Partial pressure

Source: Wikipedia, the free encyclopedia.
The atmospheric pressure is roughly equal to the sum of partial pressures of constituent gases – oxygen, nitrogen, argon, water vapor, carbon dioxide, etc.

In a mixture of

Dalton's Law
).

The partial pressure of a gas is a measure of thermodynamic activity of the gas's

arterial blood gases. That said, these pressures can also be measured in, for example, cerebrospinal fluid
.

Symbol

The symbol for pressure is usually P or p which may use a subscript to identify the pressure, and gas species are also referred to by subscript. When combined, these subscripts are applied recursively.[4][5]

Examples:

  • or = pressure at time 1
  • or = partial pressure of hydrogen
  • or or PaO2 = arterial partial pressure of oxygen
  • or or PvO2 = venous partial pressure of oxygen

Dalton's law of partial pressures

Schematic showing the concept of Dalton's Law.

Dalton's law expresses the fact that the total pressure of a mixture of ideal gases is equal to the sum of the partial pressures of the individual gases in the mixture.[6] This equality arises from the fact that in an ideal gas, the molecules are so far apart that they do not interact with each other. Most actual real-world gases come very close to this ideal. For example, given an ideal gas mixture of nitrogen (N2), hydrogen (H2) and ammonia (NH3):

where:

  • = total pressure of the gas mixture
  • = partial pressure of nitrogen (N2)
  • = partial pressure of hydrogen (H2)
  • = partial pressure of ammonia (NH3)

Ideal gas mixtures

Ideally the ratio of partial pressures equals the ratio of the number of molecules. That is, the mole fraction of an individual gas component in an ideal gas mixture can be expressed in terms of the component's partial pressure or the moles of the component:

and the partial pressure of an individual gas component in an ideal gas can be obtained using this expression:

where:  
= mole fraction of any individual gas component in a gas mixture
= partial pressure of any individual gas component in a gas mixture
= moles of any individual gas component in a gas mixture
= total moles of the gas mixture
= total pressure of the gas mixture

The mole fraction of a gas component in a gas mixture is equal to the volumetric fraction of that component in a gas mixture.[7]

The ratio of partial pressures relies on the following isotherm relation:

  • VX is the partial volume of any individual gas component (X)
  • Vtot is the total volume of the gas mixture
  • pX is the partial pressure of gas X
  • ptot is the total pressure of the gas mixture
  • nX is the amount of substance of gas (X)
  • ntot is the total amount of substance in gas mixture

Partial volume (Amagat's law of additive volume)

The partial volume of a particular gas in a mixture is the volume of one component of the gas mixture. It is useful in gas mixtures, e.g. air, to focus on one particular gas component, e.g. oxygen.

It can be approximated both from partial pressure and molar fraction:[8]

  • VX is the partial volume of an individual gas component X in the mixture
  • Vtot is the total volume of the gas mixture
  • pX is the partial pressure of gas X
  • ptot is the total pressure of the gas mixture
  • nX is the amount of substance of gas X
  • ntot is the total amount of substance in the gas mixture

Vapor pressure

A log-lin vapor pressure chart for various liquids

normal boiling point
.

The higher the vapor pressure of a liquid at a given temperature, the lower the normal boiling point of the liquid.

The vapor pressure chart displayed has graphs of the vapor pressures versus temperatures for a variety of liquids.[9] As can be seen in the chart, the liquids with the highest vapor pressures have the lowest normal boiling points.

For example, at any given temperature,

atm) of absolute vapor pressure. At higher altitudes, the atmospheric pressure is less than that at sea level, so boiling points of liquids are reduced. At the top of Mount Everest, the atmospheric pressure is approximately 0.333 atm, so by using the graph, the boiling point of diethyl ether
would be approximately 7.5 °C versus 34.6 °C at sea level (1 atm).

Equilibrium constants of reactions involving gas mixtures

It is possible to work out the equilibrium constant for a chemical reaction involving a mixture of gases given the partial pressure of each gas and the overall reaction formula. For a reversible reaction involving gas reactants and gas products, such as:

the equilibrium constant of the reaction would be:

where:  
=  the equilibrium constant of the reaction
=  coefficient of reactant
=  coefficient of reactant
=  coefficient of product
=  coefficient of product
=  the partial pressure of raised to the power of
=  the partial pressure of raised to the power of
=  the partial pressure of raised to the power of
=  the partial pressure of raised to the power of

For reversible reactions, changes in the total pressure, temperature or reactant concentrations will shift the

Le Chatelier's Principle. However, the reaction kinetics
may either oppose or enhance the equilibrium shift. In some cases, the reaction kinetics may be the overriding factor to consider.

Henry's law and the solubility of gases

Gases will dissolve in liquids to an extent that is determined by the equilibrium between the undissolved gas and the gas that has dissolved in the liquid (called the solvent).[10] The equilibrium constant for that equilibrium is:

(1)

where:

  • =  the equilibrium constant for the solvation process
  • =  partial pressure of gas in equilibrium with a solution containing some of the gas
  • =  the concentration of gas in the liquid solution

The form of the equilibrium constant shows that the concentration of a

solute gas in a solution is directly proportional to the partial pressure of that gas above the solution. This statement is known as Henry's law
and the equilibrium constant is quite often referred to as the Henry's law constant.[10][11][12]

Henry's law is sometimes written as:[13]

(2)

where is also referred to as the Henry's law constant.[13] As can be seen by comparing equations (1) and (2) above, is the reciprocal of . Since both may be referred to as the Henry's law constant, readers of the technical literature must be quite careful to note which version of the Henry's law equation is being used.

Henry's law is an approximation that only applies for dilute, ideal solutions and for solutions where the liquid solvent does not react chemically with the gas being dissolved.

In diving breathing gases

In underwater diving the physiological effects of individual component gases of breathing gases are a function of partial pressure.[14]

Using diving terms, partial pressure is calculated as:

partial pressure = (total absolute pressure) × (volume fraction of gas component)[14]

For the component gas "i":

pi = P × Fi[14]

For example, at 50 metres (164 ft) underwater, the total absolute pressure is 6 bar (600 kPa) (i.e., 1 bar of

air, oxygen 21% by volume and nitrogen
approximately 79% by volume are:

pN2 = 6 bar × 0.79 = 4.7 bar absolute
pO2 = 6 bar × 0.21 = 1.3 bar absolute
where:  
pi = partial pressure of gas component i  = in the terms used in this article
P = total pressure = in the terms used in this article
Fi = volume fraction of gas component i  =  mole fraction, , in the terms used in this article
pN2 = partial pressure of nitrogen  = in the terms used in this article
pO2 = partial pressure of oxygen  = in the terms used in this article

The minimum safe lower limit for the partial pressures of oxygen in a breathing gas mixture for diving is 0.16 bars (16 kPa) absolute.

NOAA Diving Manual recommends a maximum single exposure of 45 minutes at 1.6 bar absolute, of 120 minutes at 1.5 bar absolute, of 150 minutes at 1.4 bar absolute, of 180 minutes at 1.3 bar absolute and of 210 minutes at 1.2 bar absolute. Oxygen toxicity becomes a risk when these oxygen partial pressures and exposures are exceeded. The partial pressure of oxygen also determines the maximum operating depth of a gas mixture.[14]

Narcosis is a problem when breathing gases at high pressure. Typically, the maximum total partial pressure of narcotic gases used when planning for technical diving may be around 4.5 bar absolute, based on an equivalent narcotic depth of 35 metres (115 ft).

The effect of a toxic contaminant such as carbon monoxide in breathing gas is also related to the partial pressure when breathed. A mixture which may be relatively safe at the surface could be dangerously toxic at the maximum depth of a dive, or a tolerable level of carbon dioxide in the breathing loop of a diving rebreather may become intolerable within seconds during descent when the partial pressure rapidly increases, and could lead to panic or incapacitation of the diver.[14]

In medicine

The partial pressures of particularly oxygen () and carbon dioxide () are important parameters in tests of

arterial blood gases, but can also be measured in, for example, cerebrospinal fluid. [why?
]

Reference ranges for and
Unit
Arterial blood gas
Venous blood gas Cerebrospinal fluid Alveolar pulmonary
gas pressures
kPa
11–13[16] 4.0–5.3[16] 5.3–5.9[16] 14.2
mmHg
75–100[17] 30–40[18] 40–44[19] 107
kPa 4.7–6.0[16] 5.5–6.8[16] 5.9–6.7[16] 4.8
mmHg 35–45[17] 41–51[18] 44–50[19] 36

See also

  • Blood gas tension – Partial pressure of blood gases
  • Breathing gas – Gas used for human respiration
  • Henry's law – Gas law regarding proportionality of dissolved gas
  • Ideal gas – Mathematical model which approximates the behavior of real gases
    • Ideal gas law – Equation of the state of a hypothetical ideal gas
  • Mole fraction – Proportion of a constituent in a mixture
  • Vapor – Substances in the gas phase at a temperature lower than its critical point

References

  1. .
  2. ^ "Gas Pressure and Respiration". Lumen Learning.
  3. ^ Gas blending
  4. ^ Staff. "Symbols and Units" (PDF). Respiratory Physiology & Neurobiology : Guide for Authors. Elsevier. p. 1. Archived (PDF) from the original on 2015-07-23. Retrieved 3 June 2017. All symbols referring to gas species are in subscript,
  5. ^ Dalton's Law of Partial Pressures
  6. ^ Frostberg State University's "General Chemistry Online"
  7. ^ Page 200 in: Medical biophysics. Flemming Cornelius. 6th Edition, 2008.
  8. .
  9. ^ a b An extensive list of Henry's law constants, and a conversion tool
  10. ISSN 0360-7275
    .
  11. ^ Introductory University Chemistry, Henry's Law and the Solubility of Gases Archived 2012-05-04 at the Wayback Machine
  12. ^ a b "University of Arizona chemistry class notes". Archived from the original on 2012-03-07. Retrieved 2006-05-26.
  13. ^ a b c d e NOAA Diving Program (U.S.) (December 1979). Miller, James W. (ed.). NOAA Diving Manual, Diving for Science and Technology (2nd ed.). Silver Spring, Maryland: US Department of Commerce: National Oceanic and Atmospheric Administration, Office of Ocean Engineering.
  14. .
  15. ^ a b c d e f Derived from mmHg values using 0.133322 kPa/mmHg
  16. ^ a b Normal Reference Range Table Archived 2011-12-25 at the Wayback Machine from The University of Texas Southwestern Medical Center at Dallas. Used in Interactive Case Study Companion to Pathologic basis of disease.
  17. ^ a b The Medical Education Division of the Brookside Associates--> ABG (Arterial Blood Gas) Retrieved on Dec 6, 2009
  18. ^ a b Pathology 425 Cerebrospinal Fluid [CSF] Archived 2012-02-22 at the Wayback Machine at the Department of Pathology and Laboratory Medicine at the University of British Columbia. By G.P. Bondy. Retrieved November 2011