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pH 1

pH
In chemistry, pH is a measure of the acidity or basicity of an aqueous solution. Pure water is said to be neutral, with
a pH close to 7.0 at 25 °C (77 °F). Solutions with a pH less than 7 are said to be acidic and solutions with a pH
greater than 7 are basic or alkaline. pH measurements are important in medicine, biology, chemistry, food science,
environmental science, oceanography, civil engineering and many other applications.
In a solution pH approximates but is not equal to p[H], the negative logarithm (base 10) of the molar concentration
of dissolved hydronium ions (H3O+); a low pH indicates a high concentration of hydronium ions, while a high pH
indicates a low concentration. Crudely, this negative of the logarithm matches the number of places behind the
decimal point, so for example 0.1 molar hydrochloric acid should be near pH 1 and 0.0001 molar HCl should be near
pH 4 (the base 10 logarithms of 0.1 and 0.0001 being −1, and −4, respectively). Pure (de-ionized) water is neutral,
and can be considered either a very weak acid or a very weak base (center of the 0 to 14 pH scale), giving it a pH of
7 (at 25 °C (77 °F)), or 0.0000001 M H+.[1] For an aqueous solution to have a higher pH, a base must be dissolved in
it, which binds away many of these rare hydrogen ions. Hydrogen ions in water can be written simply as H+ or as
hydronium (H3O+) or higher species (e.g. H9O4+) to account for solvation, but all describe the same entity. Most of
the Earth's freshwater surface bodies are slightly acidic due to the abundance and absorption of carbon dioxide;[2] in
fact, for millennia in the past most fresh water bodies have long existed at a slightly acidic pH level.
However, pH is not precisely p[H], but takes into account an activity factor. This represents the tendency of
hydrogen ions to interact with other components of the solution, which affects among other things the electrical
potential read using a pH meter. As a result, pH can be affected by the ionic strength of a solution – for example, the
pH of a 0.05 M potassium hydrogen phthalate solution can vary by as much as 0.5 pH units as a function of added
potassium chloride, even though the added salt is neither acidic nor basic.[3]
Hydrogen ion activity coefficients cannot be measured directly by any thermodynamically sound method, so they are
based on theoretical calculations. Therefore the pH scale is defined in practice as traceable to a set of standard
solutions whose pH is established by international agreement.[4] Primary pH standard values are determined by the
Harned cell, a hydrogen gas electrode, using the Bates–Guggenheim Convention.

History
The concept of p[H] was first introduced by Danish chemist Søren Peder Lauritz Sørensen at the Carlsberg
Laboratory in 1909[5] [6] and revised to the modern pH in 1924 after it became apparent that electromotive force in
cells depended on activity rather than concentration of hydrogen ions.[3] In the first papers, the notation had the H as
a subscript to the lower case p, like so: pH.[7]
It is unknown what the exact definition of 'p' in pH is. A common definition often used in schools is "percentage".
However some references suggest the p stands for “Power”,[8] others refer to the German word “Potenz” (meaning
power in German),[9] still others refer to “potential”. Jens Norby published a paper in 2000 arguing that p is a
constant and stands for “negative logarithm”;[10] H then stands for Hydrogen. According to the Carlsberg Foundation
pH stands for "power of hydrogen".[8] Other suggestions that have surfaced over the years are that the p stands for
puissance (also meaning power but then the Carlsberg Laboratory was French speaking) or that pH stands for the
Latin terms pondus Hydrogenii or potentia hydrogenii. It is also suggested that Sørensen used the letters p and q
(commonly paired letters in mathematics) simply to label the test solution (p) and the reference solution (q).[11]
pH 2

Definitions

Mathematical definition
pH is defined as a negative decimal logarithm of the hydrogen ion activity in a solution.[12]

where aH is the activity of hydrogen ions in units of Mol/L (molar concentration). Activity has a sense of
concentration, however activity is always less than the concentration and is defined as a concentration (Mol/L) of an
ion multiplied by activity coefficient. The activity coefficient for diluted solutions is a real number between 0 and 1
(for concentrated solutions may be greater than 1) and it depends on many parameters of a solution, such as nature of
ion, ion force, temperature etc. For a strong electrolyte activity of an ion approaches it concentration in diluted
solutions. Activity can be measured experimentally by means of an ion-selective electrode which responds,
according to the Nernst equation, to hydrogen ion activity. pH is commonly measured by means of a glass electrode
connected to a milli-voltmeter with very high input impedance which measures the potential difference, or
electromotive force, E, between an electrode sensitive to the hydrogen ion activity and a reference electrode, such as
a calomel electrode or a silver chloride electrode. Quite often glass electrode is combined with the reference
electrode and a temperature sensor in one body. The glass electrode relatively good (95 - 99.9%) follows the Nernst
equation:

where E is a measured potential , E0 is the standard electrode potential, that is, the electrode potential for the standard
state in which the activity is one. R is the gas constant, T is the temperature in kelvins, F is the Faraday constant and
n is the number of electrons transferred (ion charge), one in this instance. The electrode potential, E, is proportional
to the logarithm of the hydrogen ion activity.
This definition, by itself, is wholly impractical, because the hydrogen ion activity is the product of the concentration
and an activity coefficient. To get proper results, the electrode must be calibrated using standard solutions of known
activity.
The operational definition of pH is officially defined by International Standard ISO 31-8 as follows:[13] For a
solution X, first measure the electromotive force EX of the galvanic cell
reference electrode|concentrated solution of KCl || solution X|H2|Pt
and then also measure the electromotive force ES of a galvanic cell that differs from the above one only by the
replacement of the solution X of unknown pH, pH(X), by a solution S of a known standard pH, pH(S). The pH of X
is then

The difference between the pH of solution X and the pH of the standard solution depends only on the difference
between two measured potentials. Thus, pH is obtained from a potential measured with an electrode calibrated
against one or more pH standards; a pH meter setting is adjusted such that the meter reading for a solution of a
standard is equal to the value pH(S). Values pH(S) for a range of standard solutions S, along with further details, are
given in the IUPAC recommendations.[14] The standard solutions are often described as standard buffer solution. In
practice, it is better to use two or more standard buffers to allow for small deviations from Nernst-law ideality in real
electrodes. Note that because the temperature occurs in the defining equations, the pH of a solution is
temperature-dependent.
Measurement of extremely low pH values, such as some very acidic mine waters,[15] requires special procedures.
Calibration of the electrode in such cases can be done with standard solutions of concentrated sulfuric acid, whose
pH 3

pH values can be calculated with using Pitzer parameters to calculate activity coefficients.[16]
pH is an example of an acidity function. Hydrogen ion concentrations can be measured in non-aqueous solvents, but
this leads, in effect, to a different acidity function, because the standard state for a non-aqueous solvent is different
from the standard state for water. Superacids are a class of non-aqueous acids for which the Hammett acidity
function, H0, has been developed.

p[H]
This was the original definition of Sørensen,[8] which was superseded in favour of pH in 1924. However, it is
possible to measure the concentration of hydrogen ions directly, if the electrode is calibrated in terms of hydrogen
ion concentrations. One way to do this, which has been used extensively, is to titrate a solution of known
concentration of a strong acid with a solution of known concentration of strong alkali in the presence of a relatively
high concentration of background electrolyte. Since the concentrations of acid and alkali are known it is easy to
calculate the concentration of hydrogen ions so that the measured potential can be correlated with concentrations.
The calibration is usually carried out using a Gran plot.[17] The calibration yieds a value for the standard electrode
potential, E0, and a slope factor, f, so that the Nernst equation in the form

can be used to derive hydrogen ion concentrations from experimental measurements of E. The slope factor is usually
slightly less than one. A slope factor of less than 0.95 indicates that the electrode is not functioning correctly. The
presence of background electrolyte ensures that the hydrogen ion activity coefficient is effectively constant during
the titration. As it is constant its value can be set to one by defining the standard state as being the solution
containing the background electrolyte. Thus, the effect of using this procedure is to make activity equal to the
numerical value of concentration.
The difference between p[H] and pH is quite small. It has been stated[18] that pH = p[H] + 0.04. It is common
practice to use the term "pH" for both types of measurement.we can report negative pH for strong acid.

pOH
pOH is sometimes used as a measure of the concentration of hydroxide ions, OH−, or alkalinity. pOH is not
measured independently, but is derived from pH. The concentration of hydroxide ions in water is related to the
concentration of hydrogen ions by
[OH−] = KW /[H+]
where KW is the self-ionisation constant of water. Taking cologarithms
pOH = pKW − pH.
So, at room temperature pOH ≈ 14 − pH. However this relationship is not strictly valid in other circumstances, such
as in measurements of soil alkalinity.
pH 4

Applications
Pure (neutral) water has a pH around 7 at 25 °C (77 °F); this value
varies with temperature. When an acid is dissolved in water the pH will
be less than 7 (if at 25 °C (77 °F)) and when a base, or alkali is
dissolved in water the pH will be greater than 7 (if at 25 °C (77 °F)). A
solution of a strong acid, such as hydrochloric acid, at concentration
1 mol dm−3 has a pH of 0. A solution of a strong alkali, such as sodium
hydroxide, at concentration 1 mol dm−3 has a pH of 14. Thus,
measured pH values will mostly lie in the range 0 to 14. Since pH is a
logarithmic scale a difference of one pH unit is equivalent to a tenfold
difference in hydrogen ion concentration.

Because the glass electrode (and other ion selective electrodes)


responds to activity, the electrode should be calibrated in a medium
similar to the one being investigated. For instance, if one wishes to
measure the pH of a seawater sample, the electrode should be
calibrated in a solution resembling seawater in its chemical
composition, as detailed below.

An approximate measure of pH may be obtained by using a pH


indicator. A pH indicator is a substance that changes color around a
particular pH value. It is a weak acid or weak base and the color
change occurs around 1 pH unit either side of its acid dissociation
constant, or pKa, value. For example, the naturally occurring indicator
litmus is red in acidic solutions (pH<7 at 25 °C (77 °F)) and blue in
Some typical pH values
alkaline (pH>7 at 25 °C (77 °F)) solutions. Universal indicator consists
of a mixture of indicators such that there is a continuous color change
from about pH 2 to pH 10. Universal indicator paper is simple paper that has been impregnated with universal
indicator.

Universal indicator components


Indicator Low pH color Transition pH range High pH color

Thymol blue (first transition) Red 1.2 – 2.8 Yellow

Methyl red Red 4.4 – 6.2 Yellow

Bromothymol blue Yellow 6.0 – 7.6 Blue

Thymol blue (second transition) Yellow 8.0 – 9.6 Blue

Phenolphthalein Colorless 8.3 – 10.0 Fuchsia

A solution whose pH is 7 (at 25 °C (77 °F)) is said to be neutral, that is, it is neither acidic nor basic. Water is subject
to a self-ionization process.
H2O H+ + OH−
The dissociation constant, KW, has a value of about 10−14, so in neutral solution of a salt both the hydrogen ion
concentration and hydroxide ion concentration are about 10−7 mol dm−3. The pH of pure water decreases with
increasing temperatures. For example, the pH of pure water at 50 °C is 6.55. Note, however, that water that has been
exposed to air is mildly acidic. This is because water absorbs carbon dioxide from the air, which is then slowly
converted into carbonic acid, which dissociates to liberate hydrogen ions:
pH 5

CO2 + H2O  H2CO3  HCO3− + H+

Examples
Substance pH

[19] <1
Lead-battery acid

[20] 2.4 - 3.4


Vinegar

[21] 4,7
Bright, acidy breakfast coffee

[20] 8.0
Baking soda

Calculation of pH for weak and strong acids


In the case of a strong acid, there is complete dissociation, so the pH is simply equal to minus the logarithm of the
acid concentration. For example, a 0.01 molar solution of hydrochloric acid has a pH of −log(0.01), that is, pH = 2.
The pH of a solution of a weak acid may be calculated by means of an ICE table. For acids with a pKa value greater
than about 2,
pH = ½ ( pKa − log c0),
where c0 is the concentration of the acid. This is equivalent to Burrows' weak acid pH equation

A more general method is as follows. Consider the case of dissolving a weak acid, HA, in water. First write down the
equilibrium expression.
HA A− + H+
The equilibrium constant for this reaction is specified by

where [] indicates a concentration. The analytical concentration of the two reagents, CA for [A−] and CH for [H+]
must be equal to the sum of concentrations of those species that contain the reagents. CH is the concentration of
added mineral acid.
CA = [A−] + Ka[A−][H+]
CH = [H+] + Ka[A−][H+]
From the first equation

Substitution of this expression into the second equation gives

This simplifies to a quadratic equation in the hydrogen ion concentration

Solution of this equation gives [H+] and hence pH.


pH 6

This method can also be used for polyprotic acids. For example, for the diprotic acid oxalic acid, writing A2− for the
oxalate ion,
CA = [A2−] + β1[A2−][H+] + β2[A2−][H+]2
CH = [H+] + β1[A2−][H+] + 2β2[A2−][H+]2
where β1 and β2 are cumulative protonation constants. Following the same procedure of substituting from the first
equation into the second, a cubic equation in [H+] results. In general, the degree of the equation is one more than the
number of ionisable protons. The solution of these equations can be obtained relatively easily with the aid of a
spreadsheet such as EXCEL or Origin. The pH always has an amount of fractional figures equal to the amount of
significant figures of the concentration.

pH in nature
pH-dependent plant pigments that can be used as pH indicators occur
in many plants, including hibiscus, marigold, red cabbage
(anthocyanin),[22] and red wine.

Seawater
The pH of seawater plays an important role in the ocean's carbon cycle
and there is evidence of ongoing ocean acidification caused by carbon
dioxide emissions.[23] However, pH measurement is complicated by
the chemical properties of seawater, and several distinct pH scales exist Hydrangea macrophylla blossoms are either pink
in chemical oceanography.[24] or blue, depending on a pH-dependent
mobilization and uptake of soil aluminium into
As part of its operational definition of the pH scale, the IUPAC defines the plants.
a series of buffer solutions across a range of pH values (often denoted
with NBS or NIST designation). These solutions have a relatively low ionic strength (~0.1) compared to that of
seawater (~0.7), and consequently are not recommended for use in characterising the pH of seawater since the ionic
strength differences cause changes in electrode potential. To resolve this problem, an alternative series of buffers
based on artificial seawater was developed.[25] This new series resolves the problem of ionic strength differences
between samples and the buffers, and the new pH scale is referred to as the total scale, often denoted as pHT.

The total scale was defined using a medium containing sulfate ions. These ions experience protonation, H+ + SO42−
⇌ HSO4−, such that the total scale includes the effect of both protons (free hydrogen ions) and hydrogen sulfate
ions:
[H+]T = [H+]F + [HSO4−]
An alternative scale, the free scale, often denoted pHF, omits this consideration and focuses solely on [H+]F, in
principle making it a simpler representation of hydrogen ion concentration. Analytically, only [H+]T can be
determined,[26] therefore, [H+]F must be estimated using the [SO42−] and the stability constant of HSO4−, KS*:
[H+]F = [H+]T − [HSO4−] = [H+]T ( 1 + [SO42−] / KS* )−1
However, it is difficult to estimate KS* in seawater, limiting the utility of the otherwise more straightforward free
scale.
Another scale, known as the seawater scale, often denoted pHSWS, takes account of a further protonation
relationship between hydrogen ions and fluoride ions, H+ + F− ⇌ HF. Resulting in the following expression for
[H+]SWS:
[H+]SWS = [H+]F + [HSO4−] + [HF]
pH 7

However, the advantage of considering this additional complexity is dependent upon the abundance of fluoride in the
medium. In seawater, for instance, sulfate ions occur at much greater concentrations (> 400 times) than those of
fluoride. Consequently, for most practical purposes, the difference between the total and seawater scales is very
small.
The following three equations summarise the three scales of pH:
pHF = − log [H+]F
pHT = − log ( [H+]F + [HSO4−] ) = − log [H+]T
pHSWS = − log ( [H+]F + [HSO4−] + [HF] ) = − log [H+]SWS
In practical terms, the three seawater pH scales differ in their values by up to 0.12 pH units, differences that are
much larger than the accuracy of pH measurements typically required, particularly in relation to the ocean's
carbonate system.[24] Since it omits consideration of sulfate and fluoride ions, the free scale is significantly different
from both the total and seawater scales. Because of the relative unimportance of the fluoride ion, the total and
seawater scales differ only very slightly.

Living systems

pH in living systems[27]
Compartment pH

Gastric acid 1

Lysosomes 4.5

Granules of chromaffin cells 5.5

Human skin 5.5

Urine 6.0

Neutral H2O at 37 °C 6.81

Cytosol 7.2

Cerebrospinal fluid (CSF) 7.3

Blood 7.34–7.45

Mitochondrial matrix 7.5

Pancreas secretions 8.1

The pH of different cellular compartments, body fluids, and organs is


usually tightly regulated in a process called acid-base homeostasis.
The pH of blood is usually slightly basic with a value of pH 7.365.
This value is often referred to as physiological pH in biology and
medicine.
Plaque can create a local acidic environment that can result in tooth
decay by demineralisation.
Enzymes and other proteins have an optimum pH range and can
become inactivated or denatured outside this range.
[28] [29] The most common disorder in acid-base homeostasis is acidosis, which
General symptoms of acidosis, resulting
from decrease in body pH. means an acid overload in the body, generally defined by pH falling
below 7.35.
pH 8

In the blood, pH can be estimated from known base excess (be) and bicarbonate concentration (HCO3) by the
following equation:[30]

References
[1] "General Chemistry Handouts, Pomona College: How to Solve Equilibrium Problems: An Approach Based on Stoichiometry Part II,
Acid-Base Reactions" (http:/ / pages. pomona. edu/ ~wes04747/ handout/ equil_io. htm). .
[2] C.Michael Hogan. 2010. Abiotic factor. Encyclopedia of Earth. eds Emily Monosson and C. Cleveland. National Council for Science and the
Environment (http:/ / www. eoearth. org/ article/ Abiotic_factor?topic=49461). Washington DC
[3] Isaac Feldman (1956). "Use and Abuse of pH measurements". Analytical Chemistry 28: 1859. doi:10.1021/ac60120a014. – cited and applied
in publicly accessible "13C and 170 NMR Binding Constant Studies of Uranyl Carbonate Complexes in Near-Neutral Aqueous Solution
Yucca Mountain Project Milestone Report 3351".
[4] "The Measurement of pH – Definition, Standards and Procedures – Report of the Working Party on pH, IUPAC Provisional
Recommendation" (http:/ / www. iupac. org/ reports/ provisional/ abstract01/ rondinini_prs. pdf). 2001. . A proposal to revise the current
IUPAC 1985 and ISO 31-8 definition of pH.
[5] 319 Sorensen, S. P. L., Enzymstudien. II, Ueber die Messung und die Bedeutung der Wasserstoffionenkonzentration bei enzymatischen
Prozessen, Biochem. Zeitschr., 1909, vol. 21, pp. 131–304.
[6] Two other publications appeared in 1909 one in French and one in Danisch
[7] "pH" (http:/ / dictionary. oed. com/ cgi/ entry/ 50176985). Oxford English Dictionary. .
[8] Carlsberg Group Company History Page (http:/ / www. carlsberggroup. com/ Company/ Research/ Pages/ pHValue. aspx)
[9] University of Waterloo – The pH Scale (http:/ / www. science. uwaterloo. ca/ ~cchieh/ cact/ c123/ ph. html)
[10] Nørby, Jens (2000). "The origin and the meaning of the little p in pH". Trends in the Biochemical Sciences 25 (1): 36–37.
doi:10.1016/S0968-0004(99)01517-0. PMID 10637613.
[11] Myers, Rollie J. (2010). "One-Hundred Years of pH". Journal of Chemical Education 87: 30. doi:10.1021/ed800002c.
[12] "pH" (http:/ / goldbook. iupac. org/ P04524. html). IUPAC Goldbook. .
[13] Quantities and units – Part 8: Physical chemistry and molecular physics, Annex C (normative): pH. International Organization for
Standardization, 1992.
[14] Covington, A. K.; Bates, R. G.; Durst, R. A. (1985). "Definitions of pH scales, standard reference values, measurement of pH, and related
terminology" (http:/ / www. iupac. org/ publications/ pac/ 1985/ pdf/ 5703x0531. pdf). Pure Appl. Chem. 57: 531–542.
doi:10.1351/pac198557030531. .
[15] Nordstrom, Darrell Kirk; Alpers, Charles N.; Ptacek, Carol J.; Blowes, David W. (2000). "Negative pH and Extremely Acidic Mine Waters
from Iron Mountain, California". Environmental Science & Technology 34: 254. doi:10.1021/es990646v.
[16] Zemaitis, J.F.; Clark, D.M; Rafal, M; Scrivner, N.C. (1986). "4". Handbook of Aqueous Electrolyte Thermodynamics: Theory & Application.
Wiley. ISBN 0816903506.
[17] Rossotti, F.J.C.; Rossotti, H. (1965). "Potentiometric titrations using Gran plots: A textbook omission". J. Chem. Ed. 42: 375–378.
doi:10.1021/ed042p375.
[18] Mendham, J.; Denney, R. C.; Barnes, J. D.; Thomas, M.J.K.; Denney, R. C.; Thomas, M. J. K. (2000), Vogel's Quantitative Chemical
Analysis (6th ed.), New York: Prentice Hall, ISBN 0-582-22628-7 Section 13.23, "Determination of pH"
[19] dekabatteries.com - Material safety data sheet, lead acid battery wet, filled with acid (US, CN, EU Version for International Trade) (http:/ /
www. dekabatteries. com/ assets/ base/ a. pdf)
[20] jackeden.com - pH Levels of Common Materials - Jack Eden (http:/ / jackeden. com/ tips/ phmat. html)
[21] coffeereview.com - Low-Acid Coffees - Coffee Review :: The World's Leading Coffee ... (http:/ / www. coffeereview. com/ article.
cfm?ID=9)
[22] "chemistry.about.com" (http:/ / chemistry. about. com/ library/ weekly/ aa012803a. htm). chemistry.about.com. 2010-06-11. . Retrieved
2010-08-26.
[23] Royal Society (2005). Ocean acidification due to increasing atmospheric carbon dioxide (http:/ / dge. stanford. edu/ labs/ caldeiralab/
Caldeira downloads/ RoyalSociety_OceanAcidification. pdf). ISBN 0854036172. .
[24] Zeebe, R. E. and Wolf-Gladrow, D. (2001) CO2 in seawater: equilibrium, kinetics, isotopes, Elsevier Science B.V., Amsterdam, Netherlands
ISBN 0444509461
[25] Hansson, I. (1973). "A new set of pH-scales and standard buffers for seawater". Deep Sea Research 20: 479–491.
doi:10.1016/0011-7471(73)90101-0.
[26] Dickson, A. G. (1984). "pH scales and proton-transfer reactions in saline media such as sea water". Geochim. Cosmochim. Acta 48:
2299–2308. doi:10.1016/0016-7037(84)90225-4.
[27] Boron, Walter, F.; Boulpaep, E.L. (2004). Medical Physiology: A Cellular And Molecular Approaoch. Elsevier/Saunders.
ISBN 1-4160-2328-3.
[28] Medical Encyclopedia: Metabolic Acidosis: Causes and symptoms (http:/ / www. nlm. nih. gov/ medlineplus/ ency/ article/ 000335. htm)
pH 9

[29] Symptoms mentioned in both metabolic and respiratory acidosis from the following two references:
- Wrongdiagnosis.com > Symptoms of Metabolic Acidosis (http:/ / www. wrongdiagnosis. com/ m/ metabolic_acidosis/ symptoms.
htm#symptom_list) Retrieved on April 13, 2009
- Wrongdiagnosis.com > Symptoms of Respiratory acidosis (http:/ / www. wrongdiagnosis. com/ r/ respiratory_acidosis/ symptoms.
htm-symptom_list) Retrieved on April 13, 2009
[30] Medical Calculators > Calculated Bicarbonate & Base Excess (http:/ / www-users. med. cornell. edu/ ~spon/ picu/ calc/ basecalc. htm) teven
Pon, MD, Weill Medical College of Cornell University

External links
• Online pH Calculator (http://www.webqc.org/phsolver.php)
Article Sources and Contributors 10

Article Sources and Contributors


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