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Thermal ionization, also known as surface ionization or contact ionization, is a physical process whereby the atoms are desorbed from a hot surface, and in the process are ionized. Thermal
ionization Ionization or ionisation is the process by which an atom or a molecule acquires a negative or positive Electric charge, charge by gaining or losing electrons, often in conjunction with other chemical changes. The resulting electrically charged at ...
is used to make simple
ion source An ion source is a device that creates atomic and molecular ions. Ion sources are used to form ions for mass spectrometers, optical emission spectrometers, particle accelerators, ion implanters and ion engines. Electron ionization Elect ...
s, for
mass spectrometry Mass spectrometry (MS) is an analytical technique that is used to measure the mass-to-charge ratio of ions. The results are presented as a ''mass spectrum'', a plot of intensity as a function of the mass-to-charge ratio. Mass spectrometry is used ...
and for generating
ion beam An ion beam is a beam of ions, a type of charged particle beam. Ion beams have many uses in electronics manufacturing (principally ion implantation) and other industries. There are many ion beam sources, some derived from the mercury vapor ...
s. Thermal ionization has seen extensive use in determining atomic weights, in addition to being used in many geological/nuclear applications.


Physics

The likelihood of ionization is a function of the filament temperature, the
work function In solid-state physics, the work function (sometimes spelled workfunction) is the minimum thermodynamic work (i.e., energy) needed to remove an electron from a solid to a point in the vacuum immediately outside the solid surface. Here "immediately" ...
of the filament substrate and the
ionization energy In physics and chemistry, ionization energy (IE) is the minimum energy required to remove the most loosely bound electron of an isolated gaseous atom, Ion, positive ion, or molecule. The first ionization energy is quantitatively expressed as : ...
of the element. This is summarised in the Saha–Langmuir equation: : \frac = \frac \exp \Bigg(\frac\Bigg) where :: \frac = ratio of ion number density to neutral number density :: \frac = ratio of statistical weights (degeneracy) of ionic (''g''+) and neutral (''g''0) states :: W =
work function In solid-state physics, the work function (sometimes spelled workfunction) is the minimum thermodynamic work (i.e., energy) needed to remove an electron from a solid to a point in the vacuum immediately outside the solid surface. Here "immediately" ...
of surface :: \Delta E_\text =
ionization energy In physics and chemistry, ionization energy (IE) is the minimum energy required to remove the most loosely bound electron of an isolated gaseous atom, Ion, positive ion, or molecule. The first ionization energy is quantitatively expressed as : ...
of desorbed element :: k =
Boltzmann constant The Boltzmann constant ( or ) is the proportionality factor that relates the average relative thermal energy of particles in a ideal gas, gas with the thermodynamic temperature of the gas. It occurs in the definitions of the kelvin (K) and the ...
:: T = surface temperature Negative ionization can also occur for elements with a large
electron affinity The electron affinity (''E''ea) of an atom or molecule is defined as the amount of energy released when an electron attaches to a neutral atom or molecule in the gaseous state to form an anion. ::X(g) + e− → X−(g) + energy This differs by si ...
\Delta E_\text against a surface of low work function.


Thermal ionization mass spectrometry

One application of thermal ionization is
thermal ionization mass spectrometry Thermal ionization mass spectrometry (TIMS), also known as surface ionization, is a highly sensitive isotope mass spectrometry characterization technique. The isotopic ratios of radionuclides are used to get an accurate measurement for the elemen ...
(TIMS). In thermal ionization mass spectrometry, a chemically purified material is placed onto a
filament The word filament, which is descended from Latin ''filum'' meaning " thread", is used in English for a variety of thread-like structures, including: Astronomy * Galaxy filament, the largest known cosmic structures in the universe * Solar filament ...
which is then heated to high temperatures to cause some of the material to be ionized as it is thermally desorbed (boiled off) the hot filament. Filaments are generally flat pieces of metal around wide, thick, bent into an upside-down U shape and attached to two contacts that supply a current. This method is widely used in
radiometric dating Radiometric dating, radioactive dating or radioisotope dating is a technique which is used to Chronological dating, date materials such as Rock (geology), rocks or carbon, in which trace radioactive impurity, impurities were selectively incorporat ...
, where the sample is ionized under vacuum. The ions being produced at the filament are focused into an ion beam and then passed through a magnetic field to separate them by mass. The relative abundances of different isotopes can then be measured, yielding isotope ratios. When these isotope ratios are measured by TIMS, mass-dependent fractionation occurs as species are emitted by the hot filament. Fractionation occurs due to the excitation of the sample and therefore must be corrected for accurate measurement of the isotope ratio.Dickin, A.P., 2005. Radiogenic Isotope Geology 2nd ed. Cambridge: Cambridge University Press. pp. 21–22 There are several advantages of the TIMS method. It has a simple design, is less expensive than other mass spectrometers, and produces stable ion emissions. It requires a stable power supply, and is suitable for species with a low ionization energy, such as
strontium Strontium is a chemical element; it has symbol Sr and atomic number 38. An alkaline earth metal, it is a soft silver-white yellowish metallic element that is highly chemically reactive. The metal forms a dark oxide layer when it is exposed to ...
and
lead Lead () is a chemical element; it has Chemical symbol, symbol Pb (from Latin ) and atomic number 82. It is a Heavy metal (elements), heavy metal that is density, denser than most common materials. Lead is Mohs scale, soft and Ductility, malleabl ...
. The disadvantages of this method stem from the maximum temperature achieved in thermal ionization. The hot filament reaches a temperature of less than , leading to the inability to create atomic ions of species with a high ionization energy, such as
osmium Osmium () is a chemical element; it has Symbol (chemistry), symbol Os and atomic number 76. It is a hard, brittle, bluish-white transition metal in the platinum group that is found as a Abundance of elements in Earth's crust, trace element in a ...
and
tungsten Tungsten (also called wolfram) is a chemical element; it has symbol W and atomic number 74. It is a metal found naturally on Earth almost exclusively in compounds with other elements. It was identified as a distinct element in 1781 and first ...
. Although the TIMS method can create molecular ions instead in this case, species with high ionization energy can be analyzed more effectively with MC-ICP-MS.


See also

*
Langmuir–Taylor detector A Langmuir–Taylor detector, also called surface ionization detector or hot wire detector, is a kind of ionization detector used in mass spectrometry, developed by John Taylor based on the work of Irving Langmuir and K. H. Kingdon. Constructio ...
*
Irving Langmuir Irving Langmuir (; January 31, 1881 – August 16, 1957) was an American chemist, physicist, and metallurgical engineer. He was awarded the Nobel Prize in Chemistry in 1932 for his work in surface chemistry. Langmuir's most famous publicatio ...
*
Meghnad Saha Meghnad Saha (6 October 1893 – 16 February 1956) was an Indian astrophysicist and politician who helped devise the theory of Thermal ionization, thermal ionisation. His Saha ionization equation, Saha ionisation equation allowed astronomers to ...


References

{{DEFAULTSORT:Thermal Ionization Ion source Ionization