Ozone or trioxygen (O3) is a triatomic molecule, consisting of three oxygen atoms. It is an allotrope of oxygen that is much less stable than the diatomic O2. Ground-level ozone is an air pollutant with harmful effects on the respiratory systems of animals and humans. Ozone in the upper atmosphere filters potentially damaging ultraviolet light from reaching the Earth's surface. It is present in low concentrations throughout the Earth's atmosphere. It has many industrial and consumer applications.
Ozone, the first allotrope of a chemical element to be recognized by science, was proposed as a distinct chemical compound by Christian Friedrich Schönbein in 1840, who named it after the Greek word for smell (ozein), from the peculiar odor in lightning storms. The formula for ozone, O3, was not determined until 1865 by Jacques-Louis Soret and confirmed by Schönbein in 1867.
Most people can detect about 0.01 ppm in air. Exposure of 0.1 to 1 ppm produces headaches, burning eyes, and irritation to the respiratory passages.
Ozone is a powerful oxidizing agent, far better than dioxygen. It is also unstable at high concentrations, decaying to ordinary diatomic oxygen (in about half an hour in atmospheric conditions):
The above reaction is accompanied by chemiluminescence. The NO2 can be further oxidized:
The NO3 formed can react with NO2 to form N2O5:
In an aqueous solution, however, two competing simultaneous reactions occur, one to produce elemental sulfur, and one to produce sulfuric acid:
Solid nitryl perchlorate can be made from NO2, ClO2, and O3 gases:
Although KO3 can be formed as above, it can also be formed from potassium hydroxide and ozone:
NaO3 and LiO3 must be prepared by action of CsO3 in liquid NH3 on an ion exchange resin containing Na+ or Li+ ions:
Treatment with ozone of calcium dissolved in ammonia leads to ammonium ozonide and not calcium ozonide:
Finally, ozone will also completely decompose urea:
The standard way to express total ozone levels (the amount of ozone in a vertical column) in the atmosphere is by using Dobson units. Concentrations at a point are measured in parts per billion (ppb) or in μg/m³.
The highest levels of ozone in the atmosphere are in the stratosphere, in a region also known as the ozone layer between about 10 km and 50 km above the surface (or between about 6 and 31 miles). Here it filters out photons with shorter wavelengths (less than 320 nm) of ultraviolet light, also called UV rays, (270 to 400 nm) from the Sun that would be harmful to most forms of life in large doses. These same wavelengths are also among those responsible for the production of vitamin D, a vitamin also produced by the human body. Ozone in the stratosphere is mostly produced from ultraviolet rays reacting with oxygen:
It is destroyed by the reaction with atomic oxygen:
The latter reaction is catalysed by the presence of certain free radicals, of which the most important are hydroxyl (OH), nitric oxide (NO) and atomic chlorine (Cl) and bromine (Br). In recent decades the amount of ozone in the stratosphere has been declining mostly because of emissions of CFCs and similar chlorinated and brominated organic molecules, which have increased the concentration of ozone-depleting catalysts above the natural background. Ozone only makes up 0.00006% of the atmosphere.
Low level ozone (or tropospheric ozone) is regarded as a pollutant by the World Health Organization and the United States Environmental Protection Agency (EPA). It is not emitted directly by car engines or by industrial operations. It is formed by the reaction of sunlight on air containing hydrocarbons and nitrogen oxides that react to form ozone directly at the source of the pollution or many kilometers down wind.
Ozone reacts directly with some hydrocarbons such as aldehydes and thus begins their removal from the air, but the products are themselves key components of smog. Ozone photolysis by UV light leads to production of the hydroxyl radical OH and this plays a part in the removal of hydrocarbons from the air, but is also the first step in the creation of components of smog such as peroxyacyl nitrates which can be powerful eye irritants. The atmospheric lifetime of tropospheric ozone is about 22 days; its main removal mechanisms are being deposited to the ground, the above mentioned reaction giving OH, and by reactions with OH and the peroxy radical HO2· (Stevenson et al, 2006).
There is evidence of significant reduction in agricultural yields because of increased ground-level ozone and pollution which interferes with photosynthesis and stunts overall growth of some plant species.
Certain examples of cities with elevated ozone readings are Houston, Texas, and Mexico City, Mexico. Houston has a reading of around 41 ppb, while Mexico City is far more hazardous, with a reading of about 125 ppb.
Although ozone was present at ground level before the Industrial Revolution, peak concentrations are now far higher than the pre-industrial levels, and even background concentrations well away from sources of pollution are substantially higher. This increase in ozone is of further concern because ozone present in the upper troposphere acts as a greenhouse gas, absorbing some of the infrared energy emitted by the earth. Quantifying the greenhouse gas potency of ozone is difficult because it is not present in uniform concentrations across the globe. However, the scientific review on the climate change (the IPCC Third Assessment Report) suggests that the radiative forcing of tropospheric ozone is about 25% that of carbon dioxide.
Ozone gas attacks any polymer possessing olefinic or double bonds within its chain structure, such materials including natural rubber, nitrile rubber, and Styrene-butadiene rubber. Products made using these polymers are especially susceptible to attack, which causes cracks to grow longer and deeper with time, the rate of crack growth depending on the load carried by the product and the concentration of ozone in the atmosphere. Such materials can be protected by adding antiozonants, such as waxes, which bond to the surface to create a protective film or blend with the material and provide long term protection. Ozone cracking used to be a serious problem in car tires for example, but the problem is now seen only in very old tires. On the other hand, many critical products like gaskets and O-rings may be attacked by ozone produced within compressed air systems. Fuel lines are often made from reinforced rubber tubing and may also be susceptible to attack, especially within engine compartments where low levels of ozone are produced from electrical equipment.
There is a great deal of evidence to show that high concentrations of ozone, created by high concentrations of pollution and daylight UV rays at the earth's surface, can harm lung function and irritate the respiratory system. A connection has also been shown to exist between increased ozone caused by thunderstorms and hospital admissions of asthma sufferers. Air quality guidelines such as those from the World Health Organization are based on detailed studies of what levels can cause measurable health effects. Exposure to ozone and the pollutants that produce it has been linked to premature death, asthma, bronchitis, heart attack, and other cardiovascular problems. According to scientists with the United States Environmental Protection Agency (EPA), susceptible people can be adversely effected by ozone levels as low as 40 ppb.
The Clean Air Act directs the EPA to set National Ambient Air Quality Standards for several pollutants, including ground-level ozone, and counties out of compliance with these standard are required to take steps to reduce their levels. In May 2008, the EPA lowered its ozone standard from 80 ppb to 75 ppb. This proved controversial, since the Agency's own scientists and advisory board had recommended lowing the standard to 60 ppb, and the World Health Organization recommends 51 ppb. Many public health and environmental groups also supported the 60 ppb standard. On the other hand, the EPA had already designated over 300 mostly urban counties as out of compliance, and lowering the standard to 75 ppb put hundreds more in non-compliance. Lowering it further to 60 ppb would likely have left most of the US in non-compliance. Manufacturers, employers, and others argued that the cost of compliance with the lower standard would be prohibitive. The EPA has also developed an Air Quality Index to help explain air pollution levels to the general public. Eight-hour average ozone concentrations of 85 to 104 ppbv are described as "Unhealthy for Sensitive Groups", 105 ppbv to 124 ppbv as "unhealthy" and 125 ppb to 404 ppb as "very unhealthy".
Ozone can also be present in indoor air pollution.
A common British folk myth dating back to the Victorian era holds that the smell of the sea is caused by ozone, and that this smell has "bracing" health benefits. Neither of these is true. The characteristic "smell of the sea" is not caused by ozone but by the presence of dimethyl sulfide generated by phytoplankton, and dimethyl sulfide, like ozone, is toxic in high concentrations.
When inhaled, ozone reacts with compounds lining the lungs to form specific, cholesterol-derived metabolites that are thought to facilitate the build-up and pathogenesis of atherosclerotic plaques (a form of heart disease). These metabolites have been confirmed as naturally occurring in human atherosclerotic arteries and are categorized into a class of secosterols termed “Atheronals”, generated by ozonolysis of cholesterol's double bond to form a 5,6 secosterol as well as a secondary condensation product via aldolization.
Ozone has been implicated to have an adverse effect on plant growth, "...Ozone reduced total chlorophylls, carotenoid and carbohydrate concentration, and increased 1-aminocyclopropane-1-carboxylic acid (ACC) content and ethylene production. In treated plants, the ascorbate leaf pool was decreased, while lipid peroxidation and solute leakage were significantly higher than in ozone-free controls. The data indicated that ozone triggered protective mechanisms against oxidative stress in citrus.
UV ozone generators employ a light source that generates a narrow-band ultraviolet light, a subset of that produced by the Sun. The Sun's UV sustains the ozone layer in the stratosphere of Earth. While standard UV ozone generators tend to be less expensive, they usually produce ozone with a concentration of about 0.5% or lower. Another disadvantage of this method is that it requires the air (oxygen) to be exposed to the UV source for a longer amount of time, and any gas that is not exposed to the UV source will not be treated. This makes UV generators impractical for use in situations that deal with rapidly moving air or water streams (in-duct air sterilization, for example). Production of ozone is one of the potential dangers of ultraviolet germicidal irradiation.
In the cold plasma method, pure oxygen gas is exposed to a plasma created by dielectric barrier discharge. The diatomic oxygen is split into single atoms, which then recombine in triplets to form ozone.
Cold plasma machines utilize pure oxygen as the input source and produce a maximum concentration of about 5% ozone. They produce far greater quantities of ozone in a given space of time compared to ultraviolet production. However, because cold plasma ozone generators are very expensive, they are found less frequently than the previous two types.
The discharges manifest as filamentary transfer of electrons (micro discharges) in a gap between two electrodes. In order to evenly distribute the micro discharges, a dielectric insulator must be used to separate the metallic electrodes and to prevent arcing.
Some cold plasma units also have the capability of producing short-lived allotropes of oxygen which include O4, O5, O6, O7, etc. These anions are even more reactive than ordinary O3.
The dominating parameter influencing ozone generation efficiency is the gas temperature, which is controlled by cooling water temperature and/or gas velocity. The cooler the water, the better the ozone synthesis. The lower the gas velocity, the higher the concentration (but the lower the net ozone produced). At typical industrial conditions, almost 90% of the effective power is dissipated as heat and needs to be removed by a sufficient cooling water flow.
Because of the high reactivity of ozone, only few materials may be used like stainless steel (quality 316L), titanium, aluminium (as long as no moisture is present), glass, polytetrafluorethylene, or polyvinylidene fluoride. Viton may be used with the restriction of constant mechanical forces and absence of humidity (humidity limitations apply depending on the formulation). Hypalon may be used with the restriction that no water come in contact with it, except for normal atmospheric levels. Embrittlement or shrinkage is the common mode of failure of elastomers with exposure to ozone. Ozone cracking is the common mode of failure of elastomer seals like O-rings.
In the laboratory, ozone can be produced by electrolysis using a 9 volt battery, a pencil graphite rod cathode, a platinum wire anode and a 3M sulfuric acid electrolyte. The half cell reactions taking place are
It can also be prepared by passing 10,000-20,000 volts DC through dry O2. This can be done with an apparatus consisting of two concentric glass tubes sealed together at the top, with in and out spigots at the top and bottom of the outer tube. The inner core should have a length of metal foil inserted into it connected to one side of the power source. The other side of the power source should be connected to another piece of foil wrapped around the outer tube. Dry O2 should be run through the tube in one spigot. As the O2 is run through one spigot into the apparatus and 10,000-20,000 volts DC are applied to the foil leads, electricity will discharge between the dry dioxygen in the middle and form O3 in O2 out the other spigot. The reaction can be summarized as follows:
Low levels of ozone have been advertised to be of some disinfectant use in residential homes, however the concentration of ozone in dry air required to have a rapid, substantial effect on airborne pathogens exceeds safe levels recommended by the U.S. Occupational Safety and Health Administration and Environmental Protection Agency. Humidity control can vastly improve both the killing power of the ozone and the rate at which it decays back to oxygen (more humidity allows more effectiveness). Spore forms of most pathogens are very tolerant of atmospheric ozone in concentrations where asthma patients start to have issues.
Industrially, ozone is used to:
Many hospitals in the U.S. and around the world use large ozone generators to decontaminate operating rooms between surgeries. The rooms are cleaned and then sealed airtight before being filled with ozone which effectively kills or neutralizes all remaining bacteria.
Ozone is used as an alternative to chlorine or chlorine dioxide in the bleaching of wood pulp . It is often used in conjunction with oxygen and hydrogen peroxide to eliminate the need for chlorine-containing compounds in the manufacture of high-quality, white paper
In the U.S., air purifiers emitting lower levels of ozone have been sold. This kind of air purifier is sometimes claimed to imitate nature's way of purifying the air without filters and to sanitize both it and household surfaces. The United States Environmental Protection Agency has declared that there is "evidence to show that at concentrations that do not exceed public health standards, ozone is not effective at removing many odor-causing chemicals" or "viruses, bacteria, mold, or other biological pollutants." Furthermore, its report states that "results of some controlled studies show that concentrations of ozone considerably higher than these [human safety] standards are possible even when a user follows the manufacturer’s operating instructions. The government successfully sued one company in 1995, ordering it to stop repeating health claims without supporting scientific studies.
Ozonated water is used to launder clothes and to sanitize food, drinking water, and surfaces in the home. According to the FDA, it is "amending the food additive regulations to provide for the safe use of ozone in gaseous and aqueous phases as an antimicrobial agent on food, including meat and poultry." Studies at California Polytechnic University demonstrated that 0.3 ppm levels of ozone dissolved in filtered tapwater can produce a reduction of more than 99.99% in such food-borne microorganisms as salmonella, E. coli 0157:H7, and Campylobacter. Ozone can be used to remove pesticide residues from fruits and vegetables.
New, patented technology uses ozone to disinfect and deodorize protective sports gear by blowing it directly into the equipment to destroy bacteria within the padding. This has proven particularly useful in battling the spread of MRSA.
Ozone is used in homes and hot tubs to kill bacteria in the water and to reduce the amount of chlorine or bromine required by reactivating them to their free state. Since ozone does not remain in the water long enough, ozone by itself is ineffective at preventing cross-contamination among bathers and must be used in conjunction with these halogens. Gaseous ozone created by ultraviolet light or by corona discharge is injected into the water.
Ozone is also widely used in treatment of water in aquariums and fish ponds. Its use can minimize bacterial growth, control parasites, eliminate transmission of some diseases, and reduce or eliminate "yellowing" of the water. Ozone must not come in contact with fish's gill structures. Natural salt water (with life forms) provides enough "instantaneous demand" that controlled amounts of ozone activate bromide ion to hypobromous acid, and the ozone entirely decays in a few seconds to minutes. If oxygen fed ozone is used, the water will be higher in dissolved oxygen, fish's gill structures will atrophy and they will become dependent on higher dissolved oxygen levels.