Carbon dioxide

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Carbon dioxide
Structural formula of carbon dioxide with bond length
Ball-and-stick model of carbon dioxide
Ball-and-stick model of carbon dioxide
Space-filling model of carbon dioxide
Space-filling model of carbon dioxide
Names
IUPAC name
Carbon dioxide
Other names
  • Carbonic acid gas
  • Carbonic anhydride
  • Carbonic dioxide
  • Carbonic oxide
  • Carbon(IV) oxide
  • Methanedione
  • R-744 (refrigerant)
  • R744 (refrigerant alternative spelling)
  • Dry ice (solid phase)
Identifiers
3D model (
JSmol
)
3DMet
1900390
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard
100.004.271 Edit this at Wikidata
EC Number
  • 204-696-9
E number E290 (preservatives)
989
KEGG
MeSH Carbon+dioxide
RTECS number
  • FF6400000
UNII
UN number 1013 (gas), 1845 (solid)
  • InChI=1S/CO2/c2-1-3 checkY
    Key: CURLTUGMZLYLDI-UHFFFAOYSA-N checkY
  • InChI=1/CO2/c2-1-3
    Key: CURLTUGMZLYLDI-UHFFFAOYAO
  • O=C=O
  • C(=O)=O
Properties
CO2
Molar mass 44.009 g·mol−1
Appearance Colorless gas
Odor
  • Low concentrations: none
  • High concentrations: sharp; acidic[1]
Density
  • 1562 kg/m3 (solid at 1 atm (100 kPa) and −78.5 °C (−109.3 °F))
  • 1101 kg/m3 (liquid at saturation −37 °C (−35 °F))
  • 1.977 kg/m3 (gas at 1 atm (100 kPa) and 0 °C (32 °F))
Critical point (T, P) 304.128(15) K[2] (30.978(15) °C), 7.3773(30) MPa[2] (72.808(30) atm)
194.6855(30) K (−78.4645(30) °C) at 1 atm (0.101325 MPa)
1.45 g/L at 25 °C (77 °F), 100 kPa (0.99 atm)
Vapor pressure 5.7292(30) MPa, 56.54(30) atm (20 °C (293.15 K))
Acidity (pKa) Carbonic acid:
pKa1 = 3.6
pKa1(apparent) = 6.35
pKa2 = 10.33
−20.5·10−6 cm3/mol
Thermal conductivity
0.01662 W·m−1·K−1 (300 K (27 °C; 80 °F))[3]
1.00045
Viscosity
  • 14.90 μPa·s at 25 °C (298 K)[4]
  • 70 μPa·s at −78.5 °C (194.7 K)
0 D
Structure
Trigonal
Linear
Thermochemistry
37.135 J/(K·mol)
214 J·mol−1·K−1
Std enthalpy of
formation
fH298)
−393.5 kJ·mol−1
Pharmacology
V03AN02 (WHO)
Hazards
NFPA 704 (fire diamond)
Lethal dose or concentration (LD, LC):
90,000 ppm (162,000 mg/m3) (human, 5 min)[6]
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 5000 ppm (9000 mg/m3)[5]
REL (Recommended)
TWA 5000 ppm (9000 mg/m3), ST 30,000 ppm (54,000 mg/m3)[5]
IDLH
(Immediate danger)
40,000 ppm (72,000 mg/m3)[5]
Safety data sheet (SDS) Sigma-Aldrich
Related compounds
Other anions
Other cations
Related carbon oxides
See Oxocarbon
Related compounds
Supplementary data page
Carbon dioxide (data page)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

Carbon dioxide is a chemical compound with the chemical formula CO2. It is made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature, and as the source of available carbon in the carbon cycle, atmospheric CO2 is the primary carbon source for life on Earth. In the air, carbon dioxide is transparent to visible light but absorbs infrared radiation, acting as a greenhouse gas. Carbon dioxide is soluble in water and is found in groundwater, lakes, ice caps, and seawater. When carbon dioxide dissolves in water, it forms carbonate and mainly bicarbonate (HCO3), which causes ocean acidification as atmospheric CO2 levels increase.[9]

It is a

parts per million (ppm)[a], or about 0.04% (as of May 2022) having risen from pre-industrial levels of 280 ppm or about 0.025%.[11][12] Burning fossil fuels is the primary cause of these increased CO2 concentrations and also the primary cause of climate change.[13]

Its concentration in Earth's pre-industrial atmosphere since late in the Precambrian was regulated by organisms and geological phenomena. Plants, algae and cyanobacteria use energy from sunlight to synthesize carbohydrates from carbon dioxide and water in a process called photosynthesis, which produces oxygen as a waste product.[14] In turn, oxygen is consumed and CO2 is released as waste by all aerobic organisms when they metabolize organic compounds to produce energy by respiration.[15] CO2 is released from organic materials when they decay or combust, such as in forest fires. Since plants require CO2 for photosynthesis, and humans and animals depend on plants for food, CO2 is necessary for the survival of life on earth.

Carbon dioxide is 53% more dense than dry air, but is long lived and thoroughly mixes in the atmosphere. About half of excess CO2 emissions to the atmosphere are absorbed by

dissolve
in water or react with acids.

CO2 is a versatile industrial material, used, for example, as an inert gas in welding and

soda water in the mouth, but at normally encountered concentrations it is odorless.[1]

Chemical and physical properties

Structure, bonding and molecular vibrations

The

carbonyls.[19] Since it is centrosymmetric, the molecule has no electric dipole moment
.

Stretching and bending oscillations of the CO2 molecule. Upper left: symmetric stretching. Upper right: antisymmetric stretching. Lower line: degenerate pair of bending modes.

As a linear triatomic molecule, CO2 has four vibrational modes as shown in the diagram. In the symmetric and the antisymmetric stretching modes, the atoms move along the axis of the molecule. There are two bending modes, which are degenerate, meaning that they have the same frequency and same energy, because of the symmetry of the molecule. When a molecule touches a surface or touches another molecule, the two bending modes can differ in frequency because the interaction is different for the two modes. Some of the vibrational modes are observed in the infrared (IR) spectrum: the antisymmetric stretching mode at wavenumber 2349 cm−1 (wavelength 4.25 μm) and the degenerate pair of bending modes at 667 cm−1 (wavelength 15 μm). The symmetric stretching mode does not create an electric dipole so is not observed in IR spectroscopy, but it is detected in Raman spectroscopy at 1388 cm−1 (wavelength 7.2 μm).[20]

In the gas phase, carbon dioxide molecules undergo significant vibrational motions and do not keep a fixed structure. However, in a Coulomb explosion imaging experiment, an instantaneous image of the molecular structure can be deduced. Such an experiment[21] has been performed for carbon dioxide. The result of this experiment, and the conclusion of theoretical calculations[22] based on an ab initio potential energy surface of the molecule, is that none of the molecules in the gas phase are ever exactly linear. This counter-intuitive result is trivially due to the fact that the nuclear motion volume element vanishes for linear geometries.[22] This is so for all molecules except diatomic molecules.

In aqueous solution

Carbon dioxide is

soluble in water, in which it reversibly forms H2CO3 (carbonic acid), which is a weak acid
since its ionization in water is incomplete.

CO2 + H2O ⇌ H2CO3

The hydration equilibrium constant of carbonic acid is, at 25 °C:

Hence, the majority of the carbon dioxide is not converted into carbonic acid, but remains as CO2 molecules, not affecting the pH.

The relative concentrations of CO2, H2CO3, and the deprotonated forms HCO3 (bicarbonate) and CO2−3(carbonate) depend on the pH. As shown in a Bjerrum plot, in neutral or slightly alkaline water (pH > 6.5), the bicarbonate form predominates (>50%) becoming the most prevalent (>95%) at the pH of seawater. In very alkaline water (pH > 10.4), the predominant (>50%) form is carbonate. The oceans, being mildly alkaline with typical pH = 8.2–8.5, contain about 120 mg of bicarbonate per liter.

Being

diprotic, carbonic acid has two acid dissociation constants
, the first one for the dissociation into the bicarbonate (also called hydrogen carbonate) ion (HCO3):

H2CO3 ⇌ HCO3 + H+
Ka1 = 2.5 × 10−4 mol/L; pKa1 = 3.6 at 25 °C.[19]

This is the true first acid dissociation constant, defined as

where the denominator includes only covalently bound H2CO3 and does not include hydrated CO2(aq). The much smaller and often-quoted value near 4.16 × 10−7 (or pKa1 = 6.38) is an apparent value calculated on the (incorrect) assumption that all dissolved CO2 is present as carbonic acid, so that

Since most of the dissolved CO2 remains as CO2 molecules, Ka1(apparent) has a much larger denominator and a much smaller value than the true Ka1.[23]

The bicarbonate ion is an

amphoteric species that can act as an acid or as a base, depending on pH of the solution. At high pH, it dissociates significantly into the carbonate
ion (CO2−3):

HCO3 ⇌ CO2−3 + H+
Ka2 = 4.69 × 10−11 mol/L; pKa2 = 10.329


In organisms, carbonic acid production is catalysed by the
enzyme known as carbonic anhydrase.

In addition to altering its acidity, the presence of carbon dioxide in water also affects its electrical properties.

Electrical conductivity of carbondioxide saturated desalinated water when heated from 20 to 98° C. The shadowed regions indicate the error bars associated with the measurements. Data on github

When carbon dioxide dissolves in desalinated water, the electrical conductivity increases significantly from below 1 μS/cm to nearly 30 μS/cm. When heated, the water begins to gradually lose the conductivity induced by the presence of , especially noticeable as temperatures exceed 30°C.

The temperature dependence of the electrical conductivity of fully deionized water without CO2 saturation is comparably low in relation to these data.

Chemical reactions of CO2

CO2 is a potent

α,β-unsaturated carbonyl compounds. However, unlike electrophiles of similar reactivity, the reactions of nucleophiles with CO2 are thermodynamically less favored and are often found to be highly reversible.[24] The reversible reaction of carbon dioxide with amines to make carbamates is used in CO2 scrubbers and has been suggested as a possible starting point for carbon capture and storage by amine gas treating
. Only very strong nucleophiles, like the
organolithium compounds react with CO2 to give carboxylates
:

MR + CO2 → RCO2M
where M =
aryl
.

In metal carbon dioxide complexes, CO2 serves as a ligand, which can facilitate the conversion of CO2 to other chemicals.[25]

The reduction of CO2 to CO is ordinarily a difficult and slow reaction:

CO2 + 2 e + 2 H+ → CO + H2O

The

redox potential for this reaction near pH 7 is about −0.53 V versus the standard hydrogen electrode. The nickel-containing enzyme carbon monoxide dehydrogenase catalyses this process.[26]

Photoautotrophs (i.e. plants and cyanobacteria) use the energy contained in sunlight to photosynthesize simple sugars
from CO2 absorbed from the air and water:

n CO2 + n H2O → (CH2O)n + n O2

Physical properties

Pellets of "dry ice", a common form of solid carbon dioxide

Carbon dioxide is colorless. At low concentrations, the gas is odorless; however, at sufficiently high concentrations, it has a sharp, acidic odor.

air.[27]

Carbon dioxide has no liquid state at pressures below 0.51795(10)

sublimes directly to a gas above this temperature. In its solid state, carbon dioxide is commonly called dry ice
.

Pressure–temperature phase diagram of carbon dioxide. Note that it is a log-lin chart.

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 dioxide (silica glass) and germanium dioxide
. Unlike silica and germania glasses, however, carbonia glass is not stable at normal pressures and reverts to gas when pressure is released.

At temperatures and pressures above the critical point, carbon dioxide behaves as a supercritical fluid known as supercritical carbon dioxide.

Table of thermal and physical properties of saturated liquid carbon dioxide:[29][30]

Temperature (°C) Density (kg/m3)
Specific heat
(kJ/(kg⋅K))
Kinematic viscosity
(m2/s)
Thermal conductivity
(W/(m⋅K))
Thermal diffusivity (m2/s)
Prandtl Number
Bulk modulus (K^-1)[clarification needed]
−50 1156.34 1.84 1.19 × 10−7 0.0855 4.02 × 10−8 2.96
−40 1117.77 1.88 1.18 × 10−7 0.1011 4.81 × 10−8 2.46
−30 1076.76 1.97 1.17 × 10−7 0.1116 5.27 × 10−8 2.22
−20 1032.39 2.05 1.15 × 10−7 0.1151 5.45 × 10−8 2.12
−10 983.38 2.18 1.13 × 10−7 0.1099 5.13 × 10−8 2.2
0 926.99 2.47 1.08 × 10−7 0.1045 4.58 × 10−8 2.38
10 860.03 3.14 1.01 × 10−7 0.0971 3.61 × 10−8 2.8
20 772.57 5 9.10 × 10−8 0.0872 2.22 × 10−8 4.1 1.40 × 10−2[clarification needed]
30 597.81 36.4 8.00 × 10−8 0.0703 0.279 × 10−8 28.7

Table of thermal and physical properties of carbon dioxide (CO2) at atmospheric pressure:[29][30]

Temperature (K) Density (kg/m3) Specific heat (kJ/(kg⋅°C))
Dynamic viscosity
(kg/(m⋅s))
Kinematic viscosity (m2/s) Thermal conductivity (W/(m⋅°C)) Thermal diffusivity (m2/s) Prandtl Number
220 2.4733 0.783 1.11 × 10−5 4.49 × 10−6 0.010805 5.92 × 10−6 0.818
250 2.1657 0.804 1.26 × 10−5 5.81 × 10−6 0.012884 7.40 × 10−6 0.793
300 1.7973 0.871 1.50 × 10−5 8.32 × 10−6 0.016572 1.06 × 10−5 0.77
350 1.5362 0.9 1.72 × 10−5 1.12 × 10−5 0.02047 1.48 × 10−5 0.755
400 1.3424 0.942 1.93 × 10−5 1.44 × 10−5 0.02461 1.95 × 10−5 0.738
450 1.1918 0.98 2.13 × 10−5 1.79 × 10−5 0.02897 2.48 × 10−5 0.721
500 1.0732 1.013 2.33 × 10−5 2.17 × 10−5 0.03352 3.08 × 10−5 0.702
550 0.9739 1.047 2.51 × 10−5 2.57 × 10−5 0.03821 3.75 × 10−5 0.685
600 0.8938 1.076 2.68 × 10−5 3.00 × 10−5 0.04311 4.48 × 10−5 0.668
650 0.8143 1.1 2.88 × 10−5 3.54 × 10−5 0.0445 4.97 × 10−5 0.712
700 0.7564 1.13 3.05 × 10−5 4.03 × 10−5 0.0481 5.63 × 10−5 0.717
750 0.7057 1.15 3.21 × 10−5 4.55 × 10−5 0.0517 6.37 × 10−5 0.714
800 0.6614 1.17 3.37 × 10−5 5.10 × 10−5 0.0551 7.12 × 10−5 0.716

Biological role

Carbon dioxide is an end product of

aerobic fungi and bacteria. In vertebrates, the carbon dioxide travels in the blood from the body's tissues to the skin (e.g., amphibians) or the gills (e.g., fish), from where it dissolves in the water, or to the lungs from where it is exhaled. During active photosynthesis, plants can absorb more carbon dioxide from the atmosphere than they release
in respiration.

Photosynthesis and carbon fixation

Overview of the Calvin cycle and carbon fixation

Carbon fixation is a biochemical process by which atmospheric carbon dioxide is incorporated by plants, algae and cyanobacteria into energy-rich organic molecules such as glucose, thus creating their own food by photosynthesis. Photosynthesis uses carbon dioxide and water to produce sugars from which other organic compounds can be constructed, and oxygen
is produced as a by-product.

ribulose bisphosphate
, as shown in the diagram at left.

RuBisCO is thought to be the single most abundant protein on Earth.[31]

Phototrophs use the products of their photosynthesis as internal food sources and as raw material for the biosynthesis of more complex organic molecules, such as polysaccharides, nucleic acids, and proteins. These are used for their own growth, and also as the basis of the food chains and webs that feed other organisms, including animals such as ourselves. Some important phototrophs, the coccolithophores synthesise hard calcium carbonate scales.[32] A globally significant species of coccolithophore is Emiliania huxleyi whose calcite scales have formed the basis of many sedimentary rocks such as limestone, where what was previously atmospheric carbon can remain fixed for geological timescales.

Overview of photosynthesis and respiration. Carbon dioxide (at right), together with water, form oxygen and organic compounds (at left) by photosynthesis (green), which can be respired (red) to water and CO2.

Plants can grow as much as 50% faster in concentrations of 1,000 ppm CO2 when compared with ambient conditions, though this assumes no change in climate and no limitation on other nutrients.[33] Elevated CO2 levels cause increased growth reflected in the harvestable yield of crops, with wheat, rice and soybean all showing increases in yield of 12–14% under elevated CO2 in FACE experiments.[34][35]

Increased atmospheric CO2 concentrations result in fewer stomata developing on plants

FACE have shown that CO2 enrichment leads to decreased concentrations of micronutrients in crop plants.[38] This may have knock-on effects on other parts of ecosystems as herbivores will need to eat more food to gain the same amount of protein.[39]

The concentration of secondary

metabolites such as phenylpropanoids and flavonoids can also be altered in plants exposed to high concentrations of CO2.[40][41]

Plants also emit CO2 during respiration, and so the majority of plants and algae, which use

C3 photosynthesis, are only net absorbers during the day. Though a growing forest will absorb many tons of CO2 each year, a mature forest will produce as much CO2 from respiration and decomposition of dead specimens (e.g., fallen branches) as is used in photosynthesis in growing plants.[42] Contrary to the long-standing view that they are carbon neutral, mature forests can continue to accumulate carbon[43] and remain valuable carbon sinks, helping to maintain the carbon balance of Earth's atmosphere. Additionally, and crucially to life on earth, photosynthesis by phytoplankton consumes dissolved CO2 in the upper ocean and thereby promotes the absorption of CO2 from the atmosphere.[44]

Toxicity

Carbon dioxide content in fresh air (averaged between sea-level and 10 kPa level, i.e., about 30 km (19 mi) altitude) varies between 0.036% (360 ppm) and 0.041% (412 ppm), depending on the location.[46]

CO2 is an asphyxiant gas and not classified as toxic or harmful in accordance with Globally Harmonized System of Classification and Labelling of Chemicals standards of United Nations Economic Commission for Europe by using the OECD Guidelines for the Testing of Chemicals. In concentrations up to 1% (10,000 ppm), it will make some people feel drowsy and give the lungs a stuffy feeling.[45] Concentrations of 7% to 10% (70,000 to 100,000 ppm) may cause suffocation, even in the presence of sufficient oxygen, manifesting as dizziness, headache, visual and hearing dysfunction, and unconsciousness within a few minutes to an hour.[47] The physiological effects of acute carbon dioxide exposure are grouped together under the term hypercapnia, a subset of asphyxiation.

Because it is heavier than air, in locations where the gas seeps from the ground (due to sub-surface volcanic or geothermal activity) in relatively high concentrations, without the dispersing effects of wind, it can collect in sheltered/pocketed locations below average ground level, causing animals located therein to be suffocated. Carrion feeders attracted to the carcasses are then also killed. Children have been killed in the same way near the city of Goma by CO2 emissions from the nearby volcano Mount Nyiragongo.[48] The Swahili term for this phenomenon is mazuku.

Rising levels of CO2 threatened the Apollo 13 astronauts who had to adapt cartridges from the command module to supply the carbon dioxide scrubber in the Apollo Lunar Module, which they used as a lifeboat.

Adaptation to increased concentrations of CO2 occurs in humans, including modified breathing and kidney bicarbonate production, in order to balance the effects of blood acidification (acidosis). Several studies suggested that 2.0 percent inspired concentrations could be used for closed air spaces (e.g. a submarine) since the adaptation is physiological and reversible, as deterioration in performance or in normal physical activity does not happen at this level of exposure for five days.[49][50] Yet, other studies show a decrease in cognitive function even at much lower levels.[51][52] Also, with ongoing respiratory acidosis, adaptation or compensatory mechanisms will be unable to reverse the condition.

Below 1%

There are few studies of the health effects of long-term continuous CO2 exposure on humans and animals at levels below 1%. Occupational CO2 exposure limits have been set in the United States at 0.5% (5000 ppm) for an eight-hour period.[53] At this CO2 concentration, International Space Station crew experienced headaches, lethargy, mental slowness, emotional irritation, and sleep disruption.[54] Studies in animals at 0.5% CO2 have demonstrated kidney calcification and bone loss after eight weeks of exposure.[55] A study of humans exposed in 2.5 hour sessions demonstrated significant negative effects on cognitive abilities at concentrations as low as 0.1% (1000 ppm) CO2 likely due to CO2 induced increases in cerebral blood flow.[51] Another study observed a decline in basic activity level and information usage at 1000 ppm, when compared to 500 ppm.[52]

However a review of the literature found that a reliable subset of studies on the phenomenon of carbon dioxide induced cognitive impairment to only show a small effect on high-level decision making (for concentrations below 5000 ppm). Most of the studies were confounded by inadequate study designs, environmental comfort, uncertainties in exposure doses and differing cognitive assessments used.[56] Similarly a study on the effects of the concentration of CO2 in motorcycle helmets has been criticized for having dubious methodology in not noting the self-reports of motorcycle riders and taking measurements using mannequins. Further when normal motorcycle conditions were achieved (such as highway or city speeds) or the visor was raised the concentration of CO2 declined to safe levels (0.2%).[57][58]

General guidelines on indoor CO2 concentration effects
Concentration Note
280 ppm Pre-industrial levels
421 ppm Current (May 2022) levels
700 ppm ASHRAE recommendation[59]
1000 ppm Cognitive impairment, Canada's long term exposure limit[60]
1000-2000 ppm Drowsiness[61]
2000-5000 ppm Headaches, sleepiness; poor concentration, loss of attention, slight nausea also possible[61]
5000 ppm USA 8h exposure limit[53]

Ventilation

A carbon dioxide sensor that measures CO2 concentration using a nondispersive infrared sensor

Poor ventilation is one of the main causes of excessive CO2 concentrations in closed spaces, leading to poor indoor air quality. Carbon dioxide differential above outdoor concentrations at steady state conditions (when the occupancy and ventilation system operation are sufficiently long that CO2 concentration has stabilized) are sometimes used to estimate ventilation rates per person.[citation needed] Higher CO2 concentrations are associated with occupant health, comfort and performance degradation.[62][63] ASHRAE Standard 62.1–2007 ventilation rates may result in indoor concentrations up to 2,100 ppm above ambient outdoor conditions. Thus if the outdoor concentration is 400 ppm, indoor concentrations may reach 2,500 ppm with ventilation rates that meet this industry consensus standard. Concentrations in poorly ventilated spaces can be found even higher than this (range of 3,000 or 4,000 ppm).

Miners, who are particularly vulnerable to gas exposure due to insufficient ventilation, referred to mixtures of carbon dioxide and nitrogen as "

canary with them as they worked. The canary is more sensitive to asphyxiant gases than humans, and as it became unconscious would stop singing and fall off its perch. The Davy lamp could also detect high levels of blackdamp (which sinks, and collects near the floor) by burning less brightly, while methane
, another suffocating gas and explosion risk, would make the lamp burn more brightly.

In February 2020, three people died from suffocation at a party in Moscow when dry ice (frozen CO2) was added to a swimming pool to cool it down.[64] A similar accident occurred in 2018 when a woman died from CO2 fumes emanating from the large amount of dry ice she was transporting in her car.[65]

Indoor air

Humans spend more and more time in a confined atmosphere (around 80-90% of the time in a building or vehicle). According to the French Agency for Food, Environmental and Occupational Health & Safety (ANSES) and various actors in France, the CO2 rate in the indoor air of buildings (linked to human or animal occupancy and the presence of combustion installations), weighted by air renewal, is “usually between about 350 and 2,500 ppm”.[66]

In homes, schools, nurseries and offices, there are no systematic relationships between the levels of CO2 and other pollutants, and indoor CO2 is statistically not a good predictor of pollutants linked to outdoor road (or air, etc.) traffic.[67] CO2 is the parameter that changes the fastest (with hygrometry and oxygen levels when humans or animals are gathered in a closed or poorly ventilated room). In poor countries, many open hearths are sources of CO2 and CO emitted directly into the living environment.[68]

Outdoor areas with elevated concentrations

Local concentrations of carbon dioxide can reach high values near strong sources, especially those that are isolated by surrounding terrain. At the Bossoleto hot spring near Rapolano Terme in Tuscany, Italy, situated in a bowl-shaped depression about 100 m (330 ft) in diameter, concentrations of CO2 rise to above 75% overnight, sufficient to kill insects and small animals. After sunrise the gas is dispersed by convection.[69] 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.[70]

Human physiology

Content

partial pressures of carbon dioxide (abbreviated pCO2
)
Blood compartment (
kPa
)
(
mm Hg
)
Venous blood carbon dioxide 5.5–6.8 41–51[71]
Alveolar pulmonary
gas pressures
4.8 36
Arterial blood carbon dioxide
4.7–6.0 35–45[71]

The body produces approximately 2.3 pounds (1.0 kg) of carbon dioxide per day per person,

arteries. The carbon dioxide content of the blood is often given as the partial pressure, which is the pressure which carbon dioxide would have had if it alone occupied the volume.[73]
In humans, the blood carbon dioxide contents are shown in the adjacent table.

Transport in the blood

CO2 is carried in blood in three different ways. Exact percentages vary between arterial and venous blood.

CO2 + H2O → H2CO3 → H+ + HCO3

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
.

Regulation of respiration

Carbon dioxide is one of the mediators of local

capillaries expand to allow a greater blood flow to that tissue.[75]

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 can cause respiratory alkalosis.[76]

Although the body requires oxygen for metabolism, low oxygen levels normally 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 losing consciousness.[74]

The respiratory centers try to maintain an arterial CO2 pressure of 40 

mmHg. With intentional hyperventilation, the CO2 content of arterial blood may be lowered to 10–20 mmHg (the oxygen content of the blood is little affected), and the respiratory drive is diminished. This is why one can hold one's breath longer after hyperventilating than without hyperventilating. This carries the risk that unconsciousness may result before the need to breathe becomes overwhelming, which is why hyperventilation is particularly dangerous before free diving.[77]

Concentrations and role in the environment

Atmosphere

Atmospheric CO2 concentration measured at Mauna Loa Observatory in Hawaii from 1958 to 2023 (also called the Keeling Curve). The rise in CO2 over that time period is clearly visible. The concentration is expressed as μmole per mole, or ppm.

In

is due to human activity.[81] Burning fossil fuels is the main cause of these increased CO2 concentrations and also the main cause of climate change.[82] Other large sources of CO2 from human activities include cement production, deforestation, and biomass
burning.

Carbon dioxide is a greenhouse gas. It absorbs and emits

μm (2,347 cm−1) (asymmetric stretching vibrational mode) and 14.99 μm (667 cm−1) (bending vibrational mode). CO2 plays a significant role in influencing Earth's surface temperature through the greenhouse effect.[83] Light emission from the Earth's surface is most intense in the infrared region between 200 and 2500 cm−1,[84] as opposed to light emission from the much hotter Sun which is most intense in the visible region. Absorption of infrared light at the vibrational frequencies of atmospheric CO2 traps energy near the surface, warming the surface of Earth and its lower atmosphere. Less energy reaches the upper atmosphere, which is therefore cooler because of this absorption.[85]

The increase in atmospheric concentrations of CO2 and other long-lived greenhouse gases such as methane increase the absorption and emission of infrared radiation by the atmosphere. This has led to a rise in average global temperature and ocean acidification. Another direct effect is the CO2 fertilization effect. The increase in atmospheric concentrations of CO2 causes a range of further effects of climate change on the environment and human living conditions.

The present atmospheric concentration of CO2 is the highest for 14 million years.[86] Concentrations of CO2 in the atmosphere were as high as 4,000 ppm during the Cambrian period about 500 million years ago, and as low as 180 ppm during the Quaternary glaciation of the last two million years.[79] Reconstructed temperature records for the last 420 million years indicate that atmospheric CO2 concentrations peaked at approximately 2,000 ppm. This peak happened during the Devonian period (400 million years ago). Another peak occurred in the Triassic period (220–200 million years ago).[87]
Annual CO2 flows from anthropogenic sources (left) into Earth's atmosphere, land, and ocean sinks (right) since the 1960s. Units in equivalent gigatonnes carbon per year.[88]

Oceans

Ocean acidification

Carbon dioxide dissolves in the ocean to form carbonic acid (H2CO3), bicarbonate (HCO3), and carbonate (CO2−3). There is about fifty times as much carbon dioxide dissolved in the oceans as exists in the atmosphere. The oceans act as an enormous carbon sink, and have taken up about a third of CO2 emitted by human activity.[89]

ocean chemistry
projected for the year 2100

Changes in ocean chemistry can have extensive direct and indirect effects on organisms and their habitats. One of the most important repercussions of increasing ocean acidity relates to the production of shells out of

saturating
concentrations of carbonate ions (CO2−3).

Very little of the extra carbon dioxide that is added into the ocean remains as dissolved carbon dioxide. The majority dissociates into additional bicarbonate and free hydrogen ions. The increase in hydrogen is larger than the increase in bicarbonate,[95] creating an imbalance in the reaction:

HCO3 ⇌ CO2−3 + H+

To maintain chemical equilibrium, some of the carbonate ions already in the ocean combine with some of the hydrogen ions to make further bicarbonate. Thus the ocean's concentration of carbonate ions is reduced, removing an essential building block for marine organisms to build shells, or calcify:

Ca2+ + CO2−3 ⇌ CaCO3

Hydrothermal vents

Carbon dioxide is also introduced into the oceans through hydrothermal vents. The Champagne hydrothermal vent, found at the Northwest Eifuku volcano in the Mariana Trench, produces almost pure liquid carbon dioxide, one of only two known sites in the world as of 2004, the other being in the Okinawa Trough.[96] The finding of a submarine lake of liquid carbon dioxide in the Okinawa Trough was reported in 2006.[97]

Production

Biological processes

Carbon dioxide is a by-product of the

bioethanol. Yeast metabolizes sugar to produce CO2 and ethanol
, also known as alcohol, as follows:

C6H12O6 → 2 CO2 + 2 CH3CH2OH

All aerobic organisms produce CO2 when they oxidize carbohydrates, fatty acids, and proteins. The large number of reactions involved are exceedingly complex and not described easily. Refer to cellular respiration, anaerobic respiration and photosynthesis. The equation for the respiration of glucose and other monosaccharides is:

C6H12O6 + 6 O2 → 6 CO2 + 6 H2O

Anaerobic organisms decompose organic material producing methane and carbon dioxide together with traces of other compounds.[98] Regardless of the type of organic material, the production of gases follows well defined kinetic pattern. Carbon dioxide comprises about 40–45% of the gas that emanates from decomposition in landfills (termed "landfill gas"). Most of the remaining 50–55% is methane.[99]

Industrial processes

Carbon dioxide can be obtained by distillation from air, but the method is inefficient. Industrially, carbon dioxide is predominantly an unrecovered waste product, produced by several methods which may be practiced at various scales.[100]

Combustion

The combustion of all carbon-based fuels, such as methane (natural gas), petroleum distillates (gasoline, diesel, kerosene, propane), coal, wood and generic organic matter produces carbon dioxide and, except in the case of pure carbon, water. As an example, the chemical reaction between methane and oxygen:

CH4 + 2 O2 → CO2 + 2 H2O

Iron is reduced from its oxides with coke in a blast furnace, producing pig iron and carbon dioxide:[101]

Fe2O3 + 3 CO → 3 CO2 + 2 Fe

By-product from hydrogen production

Carbon dioxide is a byproduct of the industrial production of hydrogen by

water gas shift reaction in ammonia production. These processes begin with the reaction of water and natural gas (mainly methane).[102] This is a major source of food-grade carbon dioxide for use in carbonation of beer and soft drinks, and is also used for stunning animals such as poultry. In the summer of 2018 a shortage of carbon dioxide for these purposes arose in Europe due to the temporary shut-down of several ammonia plants for maintenance.[103]

Thermal decomposition of limestone

It is produced by thermal decomposition of limestone, CaCO3 by heating (

calcining) at about 850 °C (1,560 °F), in the manufacture of quicklime (calcium oxide
, CaO), a compound that has many industrial uses:

CaCO3 → CaO + CO2

Acids liberate CO2 from most metal carbonates. Consequently, it may be obtained directly from natural carbon dioxide

springs, where it is produced by the action of acidified water on limestone or dolomite. The reaction between hydrochloric acid
and calcium carbonate (limestone or chalk) is shown below:

CaCO3 + 2 HCl → CaCl2 + H2CO3

The carbonic acid (H2CO3) then decomposes to water and CO2:

H2CO3 → CO2 + H2O

Such reactions are accompanied by foaming or bubbling, or both, as the gas is released. They have widespread uses in industry because they can be used to neutralize waste acid streams.

Commercial uses

Carbon dioxide is used by the food industry, the oil industry, and the chemical industry.[100] The compound has varied commercial uses but one of its greatest uses as a chemical is in the production of carbonated beverages; it provides the sparkle in carbonated beverages such as soda water, beer and sparkling wine.

Precursor to chemicals

In the chemical industry, carbon dioxide is mainly consumed as an ingredient in the production of urea, with a smaller fraction being used to produce methanol and a range of other products.[104] Some carboxylic acid derivatives such as sodium salicylate are prepared using CO2 by the Kolbe–Schmitt reaction.[105]

In addition to conventional processes using CO2 for chemical production, electrochemical methods are also being explored at a research level. In particular, the use of renewable energy for production of fuels from CO2 (such as methanol) is attractive as this could result in fuels that could be easily transported and used within conventional combustion technologies but have no net CO2 emissions.[106]

Agriculture

Plants require carbon dioxide to conduct photosynthesis. The atmospheres of greenhouses may (if of large size, must) be enriched with additional CO2 to sustain and increase the rate of plant growth.

whiteflies and spider mites in a greenhouse.[109] Some plants respond more favorably to rising carbon dioxide concentrations than others, which can lead to vegetation regime shifts like woody plant encroachment.[110]

Foods

Carbon dioxide bubbles in a soft drink

Carbon dioxide is a

INS number
290).

A candy called Pop Rocks is pressurized with carbon dioxide gas[114] at about 4,000 kPa (40 bar; 580 psi). When placed in the mouth, it dissolves (just like other hard candy) and releases the gas bubbles with an audible pop.

baking soda release carbon dioxide when heated or if exposed to acids
.

Beverages

Carbon dioxide is used to produce

real ale
, draught beer is usually transferred from kegs in a cold room or cellar to dispensing taps on the bar using pressurized carbon dioxide, sometimes mixed with nitrogen.

The taste of soda water (and related taste sensations in other carbonated beverages) is an effect of the dissolved carbon dioxide rather than the bursting bubbles of the gas.

Winemaking

Dry ice used to preserve grapes after harvest

Carbon dioxide in the form of

grape must, and thus the alcohol concentration in the finished wine. 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 gases such as nitrogen or argon
are preferred for this process by professional wine makers.

Stunning animals

Carbon dioxide is often used to "stun" animals before slaughter.[117] "Stunning" may be a misnomer, as the animals are not knocked out immediately and may suffer distress.[118][119]

Inert gas

Carbon dioxide is one of the most commonly used compressed gases for pneumatic (pressurized gas) systems in portable pressure tools. Carbon dioxide is also used as an atmosphere for

MIG welding
, CO2 use is sometimes referred to as MAG welding, for Metal Active Gas, as CO2 can react at these high temperatures. It tends to produce a hotter puddle than truly inert atmospheres, improving the flow characteristics. Although, this may be due to atmospheric reactions occurring at the puddle site. This is usually the opposite of the desired effect when welding, as it tends to embrittle the site, but may not be a problem for general mild steel welding, where ultimate ductility is not a major concern.

Carbon dioxide 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 

scanning electron microscopy[120] and in the decaffeination of coffee beans
.

Fire extinguisher

Use of a CO2 fire extinguisher

Carbon dioxide can be used to extinguish flames by flooding the environment around the flame with the gas. It does not itself react to extinguish the flame, but starves the flame of oxygen by displacing it. Some

atmospheric oxygen. They are mainly used in server rooms.[121]

Carbon dioxide has also been widely used as an extinguishing agent in fixed fire-protection systems for local application of specific hazards and total flooding of a protected space.[122] International Maritime Organization standards recognize carbon dioxide systems for fire protection of ship holds and engine rooms. Carbon dioxide-based fire-protection systems have been linked to several deaths, because it can cause suffocation in sufficiently high concentrations. A review of CO2 systems identified 51 incidents between 1975 and the date of the report (2000), causing 72 deaths and 145 injuries.[123]

Supercritical CO2 as solvent

Liquid carbon dioxide is a good

dry cleaners for this reason. It is used in the preparation of some aerogels
because of the properties of supercritical carbon dioxide.

Medical and pharmacological uses

In medicine, up to 5% carbon dioxide (130 times atmospheric concentration) is added to oxygen for stimulation of breathing after apnea and to stabilize the O2/CO2 balance in blood.

Carbon dioxide can be mixed with up to 50% oxygen, forming an inhalable gas; this is known as Carbogen and has a variety of medical and research uses.

Another medical use are the mofette, dry spas that use carbon dioxide from post-volcanic discharge for therapeutic purposes.

Energy

Supercritical CO2 is used as the working fluid in the Allam power cycle engine.

Fossil fuel recovery

Carbon dioxide is used in

crude oil, significantly reduces its viscosity, and changing surface chemistry enabling the oil to flow more rapidly through the reservoir to the removal well.[125]
In mature oil fields, extensive pipe networks are used to carry the carbon dioxide to the injection points.

In enhanced coal bed methane recovery, carbon dioxide would be pumped into the coal seam to displace methane, as opposed to current methods which primarily rely on the removal of water (to reduce pressure) to make the coal seam release its trapped methane.[126]

Bio transformation into fuel

It has been proposed that CO2 from power generation be bubbled into ponds to stimulate growth of

cyanobacterium Synechococcus elongatus has been genetically engineered to produce the fuels isobutyraldehyde and isobutanol from CO2 using photosynthesis.[128]

Researchers have developed an

electrocatalytic technique using enzymes isolated from bacteria to power the chemical reactions which convert CO2 into fuels.[129][130][131]

Refrigerant
Comparison of the pressure–temperature phase diagrams of carbon dioxide (red) and water (blue) as a log-lin chart with phase transitions points at 1 atmosphere

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. Solid carbon dioxide is always below −78.5 °C (−109.3 °F) at regular atmospheric pressure, regardless of the air temperature.

Liquid carbon dioxide (industry nomenclature R744 or R-744) was used as a refrigerant prior to the use of

R134a, a hydrofluorocarbon (HFC) compound) contributes to climate change more than CO2 does. CO2 physical properties are highly favorable for cooling, refrigeration, and heating purposes, having a high volumetric cooling capacity. Due to the need to operate at pressures of up to 130 bars (1,900 psi; 13,000 kPa), CO2 systems require highly mechanically resistant reservoirs and components that have already been developed for mass production in many sectors. In automobile air conditioning, in more than 90% of all driving conditions for latitudes higher than 50°, CO2 (R744) operates more efficiently than systems using HFCs (e.g., R134a). 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, and heat pump water heaters, among others. Coca-Cola has fielded CO2-based beverage coolers and the U.S. Army is interested in CO2 refrigeration and heating technology.[133][134]

Minor uses

A carbon-dioxide laser

Carbon dioxide is the lasing medium in a carbon-dioxide laser, which is one of the earliest type of lasers.

Carbon dioxide can be used as a means of controlling the pH of swimming pools,[135] by continuously adding gas to the water, thus keeping the pH from rising. Among the advantages of this is the avoidance of handling (more hazardous) acids. Similarly, it is also used in the maintaining reef aquaria, where it is commonly used in calcium reactors to temporarily lower the pH of water being passed over calcium carbonate in order to allow the calcium carbonate to dissolve into the water more freely, where it is used by some corals to build their skeleton.

Used as the primary coolant in the British

advanced gas-cooled reactor
for nuclear power generation.

Carbon dioxide induction is commonly used for the euthanasia of laboratory research animals. Methods to administer CO2 include placing animals directly into a closed, prefilled chamber containing CO2, or exposure to a gradually increasing concentration of CO2. The American Veterinary Medical Association's 2020 guidelines for carbon dioxide induction state that a displacement rate of 30–70% of the chamber or cage volume per minute is optimal for the humane euthanasia of small rodents.[136]: 5, 31  Percentages of CO2 vary for different species, based on identified optimal percentages to minimize distress.[136]: 22 

Carbon dioxide is also used in several related cleaning and surface-preparation techniques.

History of discovery

Crystal structure of dry ice

Carbon dioxide was the first gas to be described as a discrete substance. In about 1640,

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" (from Greek "chaos") or "wild spirit" (spiritus sylvestris).[138]

The properties of carbon dioxide were further studied 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 supported neither flame nor animal life. Black also found that when bubbled through limewater (a saturated aqueous solution of 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.[139]

Carbon dioxide was first liquefied (at elevated pressures) in 1823 by Humphry Davy and Michael Faraday.[140] The earliest description of solid carbon dioxide (dry ice) was given by the French inventor Adrien-Jean-Pierre Thilorier, who in 1835 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.[141][142]

Carbon dioxide in combination with nitrogen was known from earlier times as

suffocating mixture of nitrogen and carbon dioxide.[143]

See also

Notes

  1. ^ where "part" here means per molecule[10]
  2. ^ Sometimes spelt "choak-damp" in 19th Century texts.

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External links