Carbon dioxide

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[edit] Chemical and physical properties

For more details on this topic, see Carbon dioxide (data page).

Carbon dioxide is a colourless, odorless gas. When inhaled at concentrations much higher than usual atmospheric levels, it can produce a sour taste in the mouth and a stinging sensation in the nose and throat. These effects result from the gas dissolving in the mucous membranes and saliva, forming a weak solution of carbonic acid. This sensation can also occur during an attempt to stifle a burp after drinking a carbonated beverage. Amounts above 5,000 ppm are considered very unhealthy, and those above about 50,000 ppm (equal to 5% by volume) are considered dangerous to animal life.^[3]

At standard temperature and pressure, the density of carbon dioxide is around 1.98 kg/m³, about 1.5 times that of air. The carbon dioxide molecule (O=C=O) contains two double bonds and has a linear shape. It has no electrical dipole, and as it is fully oxidized, it is moderately reactive and is non-flammable, but will support the combustion of metals such as magnesium.

[edit] History of human understanding

Carbon dioxide was one of the first gases to be described as a substance distinct from air. In the seventeenth century, the Flemish chemist Jan Baptist van Helmont observed that when he burned charcoal in a closed vessel, the mass of the resulting ash was much less than that of the original charcoal. His interpretation was that the rest of the charcoal had been transmuted into an invisible substance he termed a "gas" or "wild spirit" (spiritus sylvestre).

The properties of carbon dioxide were studied more thoroughly in the 1750s by the Scottish physician Joseph Black. He found that limestone (calcium carbonate) could be heated or treated with acids to yield a gas he called "fixed air." He observed that the fixed air was denser than air and did not support either flame or animal life. Black also found that when bubbled through an aqueous solution of lime (calcium hydroxide), it would precipitate calcium carbonate. He used this phenomenon to illustrate that carbon dioxide is produced by animal respiration and microbial fermentation. In 1772, English chemist Joseph Priestley published a paper entitled Impregnating Water with Fixed Air in which he described a process of dripping sulfuric acid (or oil of vitriol as Priestley knew it) on chalk in order to produce carbon dioxide, and forcing the gas to dissolve by agitating a bowl of water in contact with the gas.^[6]

Carbon dioxide was first liquefied (at elevated pressures) in 1823 by Humphry Davy and Michael Faraday.^[7] The earliest description of solid carbon dioxide was given by Charles Thilorier, who in 1834 opened a pressurized container of liquid carbon dioxide, only to find that the cooling produced by the rapid evaporation of the liquid yielded a "snow" of solid CO₂.^[8]

[edit] Isolation and production

Carbon dioxide may be obtained from air distillation. However, this yields only very small quantities of CO₂. A large variety of chemical reactions yield carbon dioxide, such as the reaction between most acids and most metal carbonates. For example, the reaction between hydrochloric acid and calcium carbonate (limestone or chalk) is depicted below:

2 HCl + CaCO₃ → CaCl₂ + H₂CO₃

The H₂CO₃ then decomposes to water and CO₂. Such reactions are accompanied by foaming or bubbling, or both. In industry such reactions are widespread because they can be used to neutralize waste acid streams.

The production of quicklime (CaO) a chemical that has widespread use, from limestone by heating at about 850 °C also produces CO₂:

CaCO₃ → CaO + CO₂

The combustion of all carbon containing fuels, such as methane (natural gas), petroleum distillates (gasoline, diesel, kerosene, propane), but also of coal and wood, will yield carbon dioxide and, in most cases, water. As an example the chemical reaction between methane and oxygen is given below.

CH₄ + 2 O₂ → CO₂ + 2 H₂O

Iron is reduced from its own oxides with coke in a blast furnace, producing pig iron and carbon dioxide:

2 Fe₂O₃ + 3 C → 4 Fe + 3 CO₂

Yeast metabolizes sugar to produce carbon dioxide and ethanol, also known as alcohol, in the production of wines, beers and other spirits, but also in the production of bioethanol:

C₆H₁₂O₆ → 2 CO₂ + 2 C₂H₅OH

All aerobic organisms produce CO₂ when they oxidize carbohydrates, fatty acids, and proteins in the mitochondria of cells. The large number of reactions involved are exceedingly complex and not described easily. Refer to (cellular respiration, anaerobic respiration and photosynthesis). Photoautotrophs (i.e. plants, cyanobacteria) use another modus operandi: Plants absorb CO₂ from the air, and, together with water, react it to form carbohydrates:

nCO₂ + nH₂O → (CH₂O)_n + nO₂

Carbon dioxide is soluble in water, in which it spontaneously interconverts between CO₂ and H₂CO₃ (carbonic acid). The relative concentrations of CO₂, H₂CO₃, and the deprotonated forms HCO₃⁻ (bicarbonate) and CO₃²⁻(carbonate) depend on the pH. In neutral or slightly alkaline water (pH > 6.5), the bicarbonate form predominates (>50%) becoming the most prevalent (>95%) at the pH of seawater, while in very alkaline water (pH > 10.4) the predominant (>50%) form is carbonate. The bicarbonate and carbonate forms are very soluble, such that air-equilibrated ocean water (mildly alkaline with typical pH = 8.2 – 8.5) contains about 120 mg of bicarbonate per liter.

[edit] Uses

Carbon dioxide is used by the food industry, the oil industry, and the chemical industry.^[9] It is used in many consumer products that require pressurized gas because it is inexpensive and nonflammable, and because it undergoes a phase transition from gas to liquid at room temperature at an attainable pressure of approximately 60 bar (870 psi, 59 atm), allowing far more carbon dioxide to fit in a given container than otherwise would. Life jackets often contain canisters of pressured carbon dioxide for quick inflation. Aluminum capsules are also sold as supplies of compressed gas for airguns, paintball markers, for inflating bicycle tires, and for making seltzer. Rapid vaporization of liquid carbon dioxide is used for blasting in coal mines. High concentrations of carbon dioxide can also be used to kill pests, such as the Common Clothes Moth.

[edit] Drinks

Carbon dioxide is used to produce carbonated soft drinks and soda water. Traditionally, the carbonation in beer and sparkling wine comes about through natural fermentation, but some manufacturers carbonate these drinks artificially.

[edit] Foods

A candy called Pop Rocks is pressurized with carbon dioxide gas at about 40 bar (600 psi). When placed in the mouth, it dissolves (just like other hard candy) and releases the gas bubbles with an audible pop.

Leavening agents produce carbon dioxide to cause dough to rise. Baker's yeast produces carbon dioxide by fermentation of sugars within the dough, while chemical leaveners such as baking powder and baking soda release carbon dioxide when heated or if exposed to acids.

[edit] Pneumatic systems

Carbon dioxide is the most commonly used compressed gas for pneumatic systems in portable pressure tools and combat robots.

[edit] Fire extinguisher

Carbon dioxide extinguishes flames, and some fire extinguishers, especially those designed for electrical fires, contain liquid carbon dioxide under pressure. Carbon dioxide has also been widely used as an extinguishing agent in fixed fire protection systems for total flooding of a protected space, (National Fire Protection Association Code 12). International Maritime Organisation standards also recognise carbon dioxide systems for fire protection of ship holds and engine rooms. Carbon dioxide based fire protection systems have been linked to several deaths. A review of CO2 systems (Carbon Dioxide as a Fire Suppressant: Examining the Risks, US EPA) identified 51 incidents between 1975 and the date of the report, causing 72 deaths and 145 injuries.

[edit] Welding

Carbon dioxide also finds use as an atmosphere for welding, although in the welding arc, it reacts to oxidize most metals. Use in the automotive industry is common despite significant evidence that welds made in carbon dioxide are brittler than those made in more inert atmospheres, and that such weld joints deteriorate over time because of the formation of carbonic acid. It is used as a welding gas primarily because it is much less expensive than more inert gases such as argon or helium.

[edit] Caffeine removal

Liquid carbon dioxide is a good solvent for many lipophilic organic compounds, and is used to remove caffeine from coffee. First, the green coffee beans are soaked in water. The beans are placed in the top of a column seventy feet (21 m) high. Then super-pressurized carbon dioxide in fluid form at about 93 degrees Celsius enters at the bottom of the column. The caffeine diffuses out of the beans and into the carbon dioxide.

[edit] Pharmaceutical and other chemical processing

Carbon dioxide has begun to attract attention in the pharmaceutical and other chemical processing industries as a less toxic alternative to more traditional solvents such as organochlorides. It's used by some dry cleaners for this reason. (See green chemistry.)

In the chemical industry, carbon dioxide is used for the production of urea, carbonates and bicarbonates, and sodium salicylate.

[edit] Biological applications

Plants require carbon dioxide to conduct photosynthesis, and greenhouses may enrich their atmospheres with additional CO₂ to boost plant growth, since its low present-day atmosphere concentration is just above the "suffocation" level for green plants. A photosynthesis-related drop in carbon dioxide concentration in a greenhouse compartment can kill green plants. At high concentrations, carbon dioxide is toxic to animal life, so raising the concentration to 10,000 ppm (1%) for several hours can eliminate pests such as whiteflies and spider mites in a greenhouse.

It has been proposed that carbon dioxide from power generation be bubbled into ponds to grow algae that could then be converted into biodiesel fuel.^[10] Carbon dioxide is already increasingly used in greenhouses as the main carbon source for Spirulina algae. In medicine, up to 5% carbon dioxide is added to pure oxygen for stimulation of breathing after apnea and to stabilize the O₂/CO₂ balance in blood.

[edit] Lasers

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A common type of industrial gas laser is the carbon dioxide laser.

[edit] Polymers and plastics

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Carbon dioxide can also be combined with limonene oxide from orange peels or other epoxides to create polymers and plastics.^[11]

[edit] Oil recovery

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Carbon dioxide is used in enhanced oil recovery where it is injected into or adjacent to producing oil wells, usually under supercritical conditions. It acts as both a pressurizing agent and, when dissolved into the underground crude oil, significantly reduces its viscosity, enabling the oil to flow more rapidly through the earth to the removal well.^[12] In mature oil fields, extensive pipe networks are used to carry the carbon dioxide to the injection points.

[edit] As refrigerants

Liquid and solid carbon dioxide are important refrigerants, especially in the food industry, where they are employed during the transportation and storage of ice cream and other frozen foods. Solid carbon dioxide is called "dry ice" and is used for small shipments where refrigeration equipment is not practical.

Liquid carbon dioxide (industry nomenclature R744 / R-744) was used as a refrigerant prior to the discovery of R-12. Its physical properties are highly favorable for cooling, refrigeration, and heating purposes, having a high volumetric cooling capacity. Due to their operation at pressures of up to 130 bars, CO₂ systems require highly resistant components that have been already developed to serial production in many sectors.

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Its environmental advantages (GWP of 1, non-ozone depleting, non-toxic, non-flammable) could make it the future working fluid to replace current HFCs in cars, supermarkets, hot water heat pumps, among others. Some applications: Coca-Cola has fielded CO₂-based beverage coolers and the US Army is interested in CO₂ refrigeration and heating technology.^[13][14]

By the end of 2007, the global car industry is expected to decide on the next-generation refrigerant in car air conditioning. CO₂ is one discussed option.(see The Cool War)

[edit] Coal bed methane recovery

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In enhanced coal bed methane recovery, carbon dioxide is pumped into the coal seam to displace methane.^[15]

[edit] Wine making

Carbon dioxide in the form of dry ice is often used in the wine making process to cool down bunches of grapes quickly after picking to help prevent spontaneous fermentation by wild yeasts. The advantage of using dry ice over regular water ice is that it cools the grapes without adding any additional water that may decrease the sugar concentration in the grape must, and therefore also decrease the alcohol concentration in the finished wine.

Dry ice is also used during the cold soak phase of the wine making process to keep grapes cool. The carbon dioxide gas that results from the sublimation of the dry ice tends to settle to the bottom of tanks because it is heavier than regular air. The settled carbon dioxide gas creates an hyoxic environment which helps to prevent bacteria from growing on the grapes until it is time to start the fermentation with the desired strain of yeast.

Carbon dioxide is also used to create a hypoxic environment for carbonic maceration, the process used to produce Beaujolais wine.

Carbon dioxide is sometimes used to top up wine bottles or other storage vessels such as barrels to prevent oxidation, though it has the problem that it can dissolve into the wine, making a previously still wine slightly fizzy. For this reason, other gasses such as nitrogen or argon are preferred for this process by professional wine makers.

[edit] In the Earth's atmosphere

Main article: Carbon dioxide in the Earth's atmosphere

Carbon dioxide in earth's atmosphere is considered a trace gas currently occurring at an average concentration of about 385 parts per million by volume or 582 parts per million by mass.^[16] The mass of the Earth atmosphere is 5.14×10¹⁸ kg ^[17], so the total mass of atmospheric carbon dioxide is 3.0×10¹⁵ kg (3,000 gigatonnes). Atmospheric concentrations of carbon dioxide fluctuate slightly with the change of the seasons, driven primarily by seasonal plant growth in the Northern Hemisphere. Concentrations of carbon dioxide fall during the northern spring and summer as plants consume the gas, and rise during the northern autumn and winter as plants go dormant, die and decay (see graph at right). Concentrations also vary considerably on a regional basis: in urban areas it is generally higher and indoors it can reach 10 times the background atmospheric concentration.

Carbon dioxide is a greenhouse gas. See greenhouse effect for more.

Due to human activities such as the combustion of fossil fuels and deforestation, the concentration of atmospheric carbon dioxide has increased by about 35% since the beginning of the age of industrialization.^[19] In 1999, 2,244,804,000 (=~2.2×10⁹) metric tons of CO₂ were produced in the U.S. as a result of electric energy generation. This is an output rate of 0.6083 kg (1.341 pounds) per kWh.^[20]

Five hundred million years ago carbon dioxide was 20 times more prevalent than today, decreasing to 4–5 times during the Jurassic period and then maintained a slow decline until the industrial revolution, with a particularly swift reduction occurring 49 million years ago.^[21][22]

Up to 40% of the gas emitted by some volcanoes during subaerial volcanic eruptions is carbon dioxide.^[23] According to the best estimates, volcanoes release about 130-230 million tonnes (145-255 million tons) of CO₂ into the atmosphere each year. Carbon dioxide is also produced by hot springs such as those at the Bossoleto site near Rapolano Terme in Tuscany, Italy. Here, in a bowl-shaped depression of about 100 m diameter, local concentrations of CO₂ rise to above 75% overnight, sufficient to kill insects and small animals, but warm rapidly when sunlit and disperse by convection during the day^[24] Locally high concentrations of CO₂, produced by disturbance of deep lake water saturated with CO₂ are thought to have caused 37 fatalities at Lake Monoun, Cameroon in 1984 and 1700 casualties at Lake Nyos, Cameroon in 1986.^[25] However, emissions of CO₂ by human activities are currently more than 130 times greater than the quantity emitted by volcanoes, amounting to about 27 billion tonnes per year.^[26]

[edit] In the oceans

There is about 50 times as much carbon dissolved in the oceans in the form of CO₂ and CO₂ hydration products as exists in the atmosphere. The oceans act as an enormous carbon sink, having "absorbed about one-third of all human-generated CO₂ emissions to date."^[27] Generally, gas solubility decreases as water temperature increases. Accordingly the ability of the oceans to absorb carbon dioxide from the atmosphere decreases as ocean temperatures rise.

Most of the CO₂ taken up by the ocean forms carbonic acid. Some is consumed in photosynthesis by organisms in the water, and a small proportion of that sinks and leaves the carbon cycle. There is considerable concern that as a result of increased CO₂ in the atmosphere the acidity of seawater has been increasing and may adversely affect organisms living in the water. In particular, with increasing acidity, the availability of carbonates for forming shells decreases.^[28]

[edit] Biological role

Carbon dioxide is an end product in organisms that obtain energy from breaking down sugars, fats and amino acids with oxygen as part of their metabolism, in a process known as cellular respiration. This includes all plants, animals, many fungi and some bacteria. In higher animals, the carbon dioxide travels in the blood from the body's tissues to the lungs where it is exhaled. In plants using photosynthesis, carbon dioxide is absorbed from the atmosphere.

[edit] Role in photosynthesis

Plants remove carbon dioxide from the atmosphere by photosynthesis, also called carbon assimilation, which uses light energy to produce organic plant materials (cellulose) by combining carbon dioxide and water. Free oxygen is released as gas from the decomposition of water molecules, while the hydrogen is split into its protons and electrons and used to generate chemical energy via photophosphorylation. This energy is required for the fixation of carbon dioxide in the Calvin cycle to form sugars. These sugars can then be used for growth within the plant through respiration.

Even when vented, carbon dioxide must be introduced into greenhouses to maintain plant growth, as the concentration of carbon dioxide can fall during daylight hours to as low as 200 ppm. Plants can potentially grow up to 50 percent faster in concentrations of 1,000 ppm CO₂ when compared with ambient conditions.^[29]

Plants also emit CO₂ during respiration, so it is only during growth stages that plants are net absorbers. For example a growing forest will absorb many tons of CO₂ each year, however a mature forest will produce as much CO₂ from respiration and decomposition of dead specimens (e.g. fallen branches) as used in biosynthesis in growing plants.^[30] Regardless of this, mature forests are still valuable carbon sinks, helping maintain balance in the Earth's atmosphere. Additionally, and crucially to life on earth, phytoplankton photosynthesis absorbs dissolved CO₂ in the upper ocean and thereby promotes the absorption of CO₂ from the atmosphere.^[31]

[edit] Toxicity

Carbon dioxide content in fresh air (averaged between sea-level and 10 hPa level, i.e. about 30 km altitude) varies between 0.036% (360 ppm) and 0.039% (390 ppm), depending on the location (see graphical map of CO₂).

According to the Australian Maritime Safety Authority, "Prolonged exposure to moderate concentrations can cause acidosis and adverse effects on calcium phosphorus metabolism resulting in increased calcium deposits in soft tissue. Carbon dioxide is toxic to the heart and causes diminished contractile force. At concentrations of three per cent by volume in air, it is mildly narcotic and causes increased blood pressure and pulse rate, and causes reduced hearing. At concentrations of about five per cent by volume it causes stimulation of the respiratory centre, dizziness, confusion and difficulty in breathing accompanied by headache and shortness of breath. At about eight per cent concentration it causes headache, sweating, dim vision, tremor and loss of consciousness after exposure for between five and ten minutes." ^[32]

A natural disaster linked to CO₂ intoxication occurred during the limnic eruptions in the CO₂-rich lakes of Monoun and Nyos in the Okun range of North-West Cameroon: the gas was brutally expelled from the mountain lakes and leaked into the surrounding valleys, killing most animal forms. During the Lake Nyos tragedy of 1986, 1700 villagers and 3500 livestock died.^[33]

Due to the health risks associated with carbon dioxide exposure, the U.S. Occupational Safety and Health Administration says that average exposure for healthy adults during an eight-hour work day should not exceed 5,000 ppm (0.5%). The maximum safe level for infants, children, the elderly and individuals with cardio-pulmonary health issues is significantly less. For short-term (under ten minutes) exposure, the U.S. National Institute for Occupational Safety and Health (NIOSH) and American Conference of Government Industrial Hygienists (ACGIH) limit is 30,000 ppm (3%). NIOSH also states that carbon dioxide concentrations exceeding 4% are immediately dangerous to life and health. ^[34]

Adaptation to increased levels of CO₂ occurs in humans. Continuous inhalation of CO₂ can be tolerated at three percent inspired concentrations for at least one month and four percent inspired concentrations for over a week. It was suggested that 2.0 percent inspired concentrations could be used for closed air spaces (ex. Submarine) since the adaptation is physiological and reversible. Decrement in performance or in normal physical activity does not happen at this level.^[35][36]

These figures are valid for pure carbon dioxide. In indoor spaces occupied by people the carbon dioxide concentration will reach higher levels than in pure outdoor air. Concentrations higher than 1,000 ppm will cause discomfort in more than 20% of occupants, and the discomfort will increase with increasing CO₂ concentration. The discomfort will be caused by various gases coming from human respiration and perspiration, and not by CO₂ alone. At 2,000 ppm the majority of occupants will feel a significant degree of discomfort, and many will develop nausea and headaches. The CO₂ concentration between 300 and 2,500 ppm is used as an indicator of indoor air quality.

Acute carbon dioxide toxicity is sometimes known by the names given to it by miners: blackdamp (also called choke damp or stythe). Miners would try to alert themselves to dangerous levels of carbon dioxide in a mine shaft by bringing a caged canary with them as they worked. The canary would inevitably die before CO₂ reached levels toxic to people. (The canary would also indicate dangerous levels of methane and other gases by the same principle.)

Carbon dioxide ppm levels (CDPL) are a surrogate for measuring indoor pollutants that may cause occupants to grow drowsy, get headaches, or function at lower activity levels. To eliminate most Indoor Air Quality complaints, total indoor CDPL must be reduced to below 600. NIOSH considers that indoor air concentrations that exceed 1,000 are a marker suggesting inadequate ventilation. ASHRAE recommends they not exceed 1,000 inside a space.

[edit] Human physiology

See also: Arterial blood gas

CO₂ is carried in blood in three different ways. (The exact percentages vary depending whether it is arterial or venous blood).

• Most of it (about 70% – 80%) is converted to bicarbonate ions HCO₃⁻ by the enzyme carbonic anhydrase in the red blood cells,^[37] by the reaction CO₂ + H₂O → H₂CO₃ → H⁺ + HCO₃⁻.

• 5% – 10% is dissolved in the plasma^[37]

• 5% – 10% is bound to hemoglobin as carbamino compounds^[37]

Hemoglobin, the main oxygen-carrying molecule in red blood cells, carries both oxygen and carbon dioxide. However, the CO₂ bound to hemoglobin does not bind to the same site as oxygen. Instead, it combines with the N-terminal groups on the four globin chains. However, because of allosteric effects on the hemoglobin molecule, the binding of CO₂ decreases the amount of oxygen that is bound for a given partial pressure of oxygen. The decreased binding to carbon dioxide in the blood due to increased oxygen levels is known as the Haldane Effect, and is important in the transport of carbon dioxide from the tissues to the lungs. Conversely, a rise in the partial pressure of CO₂ or a lower pH will cause offloading of oxygen from hemoglobin, which is known as the Bohr Effect.

Carbon dioxide is one of the mediators of local autoregulation of blood supply. If its levels are high, the capillaries expand to allow a greater blood flow to that tissue.

Bicarbonate ions are crucial for regulating blood pH. A person's breathing rate influences the level of CO₂ in their blood. Breathing that is too slow or shallow causes respiratory acidosis, while breathing that is too rapid leads to hyperventilation, which may cause respiratory alkalosis.

Although the body requires oxygen for metabolism, low oxygen levels do not stimulate breathing. Rather, breathing is stimulated by higher carbon dioxide levels. As a result, breathing low-pressure air or a gas mixture with no oxygen at all (such as pure nitrogen) can lead to loss of consciousness without ever experiencing air hunger. This is especially perilous for high-altitude fighter pilots. It is also why flight attendants instruct passengers, in case of loss of cabin pressure, to apply the oxygen mask to themselves first before helping others — otherwise one risks going unconscious.^[37]

Typically the gas we exhale is about 4% to 5% carbon dioxide and 4% to 5% less oxygen than was inhaled.

According to a study by the United States Department of Agriculture, an average person's respiration generates approximately 450 liters (roughly 900 grams) of carbon dioxide per day.^[38]

[edit] See also

[edit] References

[edit] External links

• International Chemical Safety Card 0021

• CID 280 from PubChem
• CO₂ Carbon Dioxide Properties, Uses, Applications
• Dry Ice information
• Trends in Atmospheric Carbon Dioxide (NOAA)
• NASA's Orbiting Carbon Observatory
• Time Chart of Atmospheric CO₂

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