Carbon dioxide

Carbon dioxide is a chemical compound composed of two oxygen atoms covalently bonded to a single carbon atom. It is a gas at standard temperature and pressure and exists in Earth's atmosphere in this state. It is currently at a globally averaged concentration of approximately 383 ppm by volume in the Earth's atmosphere,^[1] although this varies both by location and time. Carbon dioxide's chemical formula is CO₂.

Carbon dioxide is produced by all animals, plants, fungi and microorganisms during respiration and is used by plants during photosynthesis to make sugars which may either be consumed again in respiration or used as the raw material for plant growth. It is, therefore, a major component of the carbon cycle. Carbon dioxide is generated as a byproduct of the combustion of fossil fuels or vegetable matter, among other chemical processes. Inorganic carbon dioxide is output by volcanoes and other geothermal processes such as hot springs.

Carbon dioxide is an important greenhouse gas because it transmits visible light but absorbs strongly in the infrared.

Carbon dioxide has no liquid state at pressures below 5.1 atm, but is a solid at temperatures below -78 °C. In its solid state, carbon dioxide is commonly called dry ice.

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Chemical and physical properties

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

Carbon dioxide is a colorless, 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.^[2]

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.

At −78.51° C or -109.3° F, carbon dioxide changes directly from a solid phase to a gaseous phase through sublimation, or from gaseous to solid through deposition. Solid carbon dioxide is normally called "dry ice", a generic trademark. It was first observed in 1825 by the French chemist Charles Thilorier. Dry ice is commonly used as a cooling agent, and it is relatively inexpensive. A convenient property for this purpose is that solid carbon dioxide sublimes directly into the gas phase leaving no liquid. It can often be found in groceries and laboratories, and it is also used in the shipping industry. The largest non-cooling use for dry ice is blast cleaning.

Liquid carbon dioxide forms only at pressures above 5.1 atm; the triple point of carbon dioxide is about 518 kPa at −56.6 °C (See phase diagram, above). The critical point is 7,821 kPa at 31.1 °C.

An alternative form of solid carbon dioxide, an amorphous glass-like form, is possible, although not at atmospheric pressure.^[3] This form of glass, called carbonia, was produced by supercooling heated CO₂ at extreme pressure (40–48 GPa or about 400,000 atmospheres) in a diamond anvil. This discovery confirmed the theory that carbon dioxide could exist in a glass state similar to other members of its elemental family, like silicon (silica glass) and germanium. Unlike silica and germania glasses, however, carbonia glass is not stable at normal pressures and reverts back to gas when pressure is released.

See also: Supercritical carbon dioxide and dry ice

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. He 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.^[4]

Carbon dioxide was first liquefied (at elevated pressures) in 1823 by Humphry Davy and Michael Faraday.^[5] 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.^[6]

Isolation

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 sulfuric acid and calcium carbonate (limestone or chalk) is depicted below:

H₂SO₄ + CaCO₃ → CaSO₄ + 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 oxides with coke in a blast furnace, producing pig iron and carbon dioxide:

2 Fe₂O₃ + 3 C → 4 Fe + 3 CO₂

Yeast produces carbon dioxide and ethanol, also known as alcohol, in the production of wines, beers and other spirits:

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 CO₃^2-(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.

Industrial production

Carbon dioxide is manufactured mainly from six processes:^[7]

1. As a byproduct in ammonia and hydrogen plants, where methane is converted to CO₂;
2. From combustion of carbonaceous fuels;
3. As a byproduct of fermentation;
4. From thermal decomposition of CaCO₃;
5. As a byproduct of sodium phosphate manufacture;
6. Directly from natural carbon dioxide gas wells.

Uses

Carbon dioxide is used by the food industry, the oil industry, and the chemical industry.^[7] 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.

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. 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 within the dough, while chemical leaveners such as baking powder and baking soda release carbon dioxide when heated or if exposed to acids.

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

Carbon dioxide extinguishes flames, and some fire extinguishers, especially those designed for electrical fires, contain liquid carbon dioxide under pressure. 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.

Liquid carbon dioxide is a good solvent for many 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 meters) high. The carbon dioxide fluid at about 93 degrees Celsius enters at the bottom of the column. The caffeine diffuses out of the beans and into the carbon dioxide.

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.)

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 "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.^[8] 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.

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

Carbon dioxide can also be combined with limonene oxide from orange peels or other epoxides to create polymers and plastics.^[9]

Carbon dioxide is used in enhanced oil recovery where it 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.^[10] In mature oil fields, extensive pipe networks are used to carry the carbon dioxide to the injection points.

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

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 and is likely to enjoy a renaissance due to environmental concerns. Its physical properties are highly favorable for cooling, refrigeration, and heating purposes, having a high volumetric cooling capacity. Due to its 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. In car air conditioning, in more than 90% of all driving conditions, R744 operates more efficiently than systems using R-134a. 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.^[11][12]

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)

In the Earth's atmosphere

Further information: Carbon dioxide in the Earth's atmosphere

Carbon dioxide in earth's atmosphere is considered a trace gas, and is measured in parts per million. Current average concentration is approximately 385 parts per million by volume or 582 parts per million by mass. The mass of the Earth atmosphere is 5.14×10¹⁸ kg ^[13], so the total mass of atmospheric carbon dioxide is 3.0×10¹⁵ kg (3,000 gigatonnes). Its concentration can vary considerably on a regional basis: in urban areas it is generally higher and indoors can reach 10 times the 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.^[14] In 1999, 2,244,804,000 metric tons of CO₂ were produced in the U.S. as a result of electric energy generation. This is an output rate of 0.6083kg (1.341 pounds) per kWh.^[15]

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.^[16].

Up to 40% of the gas emitted by some volcanoes during subaerial volcanic eruptions is carbon dioxide.^[17] 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^[18] Locally high concentrations of CO₂, produced by disturbance of deep lake water saturated with CO₂ are thought to have caused 37 fatalities at Monoun, Cameroon in 1984 and 1700 casualties in Nyos, Cameroon in 1986^[19]. 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 (30 billion tons).^[20]

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. Ocean acts as a carbon sink, having absorbed about one-third of human-generated CO₂ emissions to date^[21].

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.

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 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 (a limit of C3 carbon fixation photosynthesis^{[citation needed]}). A similar event on a global scale occurred after the Permian period, when Earth life almost became extinct. A repeat of such conditions (a decrease of carbon dioxide concentration to about 60-65% of its current level) would kill 99% of existing plants and undoubtedly eliminate human civilization (carbon dioxide deficit was also the most likely reason for most big life "extinctions" on the planet and will also finally end the Earth life)^{[citation needed]}. Plants can potentially grow up to 50 percent faster in concentrations of 1,000 ppm CO₂ when compared with ambient conditions.^[22]

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.^[23] 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.^[24]

Toxicity

Carbon dioxide content in fresh air varies between 0.03% (300 ppm) and 0.06% (600 ppm), depending on the location (see graphical map of CO₂ in real-time).

A person's exhaled breath is approximately 4.5% carbon dioxide.

It is dangerous when inhaled in high concentrations (greater than 5% by volume, or 50,000 ppm). The current threshold limit value (TLV) or maximum level that is considered safe for healthy adults for an eight-hour work day is 0.5% (5,000 ppm). The maximum safe level for infants, children, the elderly and individuals with cardio-pulmonary health issues is significantly less.

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 itself. 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 as 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. Carbon dioxide caused a great loss of life at Lake Nyos in Cameroon in 1986, when an upwelling of CO₂-laden lake water quickly blanketed a large surrounding populated area..^[25] The heavier carbon dioxide forced out the life-sustaining oxygen near the surface, killing nearly two thousand people.

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. OSHA limits concentrations in the workplace to 5,000 for prolonged periods. The U.S. National Institute for Occupational Safety and Health limits brief exposures (up to ten minutes) to 30,000 and considers CDPL exceeding 40,000 as "immediately dangerous to life and health." People who breathe 50,000 for more than half an hour show signs of acute hypercapnia, while breathing 70,000 – 100,000 can produce unconsciousness in only a few minutes. Accordingly, carbon dioxide, either as a gas or as dry ice, should be handled only in well-ventilated areas.

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,^[26] by the reaction CO₂ + H₂O --> H₂CO₃ --> H⁺ + HCO₃⁻.

• 5% – 10% is dissolved in the plasma^[26]

• 5% – 10% is bound to hemoglobin as carbamino compounds^[26]

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.

Hemoglobin, the main oxygen-carrying molecule in red blood cells, can carry both oxygen and carbon dioxide, although in quite different ways. 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. This is known as the Bohr Effect.

Carbon dioxide may be 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 can cause respiratory acidosis, while breathing that is too rapid may lead 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) may lead to loss of consciousness. 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 without being aware of the imminent peril.^[26]

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.^[27]

See also

References

• CO₂ Carbon Dioxide Properties, Uses, Applications

• Pressure-Temperature phase diagram for carbon dioxide
• Molview from bluerhinos.co.uk See Carbon dioxide in 3D
• Dry Ice information
• Trends in Atmospheric Carbon Dioxide (NOAA)
• Phase Diagram of Carbon Dioxide
• Experiment 071 -- Triple Point Phase Transition for Carbon Dioxide
• CO₂ as a natural refrigerant - FAQs