention time and plotted on the y-axis a signal (for example obtained by a spectrophotometer. or on the inner wall of the column tubing. In the case of HPLC the mobile phase consists of a non-polar solvent(s) such as . SFC). An eluotropic series is a list of solvents ranked according to their eluting power. different peaks or patterns on the chromatogram correspond to different components of the separated mixture. The mobile phase is the phase which moves in a definite direction.

y y y y y y hexane in normal phase or polar solvents in reverse phase chromotagraphy and the sample being separated. Preparative chromatography is used to purify sufficient quantities of a substance for further use. and if it is non polar (C-18) it is reverse phase. Column chromatography is a separation technique in which the stationary bed is within a tube. Techniques by chromatographic bed shape Column chromatography For more details on this topic. When we make one solvent immobile (by adsorption on a solid support matrix) and another mobile it results in most common applications of chromatography. The particles of the solid stationary phase or the support coated with a liquid stationary phase may fill the whole inside volume of the tube (packed column) or be concentrated on or along the inside tube wall leaving an open. see Column chromatography. except for that the solvent is driven through the column by applying positive pressure. When the sample is treated in the course of an analysis. The solvent refers to any substance capable of solubilizing other substance.g. unrestricted path for the mobile phase in the middle part of the tube (open tubular column). C. If matrix support is polar (e.) it is forward phase chromatography. Examples include the silica layer in thin layer chromatography Chromatography is based on the concept of partition coffecient. and the solvent is . Any solute will partition between two immissible solvents. and especially the liquid mobile phase in LC. It may consist of a single component or it may be a mixture of components. The stationary phase is the substance which is fixed in place for the chromatography procedure. the phase or the phases containing the analytes of interest is/are referred to as the sample whereas everything out of interest separated from the sample before or in the course of the analysis is referred to as waste. with improved separations compared to the old method. See also: Kovats' retention index The sample is the matter analyzed in chromatography. The retention time is the characteristic time it takes for a particular analyte to pass through the system (from the column inlet to the detector) under set conditions. Modern flash chromatography systems are sold as pre-packed plastic cartridges. paper.[1] In 1978.[2][3] The technique is very similar to the traditional column chromatography. Differences in rates of movement through the medium are calculated to different retention times of the sample. Still introduced a modified version of column chromatography called flash column chromatography (flash). rather than analysis. This allowed most separations to be performed in less than 20 minutes. sillica etc. W. The solute refers to the sample components in partition chromatography. The mobile phase moves through the chromatography column (the stationary phase) where the sample interacts with the stationary phase and is separated.

The introduction of gradient pumps resulted in quicker separations and less solvent usage. and the compounds within the mixture travel farther if they are non-polar. The paper is placed in a jar containing a shallow layer of solvent and sealed. Different compounds in the sample mixture travel different distances according to how strongly they interact with the stationary phase as compared to the mobile phase. The specific Retention factor (Rf) of each chemical can be used to aid in the identification of an unknown substance.pumped through the cartridge. and therefore do not travel as far. a fluidized bed is used. Systems may also be linked with detectors and fraction collectors providing automation. a polar substance. Planar chromatography Thin layer chromatography is used to separate components of chlorophyll Planar chromatography is a separation technique in which the stationary phase is present as or on a plane. serving as such or impregnated by a substance as the stationary bed (paper chromatography) or a layer of solid particles spread on a support such as a glass plate (thin layer chromatography). As the solvent rises through the paper. In expanded bed adsorption. Paper chromatography is a technique that involves placing a small dot or line of sample solution onto a strip of chromatography paper. . rather than a solid phase made by a packed bed. Paper chromatography For more details on this topic. it meets the sample mixture which starts to travel up the paper with the solvent. The plane can be a paper. More polar substances bond with the cellulose paper more quickly. for culture broths or slurries of broken cells. This paper is made of cellulose. see Paper chromatography. This allows omission of initial clearing steps such as centrifugation and filtration.

Thin layer chromatography (TLC) is a widely employed laboratory technique and is similar to paper chromatography. Operating parameters are adjusted to maximize the effect of this difference. alumina. baseline separation of the peaks can be achieved only with gradient elution and low column loadings. The speed at which any component of a mixture travels down the column in elution mode depends on many factors. Thus. and low throughput. Gas chromatography (GC). Techniques by physical state of mobile phase Gas chromatography For more details on this topic. especially at the preparative scale. and thereby be resolved. better separations. are operational complexity.[4] There are distinct differences between displacement and elution chromatography. it involves a stationary phase of a thin layer of adsorbent like silica gel. In many cases. Wide separation of peaks. Compared to paper. It is . But for two substances to travel at different speeds. Displacement chromatography The basic principle of displacement chromatography is: A molecule with a high affinity for the chromatography matrix (the displacer) will compete effectively for binding sites. In elution mode. instead of using a stationary phase of paper. two drawbacks to elution mode chromatography. The stationary phase is adhered to the inside of a small-diameter glass tube (a capillary column) or a solid matrix inside a larger metal tube (a packed column). due to gradient solvent pumping. or cellulose on a flat. due to low column loadings. and the choice between different adsorbents. inert substrate.Thin layer chromatography For more details on this topic. Gas chromatography is always carried out in a column. is a separation technique in which the mobile phase is a gas. which is typically "packed" or "capillary" (see below) . Displacement chromatography has advantages over elution chromatography in that components are resolved into consecutive zones of pure substances rather than ³peaks´. Gaussian peaks. is desired in order to achieve maximum purification. However. substances typically emerge from a column in narrow. it has the advantage of faster runs. there must be substantial differences in some interaction between the biomolecules and the chromatography matrix. Because the process takes advantage of the nonlinearity of the isotherms. For even better resolution and to allow for quantification. high-performance TLC can be used. Gas chromatography (GC) is based on a partition equilibrium of analyte between a solid stationary phase (often a liquid silicone-based material) and a mobile gas (most often Helium). a larger column feed can be separated on a given column with the purified components recovered at significantly higher concentrations. (GLC). and thus displace all molecules with lesser affinities. also sometimes known as Gas-Liquid chromatography. preferably to baseline. see Gas chromatography. see Thin layer chromatography.

silica as the stationary phase) are termed normal phase liquid chromatography (NPLC) and the opposite (e. It should also be noted that the following techniques can also be considered fast protein liquid chromatography if no pressure is used to drive the mobile phase through the stationary phase. though the high temperatures used in GC make it unsuitable for high molecular weight biopolymers or proteins (heat will denature them). Ironically the "normal phase" has fewer applications and RPLC is therefore used considerably more. it is well suited for use in the petrochemical. It is also used extensively in chemistry research. frequently encountered in biochemistry. the sample is forced through a column that is packed with a stationary phase composed of irregularly or spherically shaped particles. In the HPLC technique. Present day liquid chromatography that generally utilizes very small packing particles and a relatively high pressure is referred to as high performance liquid chromatography (HPLC). a porous monolithic layer. Affinity chromatography .g. watermethanol mixture as the mobile phase and C18 = octadecylsilyl as the stationary phase) is termed reversed phase liquid chromatography (RPLC). Liquid chromatography Preparative HPLC apparatus Liquid chromatography (LC) is a separation technique in which the mobile phase is a liquid.widely used in analytical chemistry. Liquid chromatography can be carried out either in a column or a plane. Methods in which the stationary phase is more polar than the mobile phase (e. and industrial chemical fields. toluene as the mobile phase. HPLC is historically divided into two different sub-classes based on the polarity of the mobile and stationary phases. See also Aqueous Normal Phase Chromatography. or a porous membrane by a liquid (mobile phase) at high pressure. environmental monitoring and remediation. Specific techniques which come under this broad heading are listed below.g.

see Size-exclusion chromatography. Immobilized Metal Affinity Chromatography (IMAC) is useful to separate aforementioned molecules based on the relative affinity for the metal (I. HPLC techniques exist that do utilize affinity chromatogaphy properties. Often these columns can be loaded with different metals to create a column with a targeted affinity. see Supercritical fluid chromatography. Smaller molecules are able to enter the pores of the media and. Affinity chromatography[5] is based on selective non-covalent interaction between an analyte and specific molecules. After purification.e. biotin or antigens. which bind to the stationary phase specifically. In conventional methods the stationary phase is an ion exchange resin that carries charged functional groups which interact with oppositely charged groups of the compound to be retained. Ion exchange chromatography is commonly used to purify proteins using FPLC. Traditional affinity columns are used as a preparative step to flush out unwanted biomolecules. but not very robust. and proteins. Supercritical fluid chromatography For more details on this topic. It is usually performed in columns but can also be useful in planar mode. Ion exchange chromatography uses ion exchange mechanism to separate analytes. Columns are often manually prepared. Affinity chromatography often utilizes a biomolecule's affinity for a metal (Zn. etc. However. . some of these tags are usually removed and the pure protein is obtained. Supercritical fluid chromatography is a separation technique in which the mobile phase is a fluid above and relatively close to its critical temperature and pressure. Ion exchange chromatography uses a charged stationary phase to separate charged compounds including amino acids. It is often used in biochemistry in the purification of proteins bound to tags.For more details on this topic. Techniques by separation mechanism Ion exchange chromatography For more details on this topic. see Affinity chromatography. Dionex IMAC). Size-exclusion chromatography (SEC) is also known as gel permeation chromatography (GPC) or gel filtration chromatography and separates molecules according to their size (or more accurately according to their hydrodynamic diameter or hydrodynamic volume). Fe.). These fusion proteins are labeled with compounds such as His-tags. Cu. see Ion exchange chromatography. peptides. Size-exclusion chromatography For more details on this topic. It is very specific.

The sample is spotted at one corner of a square plate. "polishing" step of a purification. The average residence time in the pores depends upon the effective size of the analyte molecules. The sample is put into direct contact with a platinum wire. Pyrolysis gas chromatography Pyrolysis gas chromatography mass spectrometry is a method of chemical analysis in which the sample is heated to decomposition to produce smaller molecules that are separated by gas chromatography and detected using mass spectrometry. the chemistry within a given column can be insufficient to separate some analytes. especially since it can be carried out under native solution conditions. However. airdried. Reversed-phase chromatography is an elution procedure used in liquid chromatography in which the mobile phase is significantly more polar than the stationary phase. Two-dimensional chromatography In some cases. This section requires expansion. Pyrolysis is the thermal decomposition of materials in an inert atmosphere or a vacuum. It is generally a low-resolution chromatography technique and thus it is often reserved for the final. It is possible to direct a series of unresolved peaks onto a second column with different physico-chemical (Chemical classification) properties. This section requires expansion.developed. Special techniques Reversed-phase chromatography For more details on this topic. it can be possible to separate compounds that are indistinguishable by one-dimensional chromatography. molecules are trapped and removed from the flow of the mobile phase. such species are the first to be eluted. This section requires expansion. see Reversed-phase chromatography. Simulated moving-bed chromatography For more details on this topic. or placed in a quartz sample tube.therefore. see Simulated moving bed. then rotated by 90° and usually redeveloped in a second solvent system. It is also useful for determining the tertiary structure and quaternary structure of purified proteins. Depending on the application even higher . molecules that are larger than the average pore size of the packing are excluded and thus suffer essentially no retention. and rapidly heated to 600 ± 1000° C. Since the mechanism of retention on this new solid support is different from the first dimensional separation.

These fragments can be separated by gas chromatography. To enable chiral separations to take place. Chiral chromatography HPLC columns (with a chiral stationary phase) in both normal and reversed phase are commercially available. Fast protein liquid chromatography For more details on this topic. inductive heating (Curie Point filament).temperatures are used. In the case of enantiomers. giving differing affinities between the analytes. where both the stationary and mobile phases are liquids. various methylating reagents can be added to a sample before pyrolysis. and good results of derivatization inside the PTV injector are published as well. Quantitative data can be acquired.650° C. Fast protein liquid chromatography (FPLC) is a term applied to several chromatography techniques which are used to purify proteins. more volatile fragments. these have no chemical or physical differences apart from being threedimensional mirror images. The main advantage is that no dedicated instrument has to be purchased and pyrolysis can be performed as part of routine GC analysis. see Countercurrent chromatography. Chiral chromatography Chiral chromatography involves the separation of stereoisomers. This is sufficient for some pyrolysis applications. Large molecules cleave at their weakest points and produce smaller. pyrolysis GC of solid and liquid samples can be performed directly inside Programmable Temperature Vaporizer (PTV) injectors that provide quick heating (up to 30°C/sec) and high maximum temperatures of 600 . either the mobile phase or the stationary phase must themselves be made chiral. In this case quartz GC inlet liners have to be used. Many of these techniques are identical to those carried out under high performance liquid chromatography. see Fast protein liquid chromatography. Three different heating techniques are used in actual pyrolyzers: Isothermal furnace. See also . Countercurrent chromatography (CCC) is a type of liquid-liquid chromatography. It involves mixing a solution of liquids. and resistive heating using platinum filaments. Besides the usage of dedicated pyrolyzers. Countercurrent chromatography For more details on this topic. however use of FPLC techniques are typically for preparing large scale batches of a purified product. allowing them to settle into layers and then separating the layers. To increase the volatility of polar fragments. The data can either be used as fingerprint to prove material identity or the GC/MS data is used to identify individual fragments to obtain structural information. Conventional chromatography or other separation processes are incapable of separating them. Pyrolysis GC chromatograms are typically complex because a wide range of different decomposition products is formed.

Experimental organic chemistry: Principles and Practice (Illustrated ed. ISBN 978-1-60327-261-2. many of the art restoration and art conservation techniques we use today to save some of the world¶s most highly valued art wouldn¶t exist ± and neither would many of these precious works of art.. C. 4. Ehrlich. pp. Moody (13 June 1989). This often odd pairing of individuals has become an essential relationship in the world of art restoration and art conservation. ISBN 978-0-89603-694-9. An Overview of Affinity Chromatography. Chem.. Without the application of chemist¶s skills and knowledge. Christopher J.. How Scientific Methods are Used in Art Restoration By Senior Conservator Peggy Van Witt © 2010 Peggy Van Witt. Mitra. 3. 1978. Chem. W. M. A.1021/jo00408a041 ^ Laurence M. George K. doi:10. 4. . WileyBlackwell. TX 78737 ^ Pascal Bailon. 2. ISBN 9780632020171. No. Org. the art community and the scientific community have joined forces.819±872. 2000. Pure & Appl. In recent years. 65. 5. Humana Press.). 43(14). Harwood. ^ Displacement Chromatography 101. ^ IUPAC Nomenclature for Chromatography IUPAC Recommendations 1993. Vol. 180±185. 1993. Austin. Wen-Jian Fung and Wolfgang Berthold. ^ Still. J. 2923± 2925. Kahn. All Rights Reserved.y y y y Aqueous Normal Phase Chromatography Flash gas chromatography Multicolumn countercurrent solvent gradient purification (MCSGP) Purnell equation y y y y Chromatography in blood processing Chromatography software Van Deemter equation Binding selectivity References 1. Inc. pp. Sachem.

To detect such pollutants.Scientists. Scientists who work in museums and art galleries engage in a broad range of art conservation and art restoration activities. computer modeling. biology. what environmental factors may be contributing to their deterioration (often called corrosion products) and the materials used in previous attempts to conserve or restore the piece of art. not to mention a serious loss of monetary value. most often studying the chemical composition and structure of artifacts. Though most of the work done by scientific art conservators for art conservation and art restoration involves the use of analytical techniques. biological activity such as the growth of mold spores or insects. many other areas of chemistry. Drastic fluctuations in relative humidity will cause dimensional changes in wood furniture. physics. mostly chemists. High relative humidity can lead to mold growth and foxing on books and prints. biodegradation studies. The harmony between the scientific community and the art world has become quite obvious. as previously mentioned. Many artifacts are sensitive to destructive environmental agents in the museum and art gallery atmospheres. To detect pests. and panel paintings. metallographic. dating methods. and engineering are involved. polychrome sculpture. kinetic studies. while low relative humidity will cause photographic prints and films to become brittle. scientists will often use such high-tech tools as ultraviolet scanners and visible illumination procedures. are employed by some of the most famous museums and galleries around the world as art conservators. They conduct many investigations into various types of artwork. measuring relative humidity. These activities include polymer chemistry. These changes often lead to cracking and splitting of the wood with loss of painted surface decoration. and corrosion engineering. which includes monitoring the air for pollutants using very technical and complicated scientific tools. imaging methodologies. . scientists employed by museums as art conservator¶s use specialized tools. Other scientific endeavors of these art conservation artists include checking the effects of the museum's environment on the artwork.

needles were used on humans to inject or withdraw fluids from humans and animals. art conservation or art restoration. Now that the scientific community and the art world have combined. Previous to their widespread use in the art conservation and art restoration world. the scientific art conservators willuse nondestructive methods during the analysis. such as ultraviolet and infrared reflectance and fluorescence. Like other scientific methods. such as a non-required sampling. known as holistic examination or just a section of it. . Other methods. modern scientific art conservator¶s methods of analysis take such a minute amount of a sample that they are in effect. are always preferable. The most commonly used method of holistic art conservation and art restoration science is x-ray radiography.The ways in which scientific art conservators approach an art conservation or art restoration is usually divided into two classes: those that provide an image of the entire object. are used to show areas of compositional difference indicating restoration or variation in the pigments used by the artist. However. needles are used to collect paint samples from paintings or inject a small dose of varnish into a hard-to-reach area of a painting. the use of x-ray technology was adopted by the art world from the arena of human and veterinary medicine. Whenever possible. which may or may not involve sampling. and those which analyze a small point on the object. nondestructive. Such nondestructive methods. where variations in the density and average atomic number of the sample attenuate an x-ray beam. leaving a negative image on film. de la 4 euro mp. with or without sampling. http://www. Chemists working in museums engage in a broad range of investigations. Though analytical techniques appear to dominate. and those that provide an analysis at a point on the object. great care must be taken to identify areas which need art restoration or art conservation. calitate.print-bannere. However. and preservation of cultural property. and engineering. most frequently studying the chemical composition and structure of artifacts. represent a second major area of research. and ultraviolet and visible illumination. With painting specimens from painted surfaces. not requiring sampling. modern methods of analysis can be employed on such minute samples that they are in effect nondestructive. and conservation. physics. play active roles in conservation science. and the materials used in their repair. samples must be taken for methods that are in principle nondestructive because the object . biology. are always preferable. fluctuations in temperature and relative humidity. A third area of interest is the evaluation of the effectiveness. and corrosion engineering.eclipsepaper. Nondestructive methods. Restoration of paper-based items such as comics.Science has helped greatly in the sampling arena by making the impact on the works of art so minute that it is essential nondestructive. many other areas of chemistry. Many feel that such a minute sample may not be representative of the entirety of the composition of the artifact but may in fact be an inclusion or contaminant introduced in patchy or small amounts to only a section of the painting. prints. the ability to analyze minute samples raises a few concerns. biological activity. suport inclus. or may have been introduced by the art conservator. In some cases. computer modeling. biodegradation studies. The effects of the museum environment. safety. dating methods. authentication. and long-term stability of materials and techniques for the conservation of works of art. restoration.vanwittart. Methods of examination may be divided into two classes: those that provide an image of the entire object (holistic examination) or a section of it. documents Home > Library > Science > Sci-Tech Encyclopedia The application of chemistry to the technical McGraw-Hill Science & Technology Encyclopedia: Art conservation chemistry Ads Bannere si printuriwww. including air pollutants. including polymer chemistry. 2 ani garantie. kinetic studies. rapiditate Eclipse Paperwww. imaging methodologies. their corrosion products.

Secondary ion mass spectrometry (SIMS) would begin to penetrate the oxidized area. ion scattering spectrometry (ISS) would see the initial fraction-of-ananometer. Rapid changes in relative humidity will cause dimensional changes in wood furniture. polychrome sculpture. predominantly adsorbed species and contaminants. embedded in transparent resin. Auger electron spectrometry (AES) would examine the bulk of the oxidized layer. and studies of technique. thermoluminescence dating for ceramics) is possible. Many artifacts are sensitive to destructive agents in the museum atmosphere. fission track dating for uranium glass. Conservation studies of the composition and technique embrace the entire spectrum of modern chemical analysis. Thus. trace-element distributions. such as ultraviolet and infrared reflectance and fluorescence. and panel paintings. Auger effect. The separation of the fake from the authentic is a small but often spectacular aspect of the technical examination of artifacts. where variations in the density and average atomic number of the sample attenuate an x-ray beam. small samples are taken under the binocular microscope. leading to cracking and splitting of the wood with loss of painted surface decoration. Secondary ion mass spectrometry (SIMS). With specimens from painted surfaces. and polished to produce a cross section for microscopic examination. High relative humidity can lead to mold growth and foxing on books and too large to fit into a sample chamber. Analytical chemistry. . A further concern arises from the differing depths from which signals originate. The most commonly employed holistic method is x-ray radiography. the issue of authenticity turns upon anachronisms in composition or technique when the artifact in question is compared to accepted artifacts of the period. This permits a study of the artist's painting technique and shows how several layers may have been built up to achieve a desired effect. See also Activation analysis. The ability to analyze minute samples introduces the serious concern that the sample may not be representative of the composition of the artifact but may be an inclusion or contaminant introduced by the experimentalist. In the examination of paintings. radiocarbon dating for organic materials. great care must be taken to identify areas of restoration. See also Chemical microscopy. More commonly. In some cases. direct age determination (dendrochronology for panel paintings. Other methods. are used to show areas of compositional difference indicating restoration or variation in the pigments used by the artist. On a metal surface. while low relative humidity will cause photographic prints and films to become brittle. leaving a negative image on film. and x-ray-induced photoelectron spectrometry (XPS) would give data on the bulk sample some 10 nm below the specimen surface. the greater part of the work in the conservation laboratory concerns the building of databases of analyses of composition. See also Luminescence analysis.

one of the most widely used sample preparation methods is solid-phase extraction (SPE) that in the mid 1990s largely replaced the conventional but time consuming liquidliquid extraction (LLE). The SPE method resembles chromatography itself: a liquid sample is passed through a packed column that selectively removes interferences or analytes.g. These pollutants cause the degradation of leather.answers. free of interferences and safe for the column. spotting of photographic prints. tarnishing of silver plate. libraries. The SPE sample preparation technique is frequently carried out in a small. and fading of dyes and Solid-Phase Extraction Posted in Column Chromatography on Dec 15. plastic column (cartridge) that looks like a 10-mL medical syringe.Oxidation of iron objects. The common air pollutants sulfur dioxide (SO2) and ozone (O3) have been monitored at elevated levels in museums. Chemical methods of analysis are used to identify degradation products and to study the kinetics of degradation mechanisms. and the development of corrosion products on lead artifacts by the action of formic and acetic acids emitted by wooden display cases have regularly been observed in museums. . and archives. Specialists in air-pollution monitoring use analytical instrumentation to measure ambient pollution levels in museums. The column is packed with a small amount (< 1. Today. especially in chromatography where samples have to be homogenous. disposable. C18-silica) which is held in place by frits.0 g) of sorbent (e. http://www. 2010 Sample preparation is a crucial step in any analytical method.

the later has its own name . mechanisms and effects .justchromatography. or even coated fibers. a 96well plate. the SPE method can also be implemented by using a micro-pipette tip. SPE is typically used to: y y y increase concentration of the analyte remove interferences (for complex organic sample matrix and also to protect the column) desalt (in ion-exchange chromatography) http://www. May 1998.1016/S0169-4332(97)00734-4 | How to Cite or Link Using DOI Copyright © 1998 Elsevier Science B. Pages 738-745 doi:10. All rights reserved Cited By in Scopus (79) Permissions & Reprints Excimer laser restoration of painted artworks: Applied Surface Science Volumes 127-129.Disposable cartridge for SPE (syringe style) However.³solid-phase microextraction´ or SPME. a disk.V.

95 S. Fotakis Foundation for Research and Technology-Hellas. surpassing by far the degree of selectivity afforded by traditional restoration methods. V. Georgiou*. C.O. 248 nm is shown to be appropriate for achieving sufficient etching rates in combination with good surface morphology. highly effective method of restoration of painted artworks. In all. Author Keywords: Physical radiation effects. with minimal light penetration to the sublayers. Crete. Furthermore. and laser-induced breakdown spectroscopy. thereby safeguarding against damage. Greece Available online 13 October 1998. these experiments indicate that optimal fluence ranges can be defined in which damaging effects to the substrate are minimal or insignificant. UV laser irradiation.Purchase $ 35. Box 1527. Broadband reflectography. In particular. excimer laser cleaning can be a highly selective process. Anglos. Tornari and C. UV ablation. and by examining the degree of photolysis of photosensitive dopants incorporated in model samples. Zafiropulos. On the basis of structural and analytical examinations. the importance of photochemical effects is addressed by chromatographic analysis of irradiated realistic samples for the detection of photoproducts. providing information on the elemental composition of the ablated material. a number of different laser analytical techniques can be used for on-line monitoring and control. Furthermore. appear to be particularly effective in this respect. Institute of Electronic Structure and Laser. Potential consequences of laser-induced photomechanical effects are addressed via the use of holographic interferometry. Art conservation/restoration Subject-index terms: LC . With proper optimization of the irradiation parameters. D. P. 71110 Heraklion. providing structural information about the uncovered layers. the plausible consequences of the laser irradiation on the state of the paintings are investigated in experiments involving model and realistic systems. Abstract Excimer laser ablation is demonstrated to afford a novel. Balas. V. The application relies on the strong UV-absorptivity of these substrates ensuring efficient material removal.

sciencedirect. Methodology and procedures 4. Introduction md5=c4a4a3cc60b6f240d34fbaa5c768ff2b&searchtype=a Chemistry and Art Chemistry and cultural heritage . Assessment of the laser-induced effects &_origin=gateway&_sort=d&_docanchor=&view=c&_searchStrId=1709356534&_rerun Origin=scholar. Ablation characteristics 3. Summary Acknowledgements References http://www.Article Outline 1.

The role of chemistry is understanting. mainly through chemical transformations.Cultural heritage is the complex of monume nts and artifacts of historical. are deeply involved with cultural heritage. Our Lady of Grace that make This most famous painting has big conservation problems up the legacy of the past and document the evolution of countries and nations. . cultural and artistic value. Chemistry and its techniques. so it can be enjoyed in the present and in the future. Leonardo da Vinci. Cultural heritage must be maintained and conveyed to the next generations. controlling and repairing such transformations. technical. preventing. Cultural goods are subject to degradation. The Last Supper. therefore. about 1495/98 Milan.

The chemical constitution and properties of such materials determine the characteristics of the final work. Saint Peter in Chains Chemistry of paintings Painting is based on colors. and the effect of aging. New colors can be formed from the . and colors are the result of interaction between light and chemical substances. in dictating rules for handling. When a painter chooses his colors. he is actually selecting what chemical substances he will lay on his table (or wall. though they often didn't understand the chemical basis for such features. Sculptors have always been concerned with the features of their materials. Chemical reactions can make dyes disappear. Michelangelo. or turn to different colors. Nowadays chemistry is actively involved in materials selection. Slightly different hues may be due to completely different chemical formulas.Ch em ist ry of sc ulpture Sculpture is the art of making statues and other works of art from hard materials such as stones and metals. the way of processing. or whatever). Colors are not stable. Moses Rome. The last issue is especially important for ancient sculptures. and in caring conservation.

temperature and humidity control. They are not. in a stable state but are subject to continuous change. therefore. Protecting the artifacts and alleviating the negative effects of such factors is a critical task for chemistry. before and Right. removal of dirty layers. Highly degraded ancient books Chemical literacy for conservation Kn owl edg e of the che mic al nat ure (co Cleaning the tympanum of the portal of Seville Cathedral. mostly due to environmental factors and human action.painting materials. like all objects. Protection of cultural heritage Cultural goods. or added by deposition. Conservation techniques include exclusion from the contact with air. It is a great challenge for chemists to prevent or slow down such changes. Spain Left. after the treatment . for instance of smokes. have a definite chemical composition and chemical reactivity.

Cited By in Scopus (28) . d) During the restoration several methods o instrumental chemical analysis have been employed y y y Evaluation of the state of the artifacts and of the ongoing processes Setup of suitable procedures for cleaning. All rights are the prerequisite for conservation and restoration.whatischemistry. structure. reactivity) and of the physical properties of the materials constituting cultural artifacts. strenghtening and protecting cultural goods Evaluation of effectivenes of the treatment and its duration in time Many powerful analytical techniques and sophisticated equipment are available to accomplish such tasks. properties.V. Issue 2. London. Pages 317-325 doi:10. National Gallery 1553 a) The restored painting. as well as their source and way of processing.unina.mposition. Tasks belonging to chemistry in the conservation and restoration of cultural heritage include: y Knowledge of the factors affecting the degradation Restoration of Holbein's painting The Ambassador.html Analytica Chimica Acta Volume 480. c).1016/S0003-2670(02)01660-4 | How to Cite or Link Using DOI Copyright © 2003 Elsevier Science B. b). http://www. 24 March 2003.

Orso Priory palace (Aosta. The main inorganic pigments used by the unknown artist. red and yellow ochre. namely mercury sulphide. Non-destructive analysis Article Outline 1. Conclusions . carbon black and lead tin yellow type I have been identified. Italy) in view of their restoration. Author Keywords: Raman microscopy. Torino. Lorenzo Appoloniab and Piero Mirti a . Italy Received 2 October 2002. Università di Torino.Permissions & Reprints Non-destructive in situ determination of pigments in 15th century wall paintings by Raman microscopy Purchase $ 41. Aosta. Piazza Narbonne 3. I-11100. and the presence of organic substances and of some decay products (calcium sulphate and oxalate) has been observed. Italy Soprintendenza per i Beni e le Attività Culturali. white lead. Pigments. accepted 23 December 2002. Wall paintings. Introduction 2. azurite. via Giuria 5. Results and discussion 5. . Description of the paintings 3. Available online 28 January 2003. revised 23 December 2002.a Dipartimento di Chimica Analitica. . I-10125.95 Alessandra Perardia. Transportable equipment. The use of a transportable instrument has made it possible to work non-destructively in situ without sampling. b Abstract Raman microscopy has been applied to the study of 15th century wall paintings in a chapel of St. Experimental 4. origin=gateway&_sort=d&_docanchor=&view=c&_searchStrId=1709370976&_rerunOri gin=scholar. Furthermore.opticsinfobase. Pages 239-246 doi:10. Finally.V. the technique is minimally destructive. Under optimal experimental parameters. showing the capability of the technique in performing depth profile analysis. Issue 5=7dd83a1e58b566fef16c1a4eb40b70a3&searchtype=a Abstract Laser-induced breakdown spectroscopy (LIBS) was employed for the in situ analysis of pigments used in painting. subjected to partial restoration. Appropriate emission lines for the identification of the metallic elements in the pigments examined are proposed. http://www.cfm?id=131378 Spectrochimica Acta Part B: Atomic Spectroscopy Volume 48. and practically nondestructive determination of pigments in painted artworks.1016/0584-8547(93)80029-T | How to Cite or Link Using DOI Copyright © 1993 Published by Elsevier B. recording LIBS spectra from successive laser pulses on the same spot of a model oil painting resulted in information regarding the pigment composition of several paint layers. Cited By in Scopus (28) Permissions & Reprints . The results of our studies demonstrate the applicability of LIBS in the rapid. a test case is presented in which an 18th century oil painting. two pulses from a laser beam focused on the sample surface result in the formation of a small crater with typical diameter around 40 mu m and depth of no more than 10 mu m. was examined by LIBS. LIBS spectra were collected from a wide variety of pigments in powder form and in oil color test samples.Acknowledgements References in situ. and the different pigments used in the original and in the restored part of the work were clearly identified. February 1993.

von Bohlena. Spain . Belgium b Received 13 July 1992. F.2004. Various pigments were identified and their mixing proportion was determined even quantitatively. Pages 379-389 Papers presented at the VIIIth International Symposium on Analytical Methodology in the Environmental Field and XIIIth Meeting of the Spanish Society of Analytical Chemistry. A. Laboratory of Analytical Chemistry.50 R. Klockenämpera. 25 October 2004. Available online 5 December 2001. Issues 1-2. Analytica Chimica Acta Volume 524. Devosb a Institut für Spektrochemie und angewandte Spektroskopie. Abstract The analytical characterization of artists' pigments is a most helpful tool for art history. Ghent University. A very gentle method of ultra-microsampling was developed that is especially applicable to paintings under restoration. Cited By in Scopus (15) Permissions & Reprints . This minute amount is sufficient for total-reflection X-ray fluorescence (TXRF) to determine most of those elements building inorganic pigments. All rights reserved.034 | How to Cite or Link Using DOI Copyright © 2004 Elsevier B.R. L.21-24 October 2003 doi:10.V. conservation and restoration of paintings.1016/j. It provides a sample mass of about 1 g and is virtually non-destructive. Moensb and W. accepted 3 September 1992.Proceedings of the fourth workshop on total-reflection x-ray fluorescence (TXRF) Analytical characterization of artists' pigments used in old and modern paintings by totalreflection X-ray fluorescence Purchase $ 31. Ghent.aca.G. Dortmund. The convenient and fast method was applied to oil paintings.06. University of A Coruna.

fungus and mould presence. and gypsum. Decaying. P. FT-IR spectroscopy and ion chromatography have been applied to the study of mortars and wall paintings in the church of Santa Mar a de Hermo (Asturias. Salts . some decay products have been determined. minium and cinnabar. 1°.Scientific analysis versus restorer¶s expertise for diagnosis prior to a restoration process: the case of Santa Maria Church (Hermo. .M. 48080 Bilbao. red ochre. Casals 2. 48004 Bilbao. Abstract Raman spectroscopy with portable fiber optics microprobe. revised 10 June 2004. Pigments. Asturias. Box 644. Pérez-Alonsoa. Madariagaa Department of Analytical Chemistry. North of Spain) Purchase $ 41. This scientific analysis was performed to compare with a diagnosis report based on restorer¶s expertise. Clear evidence of nitrate migration from the graveyard behind the northern wall of the church has been determined from the quantification of nitrate salts by ion chromatography. The detachment of the pigment grains from the wall paintings is attributed to the loss of the binding power of CaCO3 by its partial transformation into calcium nitrate due to chemical reactions with nitrates. The church showed problems of damp as well as clear evidences of flora. The combination of both vibrational spectroscopic techniques made it possible to determine the chromatic palette of the wall paintings composed of: CaCO3. accepted 10 June 2004. M. carbon black.95 M. Castroa.O. K. yellow ochre. Keywords: Wall paintings. Álvarezb and J. From the conclusions of the scientific analysis the supposedly distemper wall paintings from the XVIIth century were confirmed as frescoes and were then dated back to the XVth century by the art historians. North of Spain) before the restoration works. Spain Received 14 April 2004. Available online 3 August 2004. University of the Basque Country. a . Spain b Restorer. such as nitrate salts. In addition.

2. Nature and decay of the wall paintings 6. White washing and plasters 5.Article Outline 1. . Experimental 4. Presence of oxalates 5. Description of the church 3. Conclusions Acknowledgements References Fig.1. Discussion 5. Salts determination 5.5. Results 5. Scheme of the church and location of mortar sample points.4.3. Repainting 5. 1. Introduction 2.

2. 5. showing also bands of calcite (Ca) and nitrates (NO3). 3. . FT-IR spectrum of the innermost stratum in mortar sample 3 showing calcium carbonate (Ca). Fig. Fig. Fig. Raman spectrum of the blackish mortar sample with carbon black (1600 and 1315 cmí1) and gypsum (1135. (b) sample 1_1 with (MgCO3)4·Mg(OH)2·5H2O. FT-IR spectra: (a) pure (MgCO3)4·Mg(OH)2·5H2O standard.Fig. 493 and 414 cmí1). 1008. 4. nitrate salts (NO3) and silicates (Si).

Nitrate percentage determined in mortar samples by ion chromatography. Londonhttp://www. origin=gateway&_sort=d&_docanchor=&view=c&_searchStrId=1709371814&_rerunOri 5=a7fda6815d24e6a2d5f9d579ae800562&searchtype=a njZUG0&feature=relmfu . . Detail of one of the wall paintings from the nave. London Colour in paintings | The National Gallery.Restoring a panel painting | The National Gallery.