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Sunday, July 24, 2022

Skin cancer

From Wikipedia, the free encyclopedia

Skin cancer
Basal cell carcinoma.jpg
A basal-cell skin cancer. Note the pearly appearance and telangiectasia.

SpecialtyOncology and dermatology
SymptomsBasal-cell: painless raised area of skin that may be shiny with small blood vessel running over it or ulceration
Squamous-cell: hard lump with a scaly top
Melanoma: mole that has changed in size, shape, color, or has irregular edges
TypesBasal-cell skin cancer (BCC), squamous-cell skin cancer (SCC), melanoma
CausesUltraviolet radiation from the Sun or tanning beds
Risk factorsLight skin, poor immune function
Diagnostic methodTissue biopsy
PreventionDecreasing exposure to ultraviolet radiation, sunscreen
TreatmentSurgery, radiation therapy, fluorouracil
Frequency5.6 million (2015)
Deaths111,700 (2015)

Skin cancers are cancers that arise from the skin. They are due to the development of abnormal cells that have the ability to invade or spread to other parts of the body. There are three main types of skin cancers: basal-cell skin cancer (BCC), squamous-cell skin cancer (SCC) and melanoma. The first two, along with a number of less common skin cancers, are known as nonmelanoma skin cancer (NMSC). Basal-cell cancer grows slowly and can damage the tissue around it but is unlikely to spread to distant areas or result in death. It often appears as a painless raised area of skin that may be shiny with small blood vessels running over it or may present as a raised area with an ulcer. Squamous-cell skin cancer is more likely to spread. It usually presents as a hard lump with a scaly top but may also form an ulcer. Melanomas are the most aggressive. Signs include a mole that has changed in size, shape, color, has irregular edges, has more than one color, is itchy or bleeds.

More than 90% of cases are caused by exposure to ultraviolet radiation from the Sun. This exposure increases the risk of all three main types of skin cancer. Exposure has increased, partly due to a thinner ozone layer. Tanning beds are another common source of ultraviolet radiation. For melanomas and basal-cell cancers, exposure during childhood is particularly harmful. For squamous-cell skin cancers, total exposure, irrespective of when it occurs, is more important. Between 20% and 30% of melanomas develop from moles. People with lighter skin are at higher risk as are those with poor immune function such as from medications or HIV/AIDS. Diagnosis is by biopsy.

Decreasing exposure to ultraviolet radiation and the use of sunscreen appear to be effective methods of preventing melanoma and squamous-cell skin cancer. It is not clear if sunscreen affects the risk of basal-cell cancer. Nonmelanoma skin cancer is usually curable. Treatment is generally by surgical removal but may, less commonly, involve radiation therapy or topical medications such as fluorouracil. Treatment of melanoma may involve some combination of surgery, chemotherapy, radiation therapy and targeted therapy. In those people whose disease has spread to other areas of the body, palliative care may be used to improve quality of life. Melanoma has one of the higher survival rates among cancers, with over 86% of people in the UK and more than 90% in the United States surviving more than 5 years.

Skin cancer is the most common form of cancer, globally accounting for at least 40% of cancer cases. The most common type is nonmelanoma skin cancer, which occurs in at least 2–3 million people per year. This is a rough estimate, however, as good statistics are not kept. Of nonmelanoma skin cancers, about 80% are basal-cell cancers and 20% squamous-cell skin cancers. Basal-cell and squamous-cell skin cancers rarely result in death. In the United States, they were the cause of less than 0.1% of all cancer deaths. Globally in 2012, melanoma occurred in 232,000 people and resulted in 55,000 deaths. White people in Australia, New Zealand and South Africa have the highest rates of melanoma in the world. The three main types of skin cancer have become more common in the last 20 to 40 years, especially regions where the population is predominantly white.

Classification

There are three main types of skin cancer: basal-cell skin cancer (basal-cell carcinoma) (BCC), squamous-cell skin cancer (squamous-cell carcinoma) (SCC) and malignant melanoma.

Cancer Description Illustration
Basal-cell carcinoma Note the pearly translucency to fleshy color, tiny blood vessels on the surface, and sometimes ulceration which can be characteristics. The key term is translucency.
Basal cell carcinoma3.JPG
Squamous-cell skin carcinoma Commonly presents as a red, crusted, or scaly patch or bump. Often a very rapidly growing tumor.
Squamous Cell Carcinoma1.jpg
Malignant melanoma These are commonly asymmetrical in shape and/or pigment distribution, with an irregular border, color variation, and often greater than 6 mm diameter.
Melanoma.jpg

Basal-cell carcinomas are most commonly present on sun-exposed areas of the skin, especially the face. They rarely metastasize and rarely cause death. They are easily treated with surgery or radiation. Squamous-cell skin cancers are also common, but much less common than basal-cell cancers. They metastasize more frequently than BCCs. Even then, the metastasis rate is quite low, with the exception of SCC of the lip, ear, and in people who are immunosuppressed. Melanoma are the least frequent of the three common skin cancers. They frequently metastasize, and potentially cause death once they spread.

Less common skin cancers include: dermatofibrosarcoma protuberans, Merkel cell carcinoma, Kaposi's sarcoma, keratoacanthoma, spindle cell tumors, sebaceous carcinomas, microcystic adnexal carcinoma, Paget's disease of the breast, atypical fibroxanthoma, leiomyosarcoma, and angiosarcoma, and porocarcinoma.

BCC and SCC often carry a UV-signature mutation indicating that these cancers are caused by UVB radiation via direct DNA damage. However malignant melanoma is predominantly caused by UVA radiation via indirect DNA damage. The indirect DNA damage is caused by free radicals and reactive oxygen species. Research indicates that the absorption of three sunscreen ingredients into the skin, combined with a 60-minute exposure to UV, leads to an increase of free radicals in the skin, if applied in too little quantity and too infrequently. However, the researchers add that newer creams often do not contain these specific compounds, and that the combination of other ingredients tends to retain the compounds on the surface of the skin. They also add that frequent re-application reduces the risk of radical formation.

Signs and symptoms

There are a variety of different skin cancer symptoms. These include changes in the skin that do not heal, ulcering in the skin, discolored skin, and changes in existing moles, such as jagged edges to the mole, enlargement of the mole, changes in color, the way it feels or if it bleeds. Other common signs of skin cancer can be painful lesion that itches or burns and large brownish spot with darker speckles.

Basal-cell skin cancer

Basal-cell skin cancer (BCC) usually presents as a raised, smooth, pearly bump on the sun-exposed skin of the head, neck, torso or shoulders. Sometimes small blood vessels (called telangiectasia) can be seen within the tumor. Crusting and bleeding in the center of the tumor frequently develops. It is often mistaken for a sore that does not heal. This form of skin cancer is the least deadly, and with proper treatment can be eliminated, often without significant scarring.

Squamous-cell skin cancer

Squamous-cell skin cancer (SCC) is commonly a red, scaling, thickened patch on sun-exposed skin. Some are firm hard nodules and dome shaped like keratoacanthomas. Ulceration and bleeding may occur. When SCC is not treated, it may develop into a large mass. Squamous-cell is the second most common skin cancer. It is dangerous, but not nearly as dangerous as a melanoma.

Melanoma

Most melanoma consist of various colours from shades of brown to black. A small number of melanoma are pink, red or fleshy in colour; these are called amelanotic melanoma and tend to be more aggressive. Warning signs of malignant melanoma include change in the size, shape, color or elevation of a mole. Other signs are the appearance of a new mole during adulthood or pain, itching, ulceration, redness around the site, or bleeding at the site. An often-used mnemonic is "ABCDE", where A is for "asymmetrical", B for "borders" (irregular: "Coast of Maine sign"), C for "color" (variegated), D for "diameter" (larger than 6 mm – the size of a pencil eraser) and E for "evolving."

Other

Merkel cell carcinomas are most often rapidly growing, non-tender red, purple or skin colored bumps that are not painful or itchy. They may be mistaken for a cyst or another type of cancer.

Causes

Ultraviolet radiation from sun exposure is the primary environmental cause of skin cancer. This can occur in professions such as farming. Other risk factors that play a role include:

  • Light skin color 
  • Age 
  • Smoking tobacco
  • HPV infections increase the risk of squamous-cell skin cancer.
  • Some genetic syndromes including congenital melanocytic nevi syndrome which is characterized by the presence of nevi (birthmarks or moles) of varying size which are either present at birth, or appear within 6 months of birth. Nevi larger than 20 mm (3/4") in size are at higher risk for becoming cancerous.
  • Chronic non-healing wounds. These are called Marjolin's ulcers based on their appearance, and can develop into squamous-cell skin cancer.
  • Ionizing radiation such as X-rays, environmental carcinogens, and artificial UV radiation (e.g. tanning beds). It is believed that tanning beds are the cause of hundreds of thousands of basal and squamous-cell skin cancer. The World Health Organization now places people who use artificial tanning beds in its highest risk category for skin cancer. Alcohol consumption, specifically excessive drinking increase the risk of sunburns.
  • The use of many immunosuppressive medications increases the risk of skin cancer. Cyclosporin A, a calcineurin inhibitor for example increases the risk approximately 200 times, and azathioprine about 60 times.
  • Deliberate exposure of sensitive skin not normally exposed to sunlight during alternative wellness behaviors such as perineum sunning.

Pathophysiology

A malignant epithelial tumor that primarily originates in the epidermis, in squamous mucosa or in areas of squamous metaplasia is referred to as a squamous-cell carcinoma.

Macroscopically, the tumor is often elevated, fungating, or may be ulcerated with irregular borders. Microscopically, tumor cells destroy the basement membrane and form sheets or compact masses which invade the subjacent connective tissue (dermis). In well differentiated carcinomas, tumor cells are pleomorphic/atypical, but resembling normal keratinocytes from prickle layer (large, polygonal, with abundant eosinophilic (pink) cytoplasm and central nucleus).

Their disposal tends to be similar to that of normal epidermis: immature/basal cells at the periphery, becoming more mature to the centre of the tumor masses. Tumor cells transform into keratinized squamous cells and form round nodules with concentric, laminated layers, called "cell nests" or "epithelial/keratinous pearls". The surrounding stroma is reduced and contains inflammatory infiltrate (lymphocytes). Poorly differentiated squamous carcinomas contain more pleomorphic cells and no keratinization.

A molecular factor involved in the disease process is mutation in gene PTCH1 that plays an important role in the Sonic hedgehog signaling pathway.

Diagnosis

Diagnosis is by biopsy and histopathological examination.

Non-invasive skin cancer detection methods include photography, dermatoscopy, sonography, confocal microscopy, Raman spectroscopy, fluorescence spectroscopy, terahertz spectroscopy, optical coherence tomography, the multispectral imaging technique, thermography, electrical bio-impedance, tape stripping and computer-aided analysis.

Dermatoscopy may be useful in diagnosing basal cell carcinoma in addition to skin inspection.

There is insufficient evidence that optical coherence tomography (OCT) is useful in diagnosing melanoma or squamous cell carcinoma. OCT may have a role in diagnosing basal cell carcinoma but more data is needed to support this.

Computer-assisted diagnosis devices have been developed that analyze images from a dermatoscope or spectroscopy and can be used by a diagnostician to aid in the detection of skin cancer. CAD systems have been found to be highly sensitive in the detection of melanoma, but have a high false-positive rate. There is not yet enough evidence to recommend CAD as compared to traditional diagnostic methods.

High-frequency ultrasound (HFUS) is of unclear usefulness in the diagnosis of skin cancer. There is insufficient evidence for reflectance confocal microscopy to diagnose basal cell or squamous cell carcinoma or any other skin cancers.

Prevention

Sunscreen is effective and thus recommended to prevent melanoma and squamous-cell carcinoma. There is little evidence that it is effective in preventing basal-cell carcinoma. Other advice to reduce rates of skin cancer includes avoiding sunburning, wearing protective clothing, sunglasses and hats, and attempting to avoid sun exposure or periods of peak exposure. The U.S. Preventive Services Task Force recommends that people between 9 and 25 years of age be advised to avoid ultraviolet light.

The risk of developing skin cancer can be reduced through a number of measures including decreasing indoor tanning and mid day sun exposure, increasing the use of sunscreen, and avoiding the use of tobacco products.

The reason it is important to limit sun exposure and to avoid tanning beds is because they both involve UV light. UV light is known to damage skin cells by mutating the DNA in it. The mutated DNA can cause tumors and other growths to form on the skin. Further, there are other risk factors beside just UV exposure. Fair skin, prolonged history of sunburns, moles, and family history of skin cancer are just a few.

There is insufficient evidence either for or against screening for skin cancers. Vitamin supplements and antioxidant supplements have not been found to have an effect in prevention. Evidence for reducing melanoma risk from dietary measures is tentative, with some supportive epidemiological evidence, but no clinical trials.

Zinc oxide and titanium oxide are often used in sun screen to provide broad protection from UVA and UVB ranges.

Eating certain foods may decrease the risk of sunburns but this is much less than the protection provided by sunscreen.

A meta-analysis of skin cancer prevention in high risk individuals found evidence that topical application of T4N5 liposome lotion reduced the rate of appearance of basal cell carcinomas in people with xeroderma pigmentosum, and that acitretin taken by mouth may have a skin protective benefit in people following kidney transplant.

A research published in January 2022 by the Oregon State University College of Pharmacy showed that a vaccine that stimulates production of a protein critical to the skin's antioxidant network could reinforce people's defenses against skin cancer.

Treatment

Treatment is dependent on the specific type of cancer, location of the cancer, age of the person, and whether the cancer is primary or a recurrence. For a small basal-cell cancer in a young person, the treatment with the best cure rate (Mohs surgery or CCPDMA) might be indicated. In the case of an elderly frail man with multiple complicating medical problems, a difficult to excise basal-cell cancer of the nose might warrant radiation therapy (slightly lower cure rate) or no treatment at all. Topical chemotherapy might be indicated for large superficial basal-cell carcinoma for good cosmetic outcome, whereas it might be inadequate for invasive nodular basal-cell carcinoma or invasive squamous-cell carcinoma. In general, melanoma is poorly responsive to radiation or chemotherapy.

For low-risk disease, radiation therapy (external beam radiotherapy or brachytherapy), topical chemotherapy (imiquimod or 5-fluorouracil) and cryotherapy (freezing the cancer off) can provide adequate control of the disease; all of them, however, may have lower overall cure rates than certain type of surgery. Other modalities of treatment such as photodynamic therapy, epidermal radioisotope therapy, topical chemotherapy, electrodesiccation and curettage can be found in the discussions of basal-cell carcinoma and squamous-cell carcinoma.

Mohs' micrographic surgery (Mohs surgery) is a technique used to remove the cancer with the least amount of surrounding tissue and the edges are checked immediately to see if tumor is found. This provides the opportunity to remove the least amount of tissue and provide the best cosmetically favorable results. This is especially important for areas where excess skin is limited, such as the face. Cure rates are equivalent to wide excision. Special training is required to perform this technique. An alternative method is CCPDMA and can be performed by a pathologist not familiar with Mohs surgery.

In the case of disease that has spread (metastasized), further surgical procedures or chemotherapy may be required.

Treatments for metastatic melanoma include biologic immunotherapy agents ipilimumab, pembrolizumab, nivolumab, cemiplimab; BRAF inhibitors, such as vemurafenib and dabrafenib; and a MEK inhibitor trametinib.

Reconstruction

Currently, surgical excision is the most common form of treatment for skin cancers. The goal of reconstructive surgery is restoration of normal appearance and function. The choice of technique in reconstruction is dictated by the size and location of the defect. Excision and reconstruction of facial skin cancers is generally more challenging due to presence of highly visible and functional anatomic structures in the face.

When skin defects are small in size, most can be repaired with simple repair where skin edges are approximated and closed with sutures. This will result in a linear scar. If the repair is made along a natural skin fold or wrinkle line, the scar will be hardly visible. Larger defects may require repair with a skin graft, local skin flap, pedicled skin flap, or a microvascular free flap. Skin grafts and local skin flaps are by far more common than the other listed choices.

Skin grafting is patching of a defect with skin that is removed from another site in the body. The skin graft is sutured to the edges of the defect, and a bolster dressing is placed atop the graft for seven to ten days, to immobilize the graft as it heals in place. There are two forms of skin grafting: split thickness and full thickness. In a split thickness skin graft, a shaver is used to shave a layer of skin from the abdomen or thigh. The donor site regenerates skin and heals over a period of two weeks. In a full thickness skin graft, a segment of skin is totally removed and the donor site needs to be sutured closed.

Split thickness grafts can be used to repair larger defects, but the grafts are inferior in their cosmetic appearance. Full thickness skin grafts are more acceptable cosmetically. However, full thickness grafts can only be used for small or moderate sized defects.

Local skin flaps are a method of closing defects with tissue that closely matches the defect in color and quality. Skin from the periphery of the defect site is mobilized and repositioned to fill the deficit. Various forms of local flaps can be designed to minimize disruption to surrounding tissues and maximize cosmetic outcome of the reconstruction. Pedicled skin flaps are a method of transferring skin with an intact blood supply from a nearby region of the body. An example of such reconstruction is a pedicled forehead flap for repair of a large nasal skin defect. Once the flap develops a source of blood supply form its new bed, the vascular pedicle can be detached.

Prognosis

The mortality rate of basal-cell and squamous-cell carcinoma is around 0.3%, causing 2000 deaths per year in the US. In comparison, the mortality rate of melanoma is 15–20% and it causes 6500 deaths per year. Even though it is much less common, malignant melanoma is responsible for 75% of all skin cancer-related deaths.

The survival rate for people with melanoma depends upon when they start treatment. The cure rate is very high when melanoma is detected in early stages, when it can easily be removed surgically. The prognosis is less favorable if the melanoma has spread to other parts of the body. As of 2003 the overall five-year cure rate with Mohs' micrographic surgery was around 95 percent for recurrent basal cell carcinoma.

Australia and New Zealand exhibit one of the highest rates of skin cancer incidence in the world, almost four times the rates registered in the United States, the UK and Canada. Around 434,000 people receive treatment for non-melanoma skin cancers and 10,300 are treated for melanoma. Melanoma is the most common type of cancer in people between 15 and 44 years in both countries. The incidence of skin cancer has been increasing. The incidence of melanoma among Auckland residents of European descent in 1995 was 77.7 cases per 100,000 people per year, and was predicted to increase in the 21st century because of "the effect of local stratospheric ozone depletion and the time lag from sun exposure to melanoma development."

Epidemiology

Age-standardized death from melanoma and other skin cancers per 100,000 inhabitants in 2004

Skin cancers result in 80,000 deaths a year as of 2010, 49,000 of which are due to melanoma and 31,000 of which are due to non-melanoma skin cancers. This is up from 51,000 in 1990.

More than 3.5 million cases of skin cancer are diagnosed annually in the United States, which makes it the most common form of cancer in that country. One in five Americans will develop skin cancer at some point of their lives. The most common form of skin cancer is basal-cell carcinoma, followed by squamous cell carcinoma. Unlike for other cancers, there exists no basal and squamous cell skin cancers registry in the United States.

Melanoma

In the US in 2008, 59,695 people were diagnosed with melanoma, and 8,623 people died from it. In Australia more than 12,500 new cases of melanoma are reported each year, out of which more than 1,500 die from the disease. Australia has the highest per capita incidence of melanoma in the world.

Although the rates of many cancers in the United States is falling, the incidence of melanoma keeps growing, with approximately 68,729 melanomas diagnosed in 2004 according to reports of the National Cancer Institute.

Melanoma is the fifth most common cancer in the UK (around 13,300 people were diagnosed with melanoma in 2011), and the disease accounts for 1% all cancer deaths (around 2,100 people died in 2012).

Non-melanoma

Approximately 2,000 people die from basal or squamous cell skin cancers (non-melanoma skin cancers) in the United States each year. The rate has dropped in recent years. Most of the deaths happen to people who are elderly and might not have seen a doctor until the cancer had spread; and people with immune system disorders.

Superconducting magnet

From Wikipedia, the free encyclopedia
 
Schematic of a 20-tesla superconducting magnet with vertical bore

A superconducting magnet is an electromagnet made from coils of superconducting wire. They must be cooled to cryogenic temperatures during operation. In its superconducting state the wire has no electrical resistance and therefore can conduct much larger electric currents than ordinary wire, creating intense magnetic fields. Superconducting magnets can produce greater magnetic fields than all but the strongest non-superconducting electromagnets and can be cheaper to operate because no energy is dissipated as heat in the windings. They are used in MRI machines in hospitals, and in scientific equipment such as NMR spectrometers, mass spectrometers, fusion reactors and particle accelerators. They are also used for levitation, guidance and propulsion in a magnetic levitation (maglev) railway system being constructed in Japan.

Construction

Cooling

During operation, the magnet windings must be cooled below their critical temperature, the temperature at which the winding material changes from the normal resistive state and becomes a superconductor, which is far below room temperature in the cryogenic range. The windings are typically cooled to temperatures significantly below their critical temperature, because the lower the temperature, the better superconductive windings work—the higher the currents and magnetic fields they can stand without returning to their non-superconductive state. Two types of cooling systems are commonly used to maintain magnet windings at temperatures sufficient to maintain superconductivity:

Liquid cooled

Liquid helium is used as a coolant for many superconductive windings. It has a boiling point of 4.2 K, far below the critical temperature of most winding materials. The magnet and coolant are contained in a thermally insulated container (dewar) called a cryostat. To keep the helium from boiling away, the cryostat is usually constructed with an outer jacket containing (significantly cheaper) liquid nitrogen at 77 K. Alternatively, a thermal shield made of conductive material and maintained in 40 K-60 K temperature range, cooled by conductive connections to the cryocooler cold head, is placed around the helium-filled vessel to keep the heat input to the latter at acceptable level. One of the goals of the search for high temperature superconductors is to build magnets that can be cooled by liquid nitrogen alone. At temperatures above about 20 K cooling can be achieved without boiling off cryogenic liquids.

Mechanical cooling

Because of increasing cost and the dwindling availability of liquid helium, many superconducting systems are cooled using two stage mechanical refrigeration. In general two types of mechanical cryocoolers are employed which have sufficient cooling power to maintain magnets below their critical temperature. The Gifford-McMahon Cryocooler has been commercially available since the 1960s and has found widespread application. The G-M regenerator cycle in a cryocooler operates using a piston type displacer and heat exchanger. Alternatively, 1999 marked the first commercial application using a pulse tube cryocooler. This design of cryocooler has become increasingly common due to low vibration and long service interval as pulse tube designs utilize an acoustic process in lieu of mechanical displacement. In a typical two-stage refrigerator, the first stage will offer higher cooling capacity but at higher temperature (≈77 K) with the second stage reaching ≈4.2 K and <2.0 watts cooling power. In use, the first stage is used primarily for ancillary cooling of the cryostat with the second stage used primarily for cooling the magnet.

Coil winding materials

The maximal magnetic field achievable in a superconducting magnet is limited by the field at which the winding material ceases to be superconducting, its "critical field", Hc, which for type-II superconductors is its upper critical field. Another limiting factor is the "critical current", Ic, at which the winding material also ceases to be superconducting. Advances in magnets have focused on creating better winding materials.

The superconducting portions of most current magnets are composed of niobium-titanium. This material has critical temperature of 10 kelvins and can superconduct at up to about 15 teslas. More expensive magnets can be made of niobium-tin (Nb3Sn). These have a Tc of 18 K. When operating at 4.2 K they are able to withstand a much higher magnetic field intensity, up to 25 to 30 teslas. Unfortunately, it is far more difficult to make the required filaments from this material. This is why sometimes a combination of Nb3Sn for the high-field sections and NbTi for the lower-field sections is used. Vanadium-gallium is another material used for the high-field inserts.

High-temperature superconductors (e.g. BSCCO or YBCO) may be used for high-field inserts when required magnetic fields are higher than Nb3Sn can manage. BSCCO, YBCO or magnesium diboride may also be used for current leads, conducting high currents from room temperature into the cold magnet without an accompanying large heat leak from resistive leads.

Conductor structure

The coil windings of a superconducting magnet are made of wires or tapes of Type II superconductors (e.g.niobium-titanium or niobium-tin). The wire or tape itself may be made of tiny filaments (about 20 micrometers thick) of superconductor in a copper matrix. The copper is needed to add mechanical stability, and to provide a low resistance path for the large currents in case the temperature rises above Tc or the current rises above Ic and superconductivity is lost. These filaments need to be this small because in this type of superconductor the current only flows in a surface layer whose thickness is limited to the London penetration depth. (See Skin effect) The coil must be carefully designed to withstand (or counteract) magnetic pressure and Lorentz forces that could otherwise cause wire fracture or crushing of insulation between adjacent turns.

Operation

7 T horizontal bore superconducting magnet, part of a mass spectrometer. The magnet itself is inside the cylindrical cryostat.

Power supply

The current to the coil windings is provided by a high current, very low voltage DC power supply, since in steady state the only voltage across the magnet is due to the resistance of the feeder wires. Any change to the current through the magnet must be done very slowly, first because electrically the magnet is a large inductor and an abrupt current change will result in a large voltage spike across the windings, and more importantly because fast changes in current can cause eddy currents and mechanical stresses in the windings that can precipitate a quench (see below). So the power supply is usually microprocessor-controlled, programmed to accomplish current changes gradually, in gentle ramps. It usually takes several minutes to energize or de-energize a laboratory-sized magnet.

Persistent mode

An alternate operating mode used by most superconducting magnets is to short-circuit the windings with a piece of superconductor once the magnet has been energized. The windings become a closed superconducting loop, the power supply can be turned off, and persistent currents will flow for months, preserving the magnetic field. The advantage of this persistent mode is that stability of the magnetic field is better than is achievable with the best power supplies, and no energy is needed to power the windings. The short circuit is made by a 'persistent switch', a piece of superconductor inside the magnet connected across the winding ends, attached to a small heater. When the magnet is first turned on, the switch wire is heated above its transition temperature, so it is resistive. Since the winding itself has no resistance, no current flows through the switch wire. To go to persistent mode, the supply current is adjusted until the desired magnetic field is obtained, then the heater is turned off. The persistent switch cools to its superconducting temperature, short-circuiting the windings. Then the power supply can be turned off. The winding current, and the magnetic field, will not actually persist forever, but will decay slowly according to a normal inductive (L/R) time constant:

where is a small residual resistance in the superconducting windings due to joints or a phenomenon called flux motion resistance. Nearly all commercial superconducting magnets are equipped with persistent switches.

Magnet quench

A quench is an abnormal termination of magnet operation that occurs when part of the superconducting coil enters the normal (resistive) state. This can occur because the field inside the magnet is too large, the rate of change of field is too large (causing eddy currents and resultant heating in the copper support matrix), or a combination of the two. More rarely a defect in the magnet can cause a quench. When this happens, that particular spot is subject to rapid Joule heating from the enormous current, which raises the temperature of the surrounding regions. This pushes those regions into the normal state as well, which leads to more heating in a chain reaction. The entire magnet rapidly becomes normal (this can take several seconds, depending on the size of the superconducting coil). This is accompanied by a loud bang as the energy in the magnetic field is converted to heat, and rapid boil-off of the cryogenic fluid. The abrupt decrease of current can result in kilovolt inductive voltage spikes and arcing. Permanent damage to the magnet is rare, but components can be damaged by localized heating, high voltages, or large mechanical forces. In practice, magnets usually have safety devices to stop or limit the current when the beginning of a quench is detected. If a large magnet undergoes a quench, the inert vapor formed by the evaporating cryogenic fluid can present a significant asphyxiation hazard to operators by displacing breathable air.

A large section of the superconducting magnets in CERN's Large Hadron Collider unexpectedly quenched during start-up operations in 2008, necessitating the replacement of a number of magnets. In order to mitigate against potentially destructive quenches, the superconducting magnets that form the LHC are equipped with fast-ramping heaters which are activated once a quench event is detected by the complex quench protection system. As the dipole bending magnets are connected in series, each power circuit includes 154 individual magnets, and should a quench event occur, the entire combined stored energy of these magnets must be dumped at once. This energy is transferred into dumps that are massive blocks of metal which heat up to several hundreds of degrees Celsius due to the resistive heating in a matter of seconds. Although undesirable, a magnet quench is a "fairly routine event" during the operation of a particle accelerator.

Magnet "training"

In certain cases, superconducting magnets designed for very high currents require extensive bedding in, to enable the magnets to function at their full planned currents and fields. This is known as "training" the magnet, and involves a type of material memory effect. One situation this is required in is the case of particle colliders such as CERN's Large Hadron Collider. The magnets of the LHC were planned to run at 8 TeV (2×4 TeV) on its first run and 14 TeV (2×7 TeV) on its second run, but were initially operated at a lower energy of 3.5 TeV and 6.5 TeV per beam respectively. Because of initial crystallographic defects in the material, they will initially lose their superconducting ability ("quench") at a lower level than their design current. CERN states that this is due to electromagnetic forces causing tiny movements in the magnets, which in turn cause superconductivity to be lost when operating at the high precisions needed for their planned current. By repeatedly running the magnets at a lower current and then slightly increasing the current until they quench under control, the magnet will gradually both gain the required ability to withstand the higher currents of its design specification without quenches occurring, and have any such issues "shaken" out of them, until they are eventually able to operate reliably at their full planned current without experiencing quenches.

History

Although the idea of making electromagnets with superconducting wire was proposed by Heike Kamerlingh Onnes shortly after he discovered superconductivity in 1911, a practical superconducting electromagnet had to await the discovery of superconducting materials that could support large critical supercurrent densities in high magnetic fields. The first successful superconducting magnet was built by G.B. Yntema in 1955 using niobium wire and achieved a field of 0.7 T at 4.2 K. Then, in 1961, J.E. Kunzler, E. Buehler, F.S.L. Hsu, and J.H. Wernick made the discovery that a compound of niobium and tin could support critical-supercurrent densities greater than 100,000 amperes per square centimeter in magnetic fields of 8.8 teslas. Despite its brittle nature, niobium-tin has since proved extremely useful in supermagnets generating magnetic fields up to 20 teslas.

The persistent switch was invented in 1960 by Dwight Adams while a postdoctoral associate at Stanford University. The second persistent switch was constructed at the University of Florida by M.S. student R.D. Lichti in 1963. It has been preserved in a showcase in the UF Physics Building.

In 1962, T.G. Berlincourt and R.R. Hake discovered the high-critical-magnetic-field, high-critical-supercurrent-density properties of niobium-titanium alloys. Although niobium-titanium alloys possess less spectacular superconducting properties than niobium-tin, they are highly ductile, easily fabricated, and economical. Useful in supermagnets generating magnetic fields up to 10 teslas, niobium-titanium alloys are the most widely used supermagnet materials.

In 1986, the discovery of high temperature superconductors by Georg Bednorz and Karl Müller energized the field, raising the possibility of magnets that could be cooled by liquid nitrogen instead of the more difficult-to-work-with helium.

In 2007, a magnet with windings of YBCO achieved a world record field of 26.8 teslas. The US National Research Council has a goal of creating a 30-tesla superconducting magnet.

In 2017, a YBCO magnet created by the National High Magnetic Field Laboratory (NHMFL) broke the previous world record with a strength of 32 T. This is an all superconducting user magnet, designed to last for many decades. They hold the current record as of March 2018.

In 2019 the NHMFL also developed a non-insulated YBCO test coil which broke the lab's own world record for highest continuous magnetic field for any configuration of magnet at 45.5 T. 

Uses

An MRI machine that uses a superconducting magnet. The magnet is inside the doughnut-shaped housing and can create a 3-tesla field inside the central hole.

Superconducting magnets have a number of advantages over resistive electromagnets. They can generate magnetic fields that are up to ten times stronger than those generated by ordinary ferromagnetic-core electromagnets, which are limited to fields of around 2 T. The field is generally more stable, resulting in less noisy measurements. They can be smaller, and the area at the center of the magnet where the field is created is empty rather than being occupied by an iron core. Most importantly, for large magnets they can consume much less power. In the persistent state (above), the only power the magnet consumes is that needed for any refrigeration equipment to preserve the cryogenic temperature. Higher fields, however can be achieved with special cooled resistive electromagnets, as superconducting coils will enter the normal (non-superconducting) state (see quench, above) at high fields. Steady fields of over 40 T can now be achieved by many institutions around the world usually by combining a Bitter electromagnet with a superconducting magnet (often as an insert).

Superconducting magnets are widely used in MRI machines, NMR equipment, mass spectrometers, magnetic separation processes, and particle accelerators.

In Japan, after decades of research and development into superconducting maglev by Japanese National Railways and later Central Japan Railway Company (JR Central), the Japanese government gave permission to JR Central to build the Chūō Shinkansen, linking Tokyo to Nagoya and later to Osaka.

One of the most challenging use of SC magnets is in the LHC particle accelerator. The niobium-titanium (Nb-Ti) magnets operate at 1.9 K to allow them to run safely at 8.3 T. Each magnet stores 7 MJ. In total the magnets store 10.4 gigajoules (2.5 tons of TNT). Once or twice a day, as the protons are accelerated from 450 GeV to 7 TeV, the field of the superconducting bending magnets will be increased from 0.54 T to 8.3 T.

The central solenoid and toroidal field superconducting magnets designed for the ITER fusion reactor use niobium-tin (Nb3Sn) as a superconductor. The Central Solenoid coil will carry 46 kA and produce a field of 13.5 teslas. The 18 Toroidal Field coils at max field of 11.8 T will store 41 GJ (total?). They have been tested at a record 80 kA. Other lower field ITER magnets (PF and CC) will use niobium-titanium. Most of the ITER magnets will have their field varied many times per hour.

One high-resolution mass spectrometer is planned to use a 21-tesla SC magnet.

Globally in 2014, about five billion euros worth of economic activity resulted from which superconductivity is indispensable. MRI systems, most of which employ niobium-titanium, accounted for about 80% of that total.

Saturday, July 23, 2022

Noble gas

From Wikipedia, the free encyclopedia
 
Noble gases
Hydrogen
Helium
Lithium Beryllium
Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium
Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium
Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium

Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
halogens  alkali metals
IUPAC group number 18
Name by element helium group or
neon group
Trivial name noble gases
CAS group number
(US, pattern A-B-A)
VIIIA
old IUPAC number
(Europe, pattern A-B)
0

↓ Period
1
Image: Helium discharge tube
Helium (He)
2
2
Image: Neon discharge tube
Neon (Ne)
10
3
Image: Argon discharge tube
Argon (Ar)
18
4
Image: Krypton discharge tube
Krypton (Kr)
36
5
Image: Xenon discharge tube
Xenon (Xe)
54
6 Radon (Rn)
86
7 Oganesson (Og)
118

Legend

primordial element
element by radioactive decay
Atomic number color: red=gas

The noble gases (historically also the inert gases; sometimes referred to as aerogens) make up a class of chemical elements with similar properties; under standard conditions, they are all odorless, colorless, monatomic gases with very low chemical reactivity. The six naturally occurring noble gases are helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and the radioactive radon (Rn).

Oganesson (Og) is a synthetically produced highly radioactive element, variously predicted to be another noble gas, or to break the trend and be reactive, due to relativistic effects. In part due to the extremely short 0.7 ms half-life of its only known isotope, its chemistry has not yet been investigated.

For the first six periods of the periodic table, the noble gases are exactly the members of group 18. Noble gases are typically highly unreactive except when under particular extreme conditions. The inertness of noble gases makes them very suitable in applications where reactions are not wanted. For example, argon is used in incandescent lamps to prevent the hot tungsten filament from oxidizing; also, helium is used in breathing gas by deep-sea divers to prevent oxygen, nitrogen and carbon dioxide toxicity.

The properties of the noble gases can be well explained by modern theories of atomic structure: Their outer shell of valence electrons is considered to be "full", giving them little tendency to participate in chemical reactions, and it has been possible to prepare only a few hundred noble gas compounds. The melting and boiling points for a given noble gas are close together, differing by less than 10 °C (18 °F); that is, they are liquids over only a small temperature range.

Neon, argon, krypton, and xenon are obtained from air in an air separation unit using the methods of liquefaction of gases and fractional distillation. Helium is sourced from natural gas fields that have high concentrations of helium in the natural gas, using cryogenic gas separation techniques, and radon is usually isolated from the radioactive decay of dissolved radium, thorium, or uranium compounds. Noble gases have several important applications in industries such as lighting, welding, and space exploration. A helium-oxygen breathing gas is often used by deep-sea divers at depths of seawater over 55 m (180 ft). After the risks caused by the flammability of hydrogen became apparent in the Hindenburg disaster, it was replaced with helium in blimps and balloons.

History

Noble gas is translated from the German noun Edelgas, first used in 1898 by Hugo Erdmann to indicate their extremely low level of reactivity. The name makes an analogy to the term "noble metals", which also have low reactivity. The noble gases have also been referred to as inert gases, but this label is deprecated as many noble gas compounds are now known. Rare gases is another term that was used, but this is also inaccurate because argon forms a fairly considerable part (0.94% by volume, 1.3% by mass) of the Earth's atmosphere due to decay of radioactive potassium-40.

A line spectrum chart of the visible spectrum showing sharp lines on top.
Helium was first detected in the Sun due to its characteristic spectral lines.

Pierre Janssen and Joseph Norman Lockyer had discovered a new element on 18 August 1868 while looking at the chromosphere of the Sun, and named it helium after the Greek word for the Sun, ἥλιος (hḗlios). No chemical analysis was possible at the time, but helium was later found to be a noble gas. Before them, in 1784, the English chemist and physicist Henry Cavendish had discovered that air contains a small proportion of a substance less reactive than nitrogen. A century later, in 1895, Lord Rayleigh discovered that samples of nitrogen from the air were of a different density than nitrogen resulting from chemical reactions. Along with Scottish scientist William Ramsay at University College, London, Lord Rayleigh theorized that the nitrogen extracted from air was mixed with another gas, leading to an experiment that successfully isolated a new element, argon, from the Greek word ἀργός (argós, "idle" or "lazy"). With this discovery, they realized an entire class of gases was missing from the periodic table. During his search for argon, Ramsay also managed to isolate helium for the first time while heating cleveite, a mineral. In 1902, having accepted the evidence for the elements helium and argon, Dmitri Mendeleev included these noble gases as group 0 in his arrangement of the elements, which would later become the periodic table.

Ramsay continued his search for these gases using the method of fractional distillation to separate liquid air into several components. In 1898, he discovered the elements krypton, neon, and xenon, and named them after the Greek words κρυπτός (kryptós, "hidden"), νέος (néos, "new"), and ξένος (ksénos, "stranger"), respectively. Radon was first identified in 1898 by Friedrich Ernst Dorn, and was named radium emanation, but was not considered a noble gas until 1904 when its characteristics were found to be similar to those of other noble gases. Rayleigh and Ramsay received the 1904 Nobel Prizes in Physics and in Chemistry, respectively, for their discovery of the noble gases; in the words of J. E. Cederblom, then president of the Royal Swedish Academy of Sciences, "the discovery of an entirely new group of elements, of which no single representative had been known with any certainty, is something utterly unique in the history of chemistry, being intrinsically an advance in science of peculiar significance".

The discovery of the noble gases aided in the development of a general understanding of atomic structure. In 1895, French chemist Henri Moissan attempted to form a reaction between fluorine, the most electronegative element, and argon, one of the noble gases, but failed. Scientists were unable to prepare compounds of argon until the end of the 20th century, but these attempts helped to develop new theories of atomic structure. Learning from these experiments, Danish physicist Niels Bohr proposed in 1913 that the electrons in atoms are arranged in shells surrounding the nucleus, and that for all noble gases except helium the outermost shell always contains eight electrons. In 1916, Gilbert N. Lewis formulated the octet rule, which concluded an octet of electrons in the outer shell was the most stable arrangement for any atom; this arrangement caused them to be unreactive with other elements since they did not require any more electrons to complete their outer shell.

In 1962, Neil Bartlett discovered the first chemical compound of a noble gas, xenon hexafluoroplatinate. Compounds of other noble gases were discovered soon after: in 1962 for radon, radon difluoride (RnF
2
), which was identified by radiotracer techniques and in 1963 for krypton, krypton difluoride (KrF
2
). The first stable compound of argon was reported in 2000 when argon fluorohydride (HArF) was formed at a temperature of 40 K (−233.2 °C; −387.7 °F).

In October 2006, scientists from the Joint Institute for Nuclear Research and Lawrence Livermore National Laboratory successfully created synthetically oganesson, the seventh element in group 18, by bombarding californium with calcium.

Physical and atomic properties

Property Helium Neon Argon Krypton Xenon Radon Oganesson
Density (g/dm3) 0.1786 0.9002 1.7818 3.708 5.851 9.97 7200 (predicted)
Boiling point (K) 4.4 27.3 87.4 121.5 166.6 211.5 450±10 (predicted)
Melting point (K) 24.7 83.6 115.8 161.7 202.2 325±15 (predicted)
Enthalpy of vaporization (kJ/mol) 0.08 1.74 6.52 9.05 12.65 18.1
Solubility in water at 20 °C (cm3/kg) 8.61 10.5 33.6 59.4 108.1 230
Atomic number 2 10 18 36 54 86 118
Atomic radius (calculated) (pm) 31 38 71 88 108 120
Ionization energy (kJ/mol) 2372 2080 1520 1351 1170 1037 839 (predicted)
Electronegativity 4.16 4.79 3.24 2.97 2.58 2.60

The noble gases have weak interatomic force, and consequently have very low melting and boiling points. They are all monatomic gases under standard conditions, including the elements with larger atomic masses than many normally solid elements. Helium has several unique qualities when compared with other elements: its boiling point at 1 atm is lower than those of any other known substance; it is the only element known to exhibit superfluidity; and, it is the only element that cannot be solidified by cooling at atmospheric pressure (an effect explained by quantum mechanics as its zero point energy is too high to permit freezing) – a pressure of 25 standard atmospheres (2,500 kPa; 370 psi) must be applied at a temperature of 0.95 K (−272.200 °C; −457.960 °F) to convert it to a solid while a pressure of about 115 kbar is required at room temperature. The noble gases up to xenon have multiple stable isotopes. Radon has no stable isotopes; its longest-lived isotope, 222Rn, has a half-life of 3.8 days and decays to form helium and polonium, which ultimately decays to lead. Melting and boiling points increase going down the group.

A graph of ionization energy vs. atomic number showing sharp peaks for the noble gas atoms.
This is a plot of ionization potential versus atomic number. The noble gases, which are labeled, have the largest ionization potential for each period.

The noble gas atoms, like atoms in most groups, increase steadily in atomic radius from one period to the next due to the increasing number of electrons. The size of the atom is related to several properties. For example, the ionization potential decreases with an increasing radius because the valence electrons in the larger noble gases are farther away from the nucleus and are therefore not held as tightly together by the atom. Noble gases have the largest ionization potential among the elements of each period, which reflects the stability of their electron configuration and is related to their relative lack of chemical reactivity. Some of the heavier noble gases, however, have ionization potentials small enough to be comparable to those of other elements and molecules. It was the insight that xenon has an ionization potential similar to that of the oxygen molecule that led Bartlett to attempt oxidizing xenon using platinum hexafluoride, an oxidizing agent known to be strong enough to react with oxygen.[14] Noble gases cannot accept an electron to form stable anions; that is, they have a negative electron affinity.[28]

The macroscopic physical properties of the noble gases are dominated by the weak van der Waals forces between the atoms. The attractive force increases with the size of the atom as a result of the increase in polarizability and the decrease in ionization potential. This results in systematic group trends: as one goes down group 18, the atomic radius, and with it the interatomic forces, increases, resulting in an increasing melting point, boiling point, enthalpy of vaporization, and solubility. The increase in density is due to the increase in atomic mass.

The noble gases are nearly ideal gases under standard conditions, but their deviations from the ideal gas law provided important clues for the study of intermolecular interactions. The Lennard-Jones potential, often used to model intermolecular interactions, was deduced in 1924 by John Lennard-Jones from experimental data on argon before the development of quantum mechanics provided the tools for understanding intermolecular forces from first principles. The theoretical analysis of these interactions became tractable because the noble gases are monatomic and the atoms spherical, which means that the interaction between the atoms is independent of direction, or isotropic.

Chemical properties

An atomic shell diagram with neon core, 2 electrons in the inner shell and 8 in the outer shell.
Neon, like all noble gases, has a full valence shell. Noble gases have eight electrons in their outermost shell, except in the case of helium, which has two.

The noble gases are colorless, odorless, tasteless, and nonflammable under standard conditions. They were once labeled group 0 in the periodic table because it was believed they had a valence of zero, meaning their atoms cannot combine with those of other elements to form compounds. However, it was later discovered some do indeed form compounds, causing this label to fall into disuse.

Electron configuration

Like other groups, the members of this family show patterns in its electron configuration, especially the outermost shells resulting in trends in chemical behavior:

Z Element No. of electrons/shell
2 helium 2
10 neon 2, 8
18 argon 2, 8, 8
36 krypton 2, 8, 18, 8
54 xenon 2, 8, 18, 18, 8
86 radon 2, 8, 18, 32, 18, 8
118 oganesson 2, 8, 18, 32, 32, 18, 8 (predicted)

The noble gases have full valence electron shells. Valence electrons are the outermost electrons of an atom and are normally the only electrons that participate in chemical bonding. Atoms with full valence electron shells are extremely stable and therefore do not tend to form chemical bonds and have little tendency to gain or lose electrons. However, heavier noble gases such as radon are held less firmly together by electromagnetic force than lighter noble gases such as helium, making it easier to remove outer electrons from heavy noble gases.

As a result of a full shell, the noble gases can be used in conjunction with the electron configuration notation to form the noble gas notation. To do this, the nearest noble gas that precedes the element in question is written first, and then the electron configuration is continued from that point forward. For example, the electron notation of phosphorus is 1s2 2s2 2p6 3s2 3p3, while the noble gas notation is [Ne] 3s2 3p3. This more compact notation makes it easier to identify elements, and is shorter than writing out the full notation of atomic orbitals.

The noble gases cross the boundary between blocks—helium is an s-element whereas the rest of members are p-elements—which is unusual among the IUPAC groups. Most, if not all other IUPAC groups contain elements from one block each.

Compounds

A model of planar chemical molecule with a blue center atom (Xe) symmetrically bonded to four peripheral atoms (fluorine).
Structure of XeF
4
, one of the first noble gas compounds to be discovered

The noble gases show extremely low chemical reactivity; consequently, only a few hundred noble gas compounds have been formed. Neutral compounds in which helium and neon are involved in chemical bonds have not been formed (although some helium-containing ions exist and there is some theoretical evidence for a few neutral helium-containing ones), while xenon, krypton, and argon have shown only minor reactivity. The reactivity follows the order Ne < He < Ar < Kr < Xe < Rn ≪ Og.

In 1933, Linus Pauling predicted that the heavier noble gases could form compounds with fluorine and oxygen. He predicted the existence of krypton hexafluoride (KrF
6
) and xenon hexafluoride (XeF
6
), speculated that XeF
8
might exist as an unstable compound, and suggested that xenic acid could form perxenate salts. These predictions were shown to be generally accurate, except that XeF
8
is now thought to be both thermodynamically and kinetically unstable.

Xenon compounds are the most numerous of the noble gas compounds that have been formed. Most of them have the xenon atom in the oxidation state of +2, +4, +6, or +8 bonded to highly electronegative atoms such as fluorine or oxygen, as in xenon difluoride (XeF
2
), xenon tetrafluoride (XeF
4
), xenon hexafluoride (XeF
6
), xenon tetroxide (XeO
4
), and sodium perxenate (Na
4
XeO
6
). Xenon reacts with fluorine to form numerous xenon fluorides according to the following equations:

Xe + F2 → XeF2
Xe + 2F2 → XeF4
Xe + 3F2 → XeF6

Some of these compounds have found use in chemical synthesis as oxidizing agents; XeF
2
, in particular, is commercially available and can be used as a fluorinating agent. As of 2007, about five hundred compounds of xenon bonded to other elements have been identified, including organoxenon compounds (containing xenon bonded to carbon), and xenon bonded to nitrogen, chlorine, gold, mercury, and xenon itself. Compounds of xenon bound to boron, hydrogen, bromine, iodine, beryllium, sulphur, titanium, copper, and silver have also been observed but only at low temperatures in noble gas matrices, or in supersonic noble gas jets.

Radon is more reactive than xenon, and forms chemical bonds more easily than xenon does. However, due to the high radioactivity and short half-life of radon isotopes, only a few fluorides and oxides of radon have been formed in practice. Radon goes further towards metallic behavior than xenon; the difluoride RnF2 is highly ionic, and cationic Rn2+ is formed in halogen fluoride solutions. For this reason, kinetic hindrance makes it difficult to oxidize radon beyond the +2 state. Only tracer experiments appear to have succeeded in doing so, probably forming RnF4, RnF6, and RnO3.

Krypton is less reactive than xenon, but several compounds have been reported with krypton in the oxidation state of +2. Krypton difluoride is the most notable and easily characterized. Under extreme conditions, krypton reacts with fluorine to form KrF2 according to the following equation:

Kr + F2 → KrF2

Compounds in which krypton forms a single bond to nitrogen and oxygen have also been characterized, but are only stable below −60 °C (−76 °F) and −90 °C (−130 °F) respectively.

Krypton atoms chemically bound to other nonmetals (hydrogen, chlorine, carbon) as well as some late transition metals (copper, silver, gold) have also been observed, but only either at low temperatures in noble gas matrices, or in supersonic noble gas jets. Similar conditions were used to obtain the first few compounds of argon in 2000, such as argon fluorohydride (HArF), and some bound to the late transition metals copper, silver, and gold. As of 2007, no stable neutral molecules involving covalently bound helium or neon are known.

Extrapolation from periodic trends predict that oganesson should be the most reactive of the noble gases; more sophisticated theoretical treatments indicate greater reactivity than such extrapolations suggest, to the point where the applicability of the descriptor "noble gas" has been questioned. Oganesson is expected to be rather like silicon or tin in group 14: a reactive element with a common +4 and a less common +2 state, which at room temperature and pressure is not a gas but rather a solid semiconductor. Empirical / experimental testing will be required to validate these predictions. (On the other hand, flerovium, despite being in group 14, is predicted to be unusually volatile, which suggests noble gas-like properties.)

The noble gases—including helium—can form stable molecular ions in the gas phase. The simplest is the helium hydride molecular ion, HeH+, discovered in 1925. Because it is composed of the two most abundant elements in the universe, hydrogen and helium, it is believed to occur naturally in the interstellar medium, although it has not been detected yet. In addition to these ions, there are many known neutral excimers of the noble gases. These are compounds such as ArF and KrF that are stable only when in an excited electronic state; some of them find application in excimer lasers.

In addition to the compounds where a noble gas atom is involved in a covalent bond, noble gases also form non-covalent compounds. The clathrates, first described in 1949, consist of a noble gas atom trapped within cavities of crystal lattices of certain organic and inorganic substances. The essential condition for their formation is that the guest (noble gas) atoms must be of appropriate size to fit in the cavities of the host crystal lattice. For instance, argon, krypton, and xenon form clathrates with hydroquinone, but helium and neon do not because they are too small or insufficiently polarizable to be retained. Neon, argon, krypton, and xenon also form clathrate hydrates, where the noble gas is trapped in ice.

A skeletal structure of buckminsterfullerene with an extra atom in its center.
An endohedral fullerene compound containing a noble gas atom

Noble gases can form endohedral fullerene compounds, in which the noble gas atom is trapped inside a fullerene molecule. In 1993, it was discovered that when C
60
, a spherical molecule consisting of 60 carbon atoms, is exposed to noble gases at high pressure, complexes such as He@C
60
can be formed (the @ notation indicates He is contained inside C
60
but not covalently bound to it). As of 2008, endohedral complexes with helium, neon, argon, krypton, and xenon have been created. These compounds have found use in the study of the structure and reactivity of fullerenes by means of the nuclear magnetic resonance of the noble gas atom.

Schematic illustration of bonding and antibonding orbitals (see text)
Bonding in XeF
2
according to the 3-center-4-electron bond model

Noble gas compounds such as xenon difluoride (XeF
2
) are considered to be hypervalent because they violate the octet rule. Bonding in such compounds can be explained using a three-center four-electron bond model. This model, first proposed in 1951, considers bonding of three collinear atoms. For example, bonding in XeF
2
is described by a set of three molecular orbitals (MOs) derived from p-orbitals on each atom. Bonding results from the combination of a filled p-orbital from Xe with one half-filled p-orbital from each F atom, resulting in a filled bonding orbital, a filled non-bonding orbital, and an empty antibonding orbital. The highest occupied molecular orbital is localized on the two terminal atoms. This represents a localization of charge that is facilitated by the high electronegativity of fluorine.

The chemistry of the heavier noble gases, krypton and xenon, are well established. The chemistry of the lighter ones, argon and helium, is still at an early stage, while a neon compound is yet to be identified.

Occurrence and production

The abundances of the noble gases in the universe decrease as their atomic numbers increase. Helium is the most common element in the universe after hydrogen, with a mass fraction of about 24%. Most of the helium in the universe was formed during Big Bang nucleosynthesis, but the amount of helium is steadily increasing due to the fusion of hydrogen in stellar nucleosynthesis (and, to a very slight degree, the alpha decay of heavy elements). Abundances on Earth follow different trends; for example, helium is only the third most abundant noble gas in the atmosphere. The reason is that there is no primordial helium in the atmosphere; due to the small mass of the atom, helium cannot be retained by the Earth's gravitational field. Helium on Earth comes from the alpha decay of heavy elements such as uranium and thorium found in the Earth's crust, and tends to accumulate in natural gas deposits. The abundance of argon, on the other hand, is increased as a result of the beta decay of potassium-40, also found in the Earth's crust, to form argon-40, which is the most abundant isotope of argon on Earth despite being relatively rare in the Solar System. This process is the basis for the potassium-argon dating method. Xenon has an unexpectedly low abundance in the atmosphere, in what has been called the missing xenon problem; one theory is that the missing xenon may be trapped in minerals inside the Earth's crust. After the discovery of xenon dioxide, research showed that Xe can substitute for Si in quartz. Radon is formed in the lithosphere by the alpha decay of radium. It can seep into buildings through cracks in their foundation and accumulate in areas that are not well ventilated. Due to its high radioactivity, radon presents a significant health hazard; it is implicated in an estimated 21,000 lung cancer deaths per year in the United States alone. Oganesson does not occur in nature and is instead created manually by scientists.

Abundance Helium Neon Argon Krypton Xenon Radon
Solar System (for each atom of silicon) 2343 2.148 0.1025 5.515 × 10−5 5.391 × 10−6
Earth's atmosphere (volume fraction in ppm) 5.20 18.20 9340.00 1.10 0.09 (0.06–18) × 10−19
Igneous rock (mass fraction in ppm) 3 × 10−3 7 × 10−5 4 × 10−2 1.7 × 10−10
Gas 2004 price (USD/m3)
Helium (industrial grade) 4.20–4.90
Helium (laboratory grade) 22.30–44.90
Argon 2.70–8.50
Neon 60–120
Krypton 400–500
Xenon 4000–5000

For large-scale use, helium is extracted by fractional distillation from natural gas, which can contain up to 7% helium.

Neon, argon, krypton, and xenon are obtained from air using the methods of liquefaction of gases, to convert elements to a liquid state, and fractional distillation, to separate mixtures into component parts. Helium is typically produced by separating it from natural gas, and radon is isolated from the radioactive decay of radium compounds. The prices of the noble gases are influenced by their natural abundance, with argon being the cheapest and xenon the most expensive. As an example, the adjacent table lists the 2004 prices in the United States for laboratory quantities of each gas.

Applications

A large solid cylinder with a hole in its center and a rail attached to its side.
Liquid helium is used to cool superconducting magnets in modern MRI scanners

Noble gases have very low boiling and melting points, which makes them useful as cryogenic refrigerants. In particular, liquid helium, which boils at 4.2 K (−268.95 °C; −452.11 °F), is used for superconducting magnets, such as those needed in nuclear magnetic resonance imaging and nuclear magnetic resonance. Liquid neon, although it does not reach temperatures as low as liquid helium, also finds use in cryogenics because it has over 40 times more refrigerating capacity than liquid helium and over three times more than liquid hydrogen.

Helium is used as a component of breathing gases to replace nitrogen, due its low solubility in fluids, especially in lipids. Gases are absorbed by the blood and body tissues when under pressure like in scuba diving, which causes an anesthetic effect known as nitrogen narcosis. Due to its reduced solubility, little helium is taken into cell membranes, and when helium is used to replace part of the breathing mixtures, such as in trimix or heliox, a decrease in the narcotic effect of the gas at depth is obtained. Helium's reduced solubility offers further advantages for the condition known as decompression sickness, or the bends. The reduced amount of dissolved gas in the body means that fewer gas bubbles form during the decrease in pressure of the ascent. Another noble gas, argon, is considered the best option for use as a drysuit inflation gas for scuba diving. Helium is also used as filling gas in nuclear fuel rods for nuclear reactors.

Cigar-shaped blimp with "Good Year" written on its side.
Goodyear Blimp

Since the Hindenburg disaster in 1937, helium has replaced hydrogen as a lifting gas in blimps and balloons due to its lightness and incombustibility, despite an 8.6% decrease in buoyancy.

In many applications, the noble gases are used to provide an inert atmosphere. Argon is used in the synthesis of air-sensitive compounds that are sensitive to nitrogen. Solid argon is also used for the study of very unstable compounds, such as reactive intermediates, by trapping them in an inert matrix at very low temperatures. Helium is used as the carrier medium in gas chromatography, as a filler gas for thermometers, and in devices for measuring radiation, such as the Geiger counter and the bubble chamber. Helium and argon are both commonly used to shield welding arcs and the surrounding base metal from the atmosphere during welding and cutting, as well as in other metallurgical processes and in the production of silicon for the semiconductor industry.

Elongated glass sphere with two metal rod electrodes inside, facing each other. One electrode is blunt and another is sharpened.
15,000-watt xenon short-arc lamp used in IMAX projectors

Noble gases are commonly used in lighting because of their lack of chemical reactivity. Argon, mixed with nitrogen, is used as a filler gas for incandescent light bulbs. Krypton is used in high-performance light bulbs, which have higher color temperatures and greater efficiency, because it reduces the rate of evaporation of the filament more than argon; halogen lamps, in particular, use krypton mixed with small amounts of compounds of iodine or bromine. The noble gases glow in distinctive colors when used inside gas-discharge lamps, such as "neon lights". These lights are called after neon but often contain other gases and phosphors, which add various hues to the orange-red color of neon. Xenon is commonly used in xenon arc lamps, which, due to their nearly continuous spectrum that resembles daylight, find application in film projectors and as automobile headlamps.

The noble gases are used in excimer lasers, which are based on short-lived electronically excited molecules known as excimers. The excimers used for lasers may be noble gas dimers such as Ar2, Kr2 or Xe2, or more commonly, the noble gas is combined with a halogen in excimers such as ArF, KrF, XeF, or XeCl. These lasers produce ultraviolet light, which, due to its short wavelength (193 nm for ArF and 248 nm for KrF), allows for high-precision imaging. Excimer lasers have many industrial, medical, and scientific applications. They are used for microlithography and microfabrication, which are essential for integrated circuit manufacture, and for laser surgery, including laser angioplasty and eye surgery.

Some noble gases have direct application in medicine. Helium is sometimes used to improve the ease of breathing of asthma sufferers. Xenon is used as an anesthetic because of its high solubility in lipids, which makes it more potent than the usual nitrous oxide, and because it is readily eliminated from the body, resulting in faster recovery. Xenon finds application in medical imaging of the lungs through hyperpolarized MRI. Radon, which is highly radioactive and is only available in minute amounts, is used in radiotherapy.

Noble gases, particularly xenon, are predominantly used in ion engines due to their inertness. Since ion engines are not driven by chemical reactions, chemically inert fuels are desired to prevent unwanted reaction between the fuel and anything else on the engine.

Oganesson is too unstable to work with and has no known application other than research.

Discharge color

Colors and spectra (bottom row) of electric discharge in noble gases; only the second row represents pure gases.
Glass tube shining violet light with a wire wound over it Glass tube shining orange light with a wire wound over it Glass tube shining purple light with a wire wound over it Glass tube shining white light with a wire wound over it Glass tube shining blue light with a wire wound over it
Glass tube shining light red Glass tube shining reddish-orange Glass tube shining purple Glass tube shining bluish-white Glass tube shining bluish-violet
Illuminated light red gas discharge tubes shaped as letters H and e Illuminated orange gas discharge tubes shaped as letters N and e Illuminated light blue gas discharge tubes shaped as letters A and r Illuminated white gas discharge tubes shaped as letters K and r Illuminated violet gas discharge tubes shaped as letters X and e
Helium line spectrum Neon line spectrum Argon line spectrum Krypton line spectrum Xenon line spectrum
Helium Neon Argon Krypton Xenon

The color of gas discharge emission depends on several factors, including the following:

  • discharge parameters (local value of current density and electric field, temperature, etc. – note the color variation along the discharge in the top row);
  • gas purity (even small fraction of certain gases can affect color);
  • material of the discharge tube envelope – note suppression of the UV and blue components in the bottom-row tubes made of thick household glass.

Representation of a Lie group

From Wikipedia, the free encyclopedia https://en.wikipedia.org/wiki/Representation_of_a_Lie_group...