Atomic emission spectroscopy (AES) is a method of chemical analysis that uses the intensity of light emitted from a flame, plasma, arc, or spark at a particular wavelength to determine the quantity of an element in a sample. The wavelength of the atomic spectral line in the emission spectrum gives the identity of the element while the intensity of the emitted light is proportional to the number of atoms of the element. The sample may be excited by various methods.
Atomic Emission Spectroscopy allows us to measure interactions between electromagnetic radiation and physical atoms and molecules. This interaction is measured in the form of electromagnetic waves representing the changes in energy between atomic energy levels. When elements are burned by a flame, they emit electromagnetic radiation that can be recorded in the form of spectral lines. Each element has its own unique spectral line due to the fact that each element has a different atomic arrangement, so this method is an important tool for identifying the makeup of materials. Robert Bunsen and Gustav Kirchhoff were the first to establish atomic emission spectroscopy as a tool in chemistry. [1]
When an element is burned in a flame, its atoms move from the ground electronic state to the excited electronic state. As atoms in the excited state move back down into the ground state, they emit light. The Boltzmann expression is used to relate temperature to the number of atoms in the excited state where larger temperatures indicate a larger population of excited atoms. This relationship is written as:
where nupper and nlower are the number of atoms in the higher and lower energy levels, gupper and glower are the degeneracies in the higher and lower energy levels, and εupper and εlower are the energies of the higher and lower energy levels. The wavelengths of this light can be dispersed and measured by a monochromator, and the intensity of the light can be leveraged to determine the number of excited state electrons present. [2] For atomic emission spectroscopy, the radiation emitted by atoms in the excited state are measured specifically after they have already been excited.
Much information can be obtained from the use of atomic emission spectroscopy by interpreting the spectral lines produced from exciting an atom. The width of spectral lines can provide information about an atom’s kinetic temperature and electron density. Looking at the different intensities of spectral lines is useful for determining the chemical makeup of mixtures and materials. Atomic emission spectroscopy is mainly used for determining the makeup of mixes of molecules due to the fact that each element has its own unique spectrum. [3]
The sample of a material (analyte) is brought into the flame as a gas, sprayed solution, or directly inserted into the flame by use of a small loop of wire, usually platinum. The heat from the flame evaporates the solvent and breaks intramolecular bonds to create free atoms. The thermal energy also excites the atoms into excited electronic states that subsequently emit light when they return to the ground electronic state. Each element emits light at a characteristic wavelength, which is dispersed by a grating or prism and detected in the spectrometer.
A frequent application of the emission measurement with the flame is the regulation of alkali metals for pharmaceutical analytics. [4]
Inductively coupled plasma atomic emission spectroscopy (ICP-AES) uses an inductively coupled plasma to produce excited atoms and ions that emit electromagnetic radiation at wavelengths characteristic of a particular element. [5] [6]
Advantages of ICP-AES are the excellent limit of detection and linear dynamic range, multi-element capability, low chemical interference and a stable and reproducible signal. Disadvantages are spectral interferences (many emission lines), cost and operating expense and the fact that samples typically must be in a liquid solution. Inductively coupled plasma (ICP) source of the emission consists of an induction coil and plasma. An induction coil is a coil of wire that has an alternating current flowing through it. This current induces a magnetic field inside the coil, coupling a great deal of energy to plasma contained in a quartz tube inside the coil. Plasma is a collection of charged particles (cations and electrons) capable, by virtue of their charge, of interacting with a magnetic field. The plasmas used in atomic emissions are formed by ionizing a flowing stream of argon gas. Plasma's high-temperature results from resistive heating as the charged particles move through the gas. Because plasmas operate at much higher temperatures than flames, they provide better atomization and a higher population of excited states. The predominant form of sample matrix in ICP-AES today is a liquid sample: acidified water or solids digested into aqueous forms. Liquid samples are pumped into the nebulizer and sample chamber via a peristaltic pump. Then the samples pass through a nebulizer that creates a fine mist of liquid particles. Larger water droplets condense on the sides of the spray chamber and are removed via the drain, while finer water droplets move with the argon flow and enter the plasma. With plasma emission, it is possible to analyze solid samples directly. These procedures include incorporating electrothermal vaporization, laser and spark ablation, and glow-discharge vaporization.
Spark or arc atomic emission spectroscopy is used for the analysis of metallic elements in solid samples. For non-conductive materials, the sample is ground with graphite powder to make it conductive. In traditional arc spectroscopy methods, a sample of the solid was commonly ground up and destroyed during analysis. An electric arc or spark is passed through the sample, heating it to a high temperature to excite the atoms within it. The excited analyte atoms emit light at characteristic wavelengths that can be dispersed with a monochromator and detected. In the past, the spark or arc conditions were typically not well controlled, the analysis for the elements in the sample were qualitative. However, modern spark sources with controlled discharges can be considered quantitative. Both qualitative and quantitative spark analysis are widely used for production quality control in foundry and metal casting facilities.
Atomic absorption spectroscopy (AAS) is a spectroanalytical procedure for the quantitative measurement of chemical elements. AAS is based on the absorption of light by free metallic ions that have been atomized from a sample. An alternative technique is atomic emission spectroscopy (AES).
Spectroscopy is the field of study that measures and interprets electromagnetic spectrum. In narrower contexts, spectroscopy is the precise study of color as generalized from visible light to all bands of the electromagnetic spectrum.
Atomic, molecular, and optical physics (AMO) is the study of matter–matter and light–matter interactions, at the scale of one or a few atoms and energy scales around several electron volts. The three areas are closely interrelated. AMO theory includes classical, semi-classical and quantum treatments. Typically, the theory and applications of emission, absorption, scattering of electromagnetic radiation (light) from excited atoms and molecules, analysis of spectroscopy, generation of lasers and masers, and the optical properties of matter in general, fall into these categories.
Inductively coupled plasma mass spectrometry (ICP-MS) is a type of mass spectrometry that uses an inductively coupled plasma to ionize the sample. It atomizes the sample and creates atomic and small polyatomic ions, which are then detected. It is known and used for its ability to detect metals and several non-metals in liquid samples at very low concentrations. It can detect different isotopes of the same element, which makes it a versatile tool in isotopic labeling.
A spectral line is a weaker or stronger region in an otherwise uniform and continuous spectrum. It may result from emission or absorption of light in a narrow frequency range, compared with the nearby frequencies. Spectral lines are often used to identify atoms and molecules. These "fingerprints" can be compared to the previously collected ones of atoms and molecules, and are thus used to identify the atomic and molecular components of stars and planets, which would otherwise be impossible.
The emission spectrum of a chemical element or chemical compound is the spectrum of frequencies of electromagnetic radiation emitted due to electrons making a transition from a high energy state to a lower energy state. The photon energy of the emitted photons is equal to the energy difference between the two states. There are many possible electron transitions for each atom, and each transition has a specific energy difference. This collection of different transitions, leading to different radiated wavelengths, make up an emission spectrum. Each element's emission spectrum is unique. Therefore, spectroscopy can be used to identify elements in matter of unknown composition. Similarly, the emission spectra of molecules can be used in chemical analysis of substances.
Absorption spectroscopy is spectroscopy that involves techniques that measure the absorption of electromagnetic radiation, as a function of frequency or wavelength, due to its interaction with a sample. The sample absorbs energy, i.e., photons, from the radiating field. The intensity of the absorption varies as a function of frequency, and this variation is the absorption spectrum. Absorption spectroscopy is performed across the electromagnetic spectrum.
Plasma diagnostics are a pool of methods, instruments, and experimental techniques used to measure properties of a plasma, such as plasma components' density, distribution function over energy (temperature), their spatial profiles and dynamics, which enable to derive plasma parameters.
In physics, atomic spectroscopy is the study of the electromagnetic radiation absorbed and emitted by atoms. Since unique elements have unique emission spectra, atomic spectroscopy is applied for determination of elemental compositions. It can be divided by atomization source or by the type of spectroscopy used. In the latter case, the main division is between optical and mass spectrometry. Mass spectrometry generally gives significantly better analytical performance, but is also significantly more complex. This complexity translates into higher purchase costs, higher operational costs, more operator training, and a greater number of components that can potentially fail. Because optical spectroscopy is often less expensive and has performance adequate for many tasks, it is far more common. Atomic absorption spectrometers are one of the most commonly sold and used analytical devices.
Fluorescence spectroscopy is a type of electromagnetic spectroscopy that analyzes fluorescence from a sample. It involves using a beam of light, usually ultraviolet light, that excites the electrons in molecules of certain compounds and causes them to emit light; typically, but not necessarily, visible light. A complementary technique is absorption spectroscopy. In the special case of single molecule fluorescence spectroscopy, intensity fluctuations from the emitted light are measured from either single fluorophores, or pairs of fluorophores.
Gold fingerprinting is a method used to identify and authenticate gold items by analyzing the unique composition of impurities or trace elements within the metal. While gold itself is an inert and relatively uniform element, gold found in natural or processed items often contains small amounts of other elements, such as silver or lead. These trace elements, which vary depending on the source and refining process, serve as a "fingerprint" for the gold. By comparing the elemental composition of a gold sample to databases of known sources, experts can determine where the gold was likely mined or processed. This technique is applied in fields such as archaeology, geology, and forensic science, as it provides insights into the provenance of historical artifacts, mined gold, or stolen items.
Energy-dispersive X-ray spectroscopy, sometimes called energy dispersive X-ray analysis or energy dispersive X-ray microanalysis (EDXMA), is an analytical technique used for the elemental analysis or chemical characterization of a sample. It relies on an interaction of some source of X-ray excitation and a sample. Its characterization capabilities are due in large part to the fundamental principle that each element has a unique atomic structure allowing a unique set of peaks on its electromagnetic emission spectrum. The peak positions are predicted by the Moseley's law with accuracy much better than experimental resolution of a typical EDX instrument.
An inductively coupled plasma (ICP) or transformer coupled plasma (TCP) is a type of plasma source in which the energy is supplied by electric currents which are produced by electromagnetic induction, that is, by time-varying magnetic fields.
A glow discharge is a plasma formed by the passage of electric current through a gas. It is often created by applying a voltage between two electrodes in a glass tube containing a low-pressure gas. When the voltage exceeds a value called the striking voltage, the gas ionization becomes self-sustaining, and the tube glows with a colored light. The color depends on the gas used.
X-ray spectroscopy is a general term for several spectroscopic techniques for characterization of materials by using x-ray radiation.
Elemental analysis is a process where a sample of some material is analyzed for its elemental and sometimes isotopic composition. Elemental analysis can be qualitative, and it can be quantitative. Elemental analysis falls within the ambit of analytical chemistry, the instruments involved in deciphering the chemical nature of our world.
A flame test is relatively quick test for the presence of some elements in a sample. The technique is archaic and of questionable reliability, but once was a component of qualitative inorganic analysis. The phenomenon is related to pyrotechnics and atomic emission spectroscopy. The color of the flames is understood through the principles of atomic electron transition and photoemission, where varying elements require distinct energy levels (photons) for electron transitions.
Graphite furnace atomic absorption spectroscopy (GFAAS), also known as electrothermal atomic absorption spectroscopy (ETAAS), is a type of spectrometry that uses a graphite-coated furnace to vaporize the sample. Briefly, the technique is based on the fact that free atoms will absorb light at frequencies or wavelengths characteristic of the element of interest. Within certain limits, the amount of light absorbed can be linearly correlated to the concentration of analyte present. Free atoms of most elements can be produced from samples by the application of high temperatures. In GFAAS, samples are deposited in a small graphite or pyrolytic carbon coated graphite tube, which can then be heated to vaporize and atomize the analyte. The atoms absorb ultraviolet or visible light and make transitions to higher electronic energy levels. Applying the Beer-Lambert law directly in AA spectroscopy is difficult due to variations in the atomization efficiency from the sample matrix, and nonuniformity of concentration and path length of analyte atoms. Concentration measurements are usually determined from a working curve after calibrating the instrument with standards of known concentration. The main advantages of the graphite furnace comparing to aspiration atomic absorption are the following:
Inductively coupled plasma atomic emission spectroscopy (ICP-AES), also referred to as inductively coupled plasma optical emission spectroscopy (ICP-OES), is an analytical technique used for the detection of chemical elements. It is a type of emission spectroscopy that uses the inductively coupled plasma to produce excited atoms and ions that emit electromagnetic radiation at wavelengths characteristic of a particular element. The plasma is a high temperature source of ionised source gas. The plasma is sustained and maintained by inductive coupling from electrical coils at megahertz frequencies. The source temperature is in the range from 6000 to 10,000 K. The intensity of the emissions from various wavelengths of light are proportional to the concentrations of the elements within the sample.
Glow-discharge optical emission spectroscopy (GDOES) is a spectroscopic method for the quantitative analysis of metals and other non-metallic solids. The idea was published and patented in 1968 by Werner Grimm from Hanau, Germany.