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In [[chemistry]], the '''Henderson–Hasselbalch equation''' describes the derivation of [[pH]] as a measure of acidity (using pK<sub>a</sub>, the negative log of the [[acid dissociation constant]]) in biological and chemical systems. The equation is also useful for estimating the pH of a [[buffer solution]] and finding the [[Chemical equilibrium|equilibrium]] pH in [[acid-base reaction theories|acid-base reactions]] (it is widely used to calculate the [[isoelectric point]] of proteins).
 
The equation is given by:
 
:<math>\textrm{pH} = \textrm{pK}_{a}+ \log_{10} \left ( \frac{[\textrm{A}^-]}{[\textrm{HA}]} \right )</math>
 
Here, [HA] is the molar concentration of the undissociated weak acid, [A⁻] is the molar concentration of this acid's conjugate base and <math>\textrm{pK}_{a}</math> is <math>-\log (K_{a})</math> where <math>K_{a}</math> is the [[acid dissociation constant]], that is:
 
:<math>\textrm{pK}_{a} = - \log_{10} (K_{a}) = - \log_{10} \left ( \frac{[\mbox{H}_{3}\mbox{O}^+][\mbox{A}^-]}{[\mbox{HA}]} \right )</math> for the non-specific Brønsted acid-base reaction: <math>\mbox{HA} + \mbox{H}_{2}\mbox{O} \rightleftharpoons \mbox{A}^- + \mbox{H}_{3}\mbox{O}^+</math>
 
A second form of the equation, known as the Heylman Equation, expressed in terms of <math>K_{b}</math> where <math>K_{b}</math> is the [[acid dissociation constant#Bases|base dissociation constant]]:
<math>\textrm{pK}_{b} = - \log_{10} (K_{b}) = - \log_{10} \left ( \frac{[\mbox{O}\mbox{H}^-][\mbox{HA}]}{[\mbox{A}^-]} \right )</math>
 
In these equations, <math>\mbox{A}^-</math> denotes the ionic form of the relevant acid. Bracketed quantities such as [base] and [acid] denote the molar concentration of the quantity enclosed.
 
In analogy to the above equations, the following equation is valid:
 
:<math>\textrm{pOH} = \textrm{pK}_{b}+ \log_{10}  \left ( \frac{[\textrm{BH}^+]}{[\textrm{B}]} \right )</math>
 
Where BH<sup>+</sup> denotes the conjugate acid of the corresponding base B.
 
==Derivation==
The Henderson–Hasselbalch equation is derived from the [[acid dissociation constant]] equation by the following steps:<ref>[http://pharmaxchange.info/press/2012/10/henderson%E2%80%93hasselbalch-equation-derivation-of-pka-and-pkb/ Henderson Hasselbalch Equation: Derivation of pKa and pKb]</ref>
 
:<math>K_\textrm{a} = \frac{[\textrm{H}^+][\textrm{A}^-]} {[\textrm{HA}]}</math>
 
:<math>\log_{10}K_\textrm{a} = \log_{10} \left ( \frac{[\textrm{H}^+][\textrm{A}^-]}{[\textrm{HA}]} \right )</math>
 
:<math>\log_{10}K_\textrm{a} = \log_{10}[\textrm{H}^+] + \log_{10} \left ( \frac{[\textrm{A}^-]}{[\textrm{HA}]} \right )</math>
 
:<math>-\textrm{p}K_\textrm{a} = -\textrm{pH} + \log_{10} \left ( \frac{[\textrm{A}^-]}{[\textrm{HA}]} \right )</math>
 
:<math>\textrm{pH} = \textrm{p}K_\textrm{a} + \log_{10} \left ( \frac{[\textrm{A}^-]}{[\textrm{HA}]} \right )</math>
 
The ratio <math>[A^-]/[HA]</math> is unitless, and as such, other ratios with other units may be used. For example, the mole ratio of the components, <math>n_{A^-}/n_{HA}</math> or the fractional concentrations <math>\alpha_{A^-}/\alpha_{HA}</math> where <math>\alpha_{A^-}+\alpha_{HA}=1</math> will yield the same answer. Sometimes these other units are more convenient to use.
 
==History==
[[Lawrence Joseph Henderson]] wrote an equation, in 1908, describing the use of [[carbonic acid]] as a [[buffer solution]]. [[Karl Albert Hasselbalch]] later re-expressed that formula in [[logarithm]]ic terms, resulting in the Henderson–Hasselbalch equation [http://www.acid-base.com/history.php]. Hasselbalch was using the formula to study [[metabolic acidosis]].
 
==Limitations==
There are some significant approximations implicit in the Henderson–Hasselbalch equation. The most significant is the assumption that the concentration of the acid and its conjugate base at equilibrium will remain the same as the formal concentration. This neglects the dissociation of the acid and the binding of H+ to the base. The dissociation of water itself is neglected as well. These approximations will fail when dealing with relatively strong acids or bases (pKa more than a couple units away from 7), dilute or very concentrated solutions (less than 1 mM or greater than 1M), or heavily skewed acid/base ratios (more than 100 to 1).
Also, the equation does not take into effect the dilution factor of the acid and conjugate base in water. If the proportion of acid to base is 1, then the pH of the solution will be different if the amount of water changes from 1mL to 1L.
 
==Estimating blood pH==
The Henderson–Hasselbalch equation can be applied to relate the pH of [[blood]] to constituents of the [[bicarbonate buffering system]]:<ref name=Bray1999>[http://books.google.com.my/books?id=qyHu0Iu-XOUC&pg=PA556 page 556], section "Estimating plasma pH" in: {{Cite book  | last1 = Bray | first1 = John J. | title = Lecture notes on human physiolog | year = 1999 | publisher = Blackwell Science | location = Malden, Mass. | isbn = 978-0-86542-775-4 | pages =  }}</ref>
 
:<math> pH = pK_{a~H_2CO_3}+ \log_{10}  \left ( \frac{[HCO_3^-]}{[H_2CO_3]} \right )</math>
, where:
*pK<sub>a H<sub>2</sub>CO<sub>3</sub></sub> is the [[cologarithm]] of the [[acid dissociation constant]] of [[carbonic acid]]. It is equal to 6.1.
*[HCO<sub>3</sub><sup>-</sup>] is the concentration of [[bicarbonate]] in the blood
*[H<sub>2</sub>CO<sub>3</sub>] is the concentration of carbonic acid in the blood
 
This is useful in [[arterial blood gas]], but these usually state ''pCO<sub>2</sub>'', that is, the [[partial pressure]] of [[carbon dioxide]], rather than H<sub>2</sub>CO<sub>3</sub>. However, these are related by the equation:<ref name=Bray1999/>
 
:<math> [H_2CO_3] = k_{\rm H~CO_2}\, \times pCO_2 </math>
, where:
*[H<sub>2</sub>CO<sub>3</sub>] is the concentration of carbonic acid in the blood
*''k<sub>H CO<sub>2</sub></sub>'' is the [[Henry's law]] constant for the [[solubility]] of carbon dioxide in blood. ''k<sub>H CO<sub>2</sub></sub>'' is approximately 0.03 [[millimole|mmol]]/[[mmHg]]
*''pCO<sub>2</sub>'' is the [[partial pressure]] of [[carbon dioxide]] in the blood
 
Taken together, the following equation can be used to relate the pH of blood to the concentration of bicarbonate and the partial pressure of carbon dioxide:<ref name=Bray1999/>
 
:<math> pH = 6.1 + \log_{10}  \left ( \frac{[HCO_3^-]}{0.03 \times pCO_2} \right )</math>
, where:
*pH is the acidity in the blood
*[HCO<sub>3</sub><sup>-</sup>] is the concentration of bicarbonate in the blood
*''pCO<sub>2</sub>'' is the partial pressure of carbon dioxide in the blood
 
==See also==
*[[Acid]]
*[[base (chemistry)|Base]]
*[[Titration]]
*[[Buffer solution]]
*[[Acidosis]]
*[[Alkalosis]]
 
==References==
{{reflist}}
 
==Further reading==
* {{Cite journal| author = Lawrence J. Henderson | title = Concerning the relationship between the strength of acids and their capacity to preserve neutrality | journal = [[Am. J. Physiol.]] | date=1 May 1908| volume = 21 | pages = 173–179 | url = http://ajplegacy.physiology.org/cgi/content/abstract/21/4/465-s | format = Abstract | issue = 4 }}
* {{Cite journal| author = Hasselbalch, K. A. | title = Die Berechnung der Wasserstoffzahl des Blutes aus der freien und gebundenen Kohlensäure desselben, und die Sauerstoffbindung des Blutes als Funktion der Wasserstoffzahl | journal = [[Biochemische Zeitschrift]] | year = 1917 | volume = 78 | pages = 112–144}}
* {{Cite journal| author = Po, Henry N.; Senozan, N. M. | title = Henderson–Hasselbalch Equation: Its History and Limitations | journal = [[J. Chem. Educ.]] | year = 2001 | volume = 78 | pages = 1499–1503 | doi = 10.1021/ed078p1499| issue = 11|bibcode = 2001JChEd..78.1499P }}
* {{Cite journal| author = de Levie, Robert. | title = The Henderson–Hasselbalch Equation: Its History and Limitations | journal = [[J. Chem. Educ.]] | year = 2003 | volume = 80 | pages = 146 | doi = 10.1021/ed080p146| issue = 2|bibcode = 2003JChEd..80..146D }}
* {{Cite journal| author = de Levie, Robert | journal = [[The Chemical Educator]] | year = 2002 | volume = 7 | pages = 132–135 | doi = 10.1007/s00897020562a | title = The Henderson Approximation and the Mass Action Law of Guldberg and Waage| issue = 3}}
 
==External links==
*[http://www.changbioscience.com/calculator/HendersonHasselbach.html Henderson–Hasselbalch Calculator]
*[http://www.chembuddy.com/?left=pH-calculation&right=pH-buffers-henderson-hasselbalch Derivation and detailed discussion of Henderson–Hasselbalch equation]
*[http://isoelectric.ovh.org True example of using Henderson–Hasselbalch equation for calculation net charge of proteins]
 
{{Use dmy dates|date=September 2010}}
 
{{DEFAULTSORT:Henderson-Hasselbalch Equation}}
[[Category:Acid-base chemistry]]
[[Category:Equilibrium chemistry]]
[[Category:Equations]]
[[Category:Mathematics in medicine]]
[[Category:Respiratory therapy]]

Revision as of 23:32, 2 February 2014

In chemistry, the Henderson–Hasselbalch equation describes the derivation of pH as a measure of acidity (using pKa, the negative log of the acid dissociation constant) in biological and chemical systems. The equation is also useful for estimating the pH of a buffer solution and finding the equilibrium pH in acid-base reactions (it is widely used to calculate the isoelectric point of proteins).

The equation is given by:

Here, [HA] is the molar concentration of the undissociated weak acid, [A⁻] is the molar concentration of this acid's conjugate base and is where is the acid dissociation constant, that is:

for the non-specific Brønsted acid-base reaction:

A second form of the equation, known as the Heylman Equation, expressed in terms of where is the base dissociation constant:

In these equations, denotes the ionic form of the relevant acid. Bracketed quantities such as [base] and [acid] denote the molar concentration of the quantity enclosed.

In analogy to the above equations, the following equation is valid:

Where BH+ denotes the conjugate acid of the corresponding base B.

Derivation

The Henderson–Hasselbalch equation is derived from the acid dissociation constant equation by the following steps:[1]

The ratio is unitless, and as such, other ratios with other units may be used. For example, the mole ratio of the components, or the fractional concentrations where will yield the same answer. Sometimes these other units are more convenient to use.

History

Lawrence Joseph Henderson wrote an equation, in 1908, describing the use of carbonic acid as a buffer solution. Karl Albert Hasselbalch later re-expressed that formula in logarithmic terms, resulting in the Henderson–Hasselbalch equation [1]. Hasselbalch was using the formula to study metabolic acidosis.

Limitations

There are some significant approximations implicit in the Henderson–Hasselbalch equation. The most significant is the assumption that the concentration of the acid and its conjugate base at equilibrium will remain the same as the formal concentration. This neglects the dissociation of the acid and the binding of H+ to the base. The dissociation of water itself is neglected as well. These approximations will fail when dealing with relatively strong acids or bases (pKa more than a couple units away from 7), dilute or very concentrated solutions (less than 1 mM or greater than 1M), or heavily skewed acid/base ratios (more than 100 to 1). Also, the equation does not take into effect the dilution factor of the acid and conjugate base in water. If the proportion of acid to base is 1, then the pH of the solution will be different if the amount of water changes from 1mL to 1L.

Estimating blood pH

The Henderson–Hasselbalch equation can be applied to relate the pH of blood to constituents of the bicarbonate buffering system:[2]

, where:

This is useful in arterial blood gas, but these usually state pCO2, that is, the partial pressure of carbon dioxide, rather than H2CO3. However, these are related by the equation:[2]

, where:

Taken together, the following equation can be used to relate the pH of blood to the concentration of bicarbonate and the partial pressure of carbon dioxide:[2]

, where:

  • pH is the acidity in the blood
  • [HCO3-] is the concentration of bicarbonate in the blood
  • pCO2 is the partial pressure of carbon dioxide in the blood

See also

References

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    Discover out more about real estate funding in the area, together with info on international funding incentives and property possession. Many Singaporeans have been investing in property across the causeway in recent years, attracted by comparatively low prices. However, those who need to exit their investments quickly are likely to face significant challenges when trying to sell their property – and could finally be stuck with a property they can't sell. Career improvement programmes, in-house valuation, auctions and administrative help, venture advertising and marketing, skilled talks and traisning are continuously planned for the sales associates to help them obtain better outcomes for his or her shoppers while at Knight Frank Singapore. No change Present Rules

    Extending the tax exemption would help. The exemption, which may be as a lot as $2 million per family, covers individuals who negotiate a principal reduction on their existing mortgage, sell their house short (i.e., for lower than the excellent loans), or take part in a foreclosure course of. An extension of theexemption would seem like a common-sense means to assist stabilize the housing market, but the political turmoil around the fiscal-cliff negotiations means widespread sense could not win out. Home Minority Chief Nancy Pelosi (D-Calif.) believes that the mortgage relief provision will be on the table during the grand-cut price talks, in response to communications director Nadeam Elshami. Buying or promoting of blue mild bulbs is unlawful.

    A vendor's stamp duty has been launched on industrial property for the primary time, at rates ranging from 5 per cent to 15 per cent. The Authorities might be trying to reassure the market that they aren't in opposition to foreigners and PRs investing in Singapore's property market. They imposed these measures because of extenuating components available in the market." The sale of new dual-key EC models will even be restricted to multi-generational households only. The models have two separate entrances, permitting grandparents, for example, to dwell separately. The vendor's stamp obligation takes effect right this moment and applies to industrial property and plots which might be offered inside three years of the date of buy. JLL named Best Performing Property Brand for second year running

    The data offered is for normal info purposes only and isn't supposed to be personalised investment or monetary advice. Motley Fool Singapore contributor Stanley Lim would not personal shares in any corporations talked about. Singapore private home costs increased by 1.eight% within the fourth quarter of 2012, up from 0.6% within the earlier quarter. Resale prices of government-built HDB residences which are usually bought by Singaporeans, elevated by 2.5%, quarter on quarter, the quickest acquire in five quarters. And industrial property, prices are actually double the levels of three years ago. No withholding tax in the event you sell your property. All your local information regarding vital HDB policies, condominium launches, land growth, commercial property and more

    There are various methods to go about discovering the precise property. Some local newspapers (together with the Straits Instances ) have categorised property sections and many local property brokers have websites. Now there are some specifics to consider when buying a 'new launch' rental. Intended use of the unit Every sale begins with 10 p.c low cost for finish of season sale; changes to 20 % discount storewide; follows by additional reduction of fiftyand ends with last discount of 70 % or extra. Typically there is even a warehouse sale or transferring out sale with huge mark-down of costs for stock clearance. Deborah Regulation from Expat Realtor shares her property market update, plus prime rental residences and houses at the moment available to lease Esparina EC @ Sengkang
  • One of the biggest reasons investing in a Singapore new launch is an effective things is as a result of it is doable to be lent massive quantities of money at very low interest rates that you should utilize to purchase it. Then, if property values continue to go up, then you'll get a really high return on funding (ROI). Simply make sure you purchase one of the higher properties, reminiscent of the ones at Fernvale the Riverbank or any Singapore landed property Get Earnings by means of Renting

    In its statement, the singapore property listing - website link, government claimed that the majority citizens buying their first residence won't be hurt by the new measures. Some concessions can even be prolonged to chose teams of consumers, similar to married couples with a minimum of one Singaporean partner who are purchasing their second property so long as they intend to promote their first residential property. Lower the LTV limit on housing loans granted by monetary establishments regulated by MAS from 70% to 60% for property purchasers who are individuals with a number of outstanding housing loans on the time of the brand new housing purchase. Singapore Property Measures - 30 August 2010 The most popular seek for the number of bedrooms in Singapore is 4, followed by 2 and three. Lush Acres EC @ Sengkang

    Discover out more about real estate funding in the area, together with info on international funding incentives and property possession. Many Singaporeans have been investing in property across the causeway in recent years, attracted by comparatively low prices. However, those who need to exit their investments quickly are likely to face significant challenges when trying to sell their property – and could finally be stuck with a property they can't sell. Career improvement programmes, in-house valuation, auctions and administrative help, venture advertising and marketing, skilled talks and traisning are continuously planned for the sales associates to help them obtain better outcomes for his or her shoppers while at Knight Frank Singapore. No change Present Rules

    Extending the tax exemption would help. The exemption, which may be as a lot as $2 million per family, covers individuals who negotiate a principal reduction on their existing mortgage, sell their house short (i.e., for lower than the excellent loans), or take part in a foreclosure course of. An extension of theexemption would seem like a common-sense means to assist stabilize the housing market, but the political turmoil around the fiscal-cliff negotiations means widespread sense could not win out. Home Minority Chief Nancy Pelosi (D-Calif.) believes that the mortgage relief provision will be on the table during the grand-cut price talks, in response to communications director Nadeam Elshami. Buying or promoting of blue mild bulbs is unlawful.

    A vendor's stamp duty has been launched on industrial property for the primary time, at rates ranging from 5 per cent to 15 per cent. The Authorities might be trying to reassure the market that they aren't in opposition to foreigners and PRs investing in Singapore's property market. They imposed these measures because of extenuating components available in the market." The sale of new dual-key EC models will even be restricted to multi-generational households only. The models have two separate entrances, permitting grandparents, for example, to dwell separately. The vendor's stamp obligation takes effect right this moment and applies to industrial property and plots which might be offered inside three years of the date of buy. JLL named Best Performing Property Brand for second year running

    The data offered is for normal info purposes only and isn't supposed to be personalised investment or monetary advice. Motley Fool Singapore contributor Stanley Lim would not personal shares in any corporations talked about. Singapore private home costs increased by 1.eight% within the fourth quarter of 2012, up from 0.6% within the earlier quarter. Resale prices of government-built HDB residences which are usually bought by Singaporeans, elevated by 2.5%, quarter on quarter, the quickest acquire in five quarters. And industrial property, prices are actually double the levels of three years ago. No withholding tax in the event you sell your property. All your local information regarding vital HDB policies, condominium launches, land growth, commercial property and more

    There are various methods to go about discovering the precise property. Some local newspapers (together with the Straits Instances ) have categorised property sections and many local property brokers have websites. Now there are some specifics to consider when buying a 'new launch' rental. Intended use of the unit Every sale begins with 10 p.c low cost for finish of season sale; changes to 20 % discount storewide; follows by additional reduction of fiftyand ends with last discount of 70 % or extra. Typically there is even a warehouse sale or transferring out sale with huge mark-down of costs for stock clearance. Deborah Regulation from Expat Realtor shares her property market update, plus prime rental residences and houses at the moment available to lease Esparina EC @ Sengkang

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