Nitric oxide
From Free net encyclopedia
General |
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Name | Nitrogen monoxide |
Chemical formula | NO |
Appearance | Colorless gas |
Physical |
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Formula weight | 30.0 amu |
Melting point | 109 K (-164 °C) |
Boiling point | 121 K (-152 °C) |
Density | 1.3 ×103 kg/m3 (liquid) |
Solubility | 0.0056 g in 100g water |
Thermochemistry |
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ΔfH0gas | 90 kJ/mol |
ΔfH0liquid | 87.7 kJ/mol |
S0gas, 1 bar | 211 J/mol·K |
Safety | |
Ingestion | Used for medicinal purposes but has side effects and dangerous in overdose |
Inhalation | Dangerous, may be fatal. |
Skin | Irritant. |
Eyes | May cause irritation |
More info | Hazardous Chemical Database |
SI units were used where possible. Unless otherwise stated, standard conditions were used. Disclaimer and references </font> |
Contents |
Production and environmental effects
At high temperatures, molecular nitrogen and oxygen can combine to form nitric oxide. A major natural source is lightning. Human activity has drastically increased the production of nitric oxide in combustion chambers. One purpose of catalytic converters in cars is to partially reverse this reaction.
Nitric oxide in the air may later convert to nitric acid, which has been implicated in acid rain. Furthermore, both NO and NO2 participate in ozone layer depletion.
Technical applications
Nitric oxide has some industrial uses. As a raw material it is used in the semiconductor industry for various processes. In one of its applications it is used along with nitrous oxide to form oxynitride gates in CMOS devices. It is an intermediate of the Ostwald process, which converts ammonia into nitric acid.
Nitric oxide can be used for detecting surface radicals on polymers. Quenching of surface radicals with nitric oxide results in incorporation of nitrogen, which can be quantified by means of X-ray photoelectron spectroscopy.
Because of its production in allergic reactions, there is research on using levels of exhaled nitric oxide to optimize treatment of asthma.
It has also recently been seeing use as a supplement in bodybuilding. It is believed that it's dialation of the blood vessels increases blood flow to the muscles, which in turn leads to increased strength, endurance and muscle size. As it is a fairly new product on the market, there is as of yet little research to conclusivley prove or disprove these claims. Nitric oxide supplements do not actually contain Nitric oxide, but rather arginine and other precursors such as citrulline, Pycnogenol, L-aspartic acid, and ginsenosides which the body synthesizes into Nitric oxide.
Biological functions
See also: Endothelium-derived relaxing factor (EDRF) and signal transduction
In the body, nitric oxide serves several roles, mainly involving small blood vessels. Nitric oxide is synthesized from L-arginine and oxygen by various nitric oxide synthase (NOS) enzymes. The endothelium (inner lining) of blood vessels uses nitric oxide to signal the surrounding smooth muscle to relax, thus dilating the artery and increasing blood flow. This phenomenon is thought to be central to endothelial health. A large percentage of humans are deficient in their manufacture of nitric oxide, placing them at increased risk of cardiovascular disease. This underlies the action of nitroglycerin, amyl nitrate and other nitrate derivatives in the treatment of heart disease: The compounds are converted to nitric oxide (by a process that is not completely understood), which in turn dilates the coronary artery (blood vessels around the heart), thereby increasing its blood supply. A chemical known as asymmetric dimethylarginine can interfere with the production of nitric oxide and is considered a marker of cardiovascular disease.
Macrophages, cells of the immune system, produce nitric oxide in order to kill invading bacteria. Under certain conditions, this can backfire: Fulminant infection (sepsis) causes excess production of nitric oxide by macrophages, leading to vasodilatation (widening of blood vessels), probably one of the main causes of hypotension (low blood pressure) in sepsis.
Nitric oxide also serves as a neurotransmitter between nerve cells. Unlike most other neurotransmitters that only transmit information from a presynaptic to a postsynaptic neuron, the small nitric oxide molecule can diffuse all over and can thereby act on several nearby neurons, even on those not connected by a synapse. It is conjectured that this process may be involved in memory through the maintenance of long-term potentiation. Nitric oxide is an important non-adrenergic, non-cholinergic (NANC) neurotransmitter in various parts of the gastrointestinal tract. It causes relaxation of the gastrointestinal smooth muscle. In the stomach it increases the capacity of the fundus to store food/fluids.
Production of NO also plays a role in development and maintenance of erection by stimulating PDE5-related intracellular cGMP in the smooth muscle cells surrounding the blood vessels supplying the corpus cavernosum; through relaxation of these muscles, more blood can flow in. This is the biological basis of sildenafil (Viagra)or tadalafil (Cialis), which works to turn off the enzyme that converts cGMP to GMP. The high levels of cGMP that result lead to vasodilation and hence erection. The effects of the recreational drugs known as poppers are also thought to be due to nitric oxide.
The discovery of the biological functions of nitric oxide in the 1980s came as a complete surprise and caused quite a stir. Nitric oxide was named "Molecule of the Year" in 1992 by the journal Science, a Nitric Oxide Society was founded, and a scientific journal devoted entirely to nitric oxide was created. The Nobel Prize in Physiology or Medicine in 1998 was awarded to Ferid Murad, Robert F. Furchgott, and Louis Ignarro for the discovery of the signalling properties of nitric oxide. It is estimated that yearly about 3,000 scientific articles about the biological roles of nitric oxide are published.
Chemistry
The chemistry of nitric oxide is very rich. The following is a brief overview of its preparation and reactivity.
Preparation
As stated above, nitric oxide can be produced from the elements at high temperatures. It can be produced from nitric oxide,
8HNO3 + 3Cu → 3Cu(NO3)2 + 4H2O + 2NO
or from the following aqueous reactions,
2NaNO2 + 2NaI + 2H2SO4 → I2 + 4NaHSO4 + 2NO
2NaNO2 + 2FeSO4 + 3H2SO4 → Fe2(SO4)3 + 2NaHSO4 + 2H2O + 2NO
The iron (II) sulfate reaction is a simple method that has been used in undergraduate labs for gas experiments. NO can be produced from the following non-aqueous reagents,
3KNO2(l) + KNO3 (l) + Cr2O3(s) → 2K2CrO4 (s) + 4NO
Commercially, NO is produced by the oxidation of ammonia at 750 to 900 °C in the presence of platinum. The combination of the elements at high temperatures has not been developed into a practical commercial synthesis.
Reactions
When exposed to oxygen, NO is converted into NO2. This has been speculated as occurring via the ONOONO intermediate. In water NO will react with oxygen and water to form HNO2. The reaction is thought to be the following:
4NO + O2 + 2H2O → 4HNO2
NO will react with fluorine, chlorine, and bromine to from the XNO species, known as the nitrosyl halides. Nitrosyl iodide can form but is an extremely short lived species and tends to reform I2.
NO will react with CF3I to form CF3NO and I2. CF3NO is one of the few known blue gases in contrast to NO and CF3I which are both colorless.
At 25 °C and 1 atm NO is thermodynamically unstable. In the 30 to 50 °C range, NO rapidly decomposes to N2O and NO2.
NO reacts with superoxide in a diffusion limited reaction to form peroxynitrite (ONOO-), a potent oxidizing and nitrating agent.
Coordination Chemistry
NO can also behave as a ligand bonded to transition metal complexes. The most common bonding mode of NO is the terminal linear type (M-NO). These groups can have a bond angle of 160-180° but are still termed as linear. In this case the NO group is formally consider a 2-electron donor but actually will donate the free electron to the metal center to become a 3-electron donor of the type NO+. This is what leads to the slightly bent linear geometry.
Nitric oxide can also donate only one electron to the metal. This leads to a bent MNO group where the bond angle is between 120-140°
The NO group can also bridge between metal centers through the nitrogen. The μ2-symmetric or unsymmetric, μ3 and μ4 bonding modes are possible.
Reactions of Coordinated NO
The reactive chemistry of coordinated NO is extensive and will only be mentioned briefly. Some reactions that can occur include:
Cp2NbMe2 + NO → Cp2(Me)Nb(O)NMe + heat → Cp2Nb(O)Me + ½MeN=NMe
(In the second part of this reaction the O is bonded both to the Nb atom and N atom, the N atom is bonded to Nb, O, and Me. This would be easier to understand if it was drawn out.)
(Ph3P)2(CO)ClOsNO + HCl → (Ph3P)2(CO)ClOsN(H)O
Generic oxidation can also occur
L’’n’’MNO + ½O2 → L’’n’’MNO2
That is just a taste.
Characterization of Coordinated NO
Terminal NO groups can be recognized by their strong IR signals at 1610cm-1. Bent dervatives have frequencies below 1610cm-1.
Measurement of nitric oxide
Nitric oxide can be measured using a simple chemiluminescent reaction involving ozone.
A sample containing nitric oxide is mixed with a large quantity of ozone. The nitric oxide reacts with the ozone to produce oxygen and nitrogen dioxide. This reaction also produces light (chemiluminescence), which can be measured using a photodetector. The amount of light produced is proportional to the amount of nitric oxide in the sample.
- NO + O3 → NO2 + O2 + light
There are other methods of testing, including electrochemical methods, where nitric oxide in a test sample reacts to produce a current or voltage difference on a surface.
Reference
- F.A. Cotton, G. Wilkinson, C.A. Murillo, M. Bochmann; Advanced Inorganic Chemistry, 6th ed. Wiley-Interscience, New York, 1999.
- R.B. King; Inorganic Chemistry of Main Group Elements, VCH Publishers, New York, 1995.
External links
- National Pollutant Inventory - Oxides of nitrogen Fact Sheet
- Nitric Oxide: Biology and Chemistry, peer reviewed scientific journal
- 1998 Nobel Prize in Physiology/Medicine for discovery of NO's role in cardiovascular regulation
- Microscale Gas Chemistry: Experiments with Nitrogen Oxidesbg:Азотен оксид
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