Acids and bases

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Acid dissociation constant Acid-base extraction Acid€base reaction Acid€base titration Dissociation constant Acidity function Buffer solutions pH Proton affinity Amphoterism Self-ionization of water Acid strength Acid types

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Br•nsted Lewis Mineral Organic Strong Superacids Weak Base types

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Br•nsted Lewis Organic Strong Superbases Non-nucleophilic Weak

In chemistry, pH is a measure of the acidity or basicity of an aqueous solution. Solutions with a pH less than 7 are said to be acidic and solutions with a pH greater than 7 are basic or alkaline. Pure water has a pH very close to 7. The pH scale is traceable to a set of standard solutions whose pH is established by international agreement. Primary pH standard values are determined using a concentration cell with transference, by measuring the potential difference between a hydrogen electrode and a standard electrode such as the silver chloride electrode. Measurement of pH for aqueous solutions can be done with a glass electrode and a pH meter, or using indicators. pH measurements are important in medicine, biology, chemistry, agriculture, forestry, food science, environmental science, oceanography, civil engineering, chemical engineering, nutrition, water treatment & water purification, and many other applications.

is measured. It follows that electrode potential is proportional to pH when pH is defined in terms of activity. This method of calibration avoids the need to know the standard electrode potential. the cell is filled with a solution of known hydrogen ion activity and the emf. others refer to French puissance (also meaning "power". the notation had the "H" as a subscript to the lowercase "p". A combined glass electrode has an in-built reference electrode. The reference electrode may be a silver chloride electrode or a calomel electrode. in a solution.f.[1] 2 History The concept of p[H] was first introduced by Danish chemist S•ren Peder Lauritz S•rensen at the Carlsberg Laboratory in 1909[2] and revised to the modern pH in 1924 to accommodate definitions and measurements in terms of electrochemical cells. which are used to measure pH. electrode potential. It is also suggested that S•rensen used the letters "p" and "q" (commonly paired letters in mathematics) simply to label the test solution (p) and the reference solution (q). Two or more the . which. but according to the Carlsberg Foundation pH stands for "power of hydrogen".m. T is the temperature in kelvin. The difference between the two measured emf values is proportional to pH. For H+ number of electrons transferred is one. potentia hydrogenii. It is calibrated against buffer solutions of known hydrogen ion activity. The proportionality constant. as also in the term pKa. Reference electrode | concentrated solution of KCl || test solution | H2 | Pt Firstly. The hydrogen-ion selective electrode is a standard hydrogen electrode. This definition was adopted because ion-selective electrodes. or potential hydrogen. F is the Faraday constant. of the same cell containing the solution of unknown pH is measured. It has also been suggested that the "p" stands for the German Potenz (meaning "power"). a glass electrode is used rather than the cumbersome hydrogen electrode. more often expressed as the measure of the hydronium ion concentration. follows the Nernst equation. based on the fact that the Carlsberg Laboratory was French-speaking). To apply this process in practice. 1/z is ideally equal to "Nerstian slope". Definition and measurement pH pH is defined as the decimal logarithm of the reciprocal of the hydrogen ion activity. R is the gas constant. Then the emf. ES. The exact meaning of the "p" in "pH" is disputed. for the hydrogen ion can be written as where E is a measured potential. In the first papers. as so: pH. pH is the negative logarithm of the activity of the (solvated) hydronium ion. aH+. E. Other suggestions have surfaced over the years that the "p" stands for the Latin terms pondus hydrogenii. respond to activity. E0 is the standard electrode potential. Ideally. used for acid dissociation constants. Current usage in chemistry is that p stands for "decimal cologarithm of". IUPAC has proposed the use of a set of buffer solutions of known H+ activity. EX. others refer to "potential".PH In technical terms.) between a reference electrode and an electrode sensitive to the hydrogen ion activity when they are both immersed in the same aqueous solution. Precise measurement of pH is presented in International Standard ISO 31-8 as follows:[3] A galvanic cell is set up to measure the electromotive force (e.

are given in the IUPAC recommendations. 3 p[H] This was the original definition of S•rensen. Thus. if the electrode is calibrated in terms of hydrogen ion concentrations. is usually slightly less than one. The calibration is usually carried out using a Gran plot. the electrode should be calibrated in a solution resembling seawater in its chemical composition. One way to do this.PH buffer solutions are used in order to accommodate the fact that the "slope" may differ slightly from ideal. It has been stated[4] that pH = p[H] + 0.04. The presence of background electrolyte ensures that the hydrogen ion activity coefficient is effectively constant during the titration. . f. 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. it is easy to calculate the concentration of hydrogen ions so that the measured potential can be correlated with concentrations. E0. f. When more than two buffer solutions are used the electrode is calibrated by fitting observed pH values to a straight line with respect to standard buffer values. so that the Nernst equation in the form can be used to derive hydrogen ion concentrations from experimental measurements of E. using the "slope" control. the electrode is first immersed in a standard solution and the reading on a pH meter is adjusted to be equal to the standard buffer's value. Commercial standard buffer solutions usually come with information on the value at 25‚ƒC and a correction factor to be applied for other temperatures. A slope factor of less than 0. The reading from a second standard buffer solution is then adjusted. its value can be set to one by defining the standard state as being the solution containing the background electrolyte. As it is constant. as detailed below. The difference between p[H] and pH is quite small. The slope factor. which has been used extensively. Further details. it is possible to measure the concentration of hydrogen ions directly. It is common practice to use the term "pH" for both types of measurement. and a slope factor. the effect of using this procedure is to make activity equal to the numerical value of concentration. to be equal to the pH for that solution. For instance. The calibration yields a value for the standard electrode potential. However. if one wishes to measure the pH of a seawater sample.95 indicates that the electrode is not functioning correctly. Since the concentrations of acid and alkali are known. which was superseded in favor of pH in 1924. The pH scale is logarithmic and therefore pH is a dimensionless quantity. The glass electrode (and other ion selective electrodes) should be calibrated in a medium similar to the one being investigated. To implement this approach to calibration.

6 8. The concentration of hydroxide ions in water is related to the concentration of hydrogen ions by Relation between p[OH] and p[H] (red = acid region. pOH values are derived from pH measurements. Universal indicator paper is made from absorbent paper that has been impregnated with universal indicator. such as in measurements of soil alkalinity.3‚€‚10.0‚€‚9.2‚€‚2. OH•. Visual comparison of the color of a test solution with a standard color chart provides a means to measure pH accurate to the nearest whole number.8 4. using a colorimeter of spectrophotometer. at room temperature pOH ‚ 14 • pH.2 6.6 8. Taking logarithms So. Chart showing the variation of color of universal indicator paper with pH Universal indicator components Indicator Thymol blue (first transition) Methyl red Bromothymol blue Low pH color Transition pH range High pH color Red Red Yellow 1. or alkalinity. Universal indicator consists of a mixture of indicators such that there is a continuous color change from about pH 2 to pH 10.0 Yellow Yellow Blue Blue Fuchsia Thymol blue (second transition) Yellow Phenolphthalein Colorless pOH pOH is sometimes used as a measure of the concentration of hydroxide ions. . blue = basic region) where KW is the self-ionisation constant of water.PH 4 pH indicators Indicators may be used to measure pH. by making use of the fact that their color changes with pH. More precise measurements are possible if the color is measured spectrophotometrically.0‚€‚7. However this relationship is not strictly valid in other circumstances.4‚€‚6.

pH values based on these measurements belong to a different scale from aqueous pH values. the Hammett acidity function. It cannot be assumed that liquid junction potentials are independent of pH. Various factors contribute to this. For example. can be defined as: where €H+ is the chemical potential of the hydrogen ion. has been developed in connection with Superacids. Also.5 (ca. This scale applies to liquids. R is the gas constant and T is the thermodynamic temperature.003‚mol dm•3 acid) and above about 10. gases and even solids. Hydrogen ion activity. 0. because the electrode becomes sensitive to the concentration of cations such as Na+ and K+ in the solution. At high pH the glass electrode may be affected by "alkaline error". 0. Non-aqueous solutions Hydrogen ion concentrations (activities) can be measured in non-aqueous solvents. the Nernst law breaks down under those conditions.PH 5 Extremes of pH Measurement of pH below about 2. The concept of "Unified pH scale" has been developed on the basis of the absolute chemical potential of the proton. because activities relate to different standard states. when using the glass electrode. Runoff from mines or mine tailings can produce some very low pH values. €oH+ is its chemical potential in the chosen standard state. H0.5 (ca. Therefore pH values on the different scales cannot be compared directly. Other acidity functions can be defined. extreme pH implies that the solution is concentrated.[5] Specially constructed electrodes are available which partly overcome these problems. so electrode potentials are affected by ionic strength variation. pH is an example of an acidity function.[6] .0003‚mol dm•3 alkali) requires special procedures because. aH+.

even though the salt is neither acidic nor basic. Seawater The pH of seawater plays an important role in the ocean's carbon cycle. These ions experience protonation. this value varies with temperature. Note. pH measurement is complicated by the chemical properties of seawater. Since pH is a logarithmic scale. which is then slowly converted into bicarbonate and hydrogen ions: pH values of some common substances pH in nature pH-dependent plant pigments that can be used as pH indicators occur in many plants. This is because water absorbs carbon dioxide from the air. at concentration 1‚mol dm•3.1) compared to that of seawater (~0. the pH will be greater than that of pure water.7). the pH will be less than that of pure water. however. lactic acid is produced by muscle activity. and there is evidence of ongoing ocean acidification caused by carbon dioxide emissions. A solution of a strong acid. is pH-dependent. are not recommended for use in characterizing the pH of seawater. so Kw varies with ionic strength. so the pH of pure water is about 7 at 25‚ƒC. is dissolved in water. For example.[7] As part of its operational definition of the pH scale.PH 6 Applications Water has a pH of pKw/2. The functioning of the oxygen-transport enzyme hemoglobin is affected by pH in a process known as the Root effect. an alternative series of buffers based on artificial seawater was developed. For example. at concentration 1‚mol dm•3 has a pH of 0. H+ + SO42• ƒ HSO4•. The juice of citrus fruits is acidic because of the presence of citric acid. since the ionic strength differences cause changes in electrode potential. The total scale was defined using a medium containing sulfate ions. the pH of pure water at 50‚ƒC is 6. When a base. often denoted as pHT. has a pH of 14. measured pH values will lie mostly in the range 0 to 14. To resolve this problem. The pH of pure water decreases with increasing temperatures. Thus. including hibiscus. such as sodium hydroxide. that water that has been exposed to air is mildly acidic. and several distinct pH scales exist in chemical oceanography. a difference of one pH unit is equivalent to a tenfold difference in hydrogen ion concentration.55. such that the total scale includes the effect of both protons (free hydrogen ions) and hydrogen sulfate ions: [H+]T = [H+]F + [HSO4•] . and. red cabbage (anthocyanin) and red wine. The pH of an aqueous solution of a salt such as sodium chloride is slightly different from that of pure water. or alkali. as a consequence. This is because the hydrogen and hydroxide ions' activity is dependent on ionic strength. However. Other carboxylic acids occur in many living systems. and the new pH scale is referred to as the total scale. When an acid is dissolved in water. These solutions have a relatively low ionic strength (~0. A solution of a strong alkali. the IUPAC defines a series of buffer solutions across a range of pH values (often denoted with NBS or NIST designation). This new series resolves the problem of ionic strength differences between samples and the buffers. such as ATP. such as hydrochloric acid. The state of protonation of phosphate derivatives.

Because of the relative unimportance of the fluoride ion. it is difficult to estimate KS* in seawater. differences that are much larger than the accuracy of pH measurements typically required. sulfate ions occur at much greater concentrations (> 400 times) than those of fluoride.1 The pH of different cellular compartments. in principle making it a simpler representation of hydrogen ion concentration.5 pH Granules of chromaffin cells 5. body fluids. often denoted pHF. the total and seawater scales differ only very slightly. In seawater.0 6. which means an acid overload in the body. Only [H+]T can be determined. Another scale. the three seawater pH scales differ in their values by up to 0. the free scale. The following three equations summaries 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.81 7. The most common disorder in acid-base homeostasis is acidosis. and organs is usually tightly regulated in a process called acid-base homeostasis. limiting the utility of the otherwise more straightforward free scale. in relation to the ocean's carbonate system.45 7.* Alkalosis is the opposite condition. therefore [H+]F must be estimated using the [SO42•] and the stability constant of HSO4•. [H+]F = [H+]T • [HSO4•] = [H+]T ( 1 + [SO42•] / KS* )•1 7 Living systems pH in living systems Compartment Gastric acid Lysosomes 1 4. the advantage of considering this additional complexity is dependent upon the abundance of fluoride in the medium. known as the seawater scale. Since it omits consideration of sulfate and fluoride ions.2 7. in particular. generally defined by pH falling below 7. the free scale is significantly different from both the total and seawater scales. omits this consideration and focuses solely on [H+]F. KS*: However. As a consequence.PH An alternative scale. Resulting in the following expression for [H+]SWS: [H+]SWS = [H+]F + [HSO4•] + [HF] However.34€7. for most practical purposes.5 8. with blood .5 Human skin Urine Pure H2O at 37 ƒC Cytosol Cerebrospinal fluid (CSF) Blood Mitochondrial matrix Pancreas secretions 5.5 7. H+ + F• ƒ HF. for instance.12 pH units. takes account of a further protonation relationship between hydrogen ions and fluoride ions. often denoted pHSWS.5 6. the difference between the total and seawater scales is very small.35.

A complicating factor is that water itself is a weak acid and a weak base.365. The pH of a 0. The p[OH] value of a 0. for example. This equilibrium needs to be taken into account at high pH and when the solute concentration is extremely low. Hydrochloric acid (HCl) is an example of a strong acid.01). that is. Kw has a value of about 10•14 at 25‚ƒC. that is. 8 Calculations of pH The calculation of the pH of a solution containing acids and/or bases is an example of a chemical speciation calculation.3. The pH of a solution containing a weak acid requires the solution of a quadratic equation. Electrical charges are omitted from subsequent equations for the sake of generality . Consider. This value is often referred to as physiological pH in biology and medicine. From the definition of p[OH] above. so pure water has a pH of about 7. an acid dissociation constant is defined as follows.89 results. NaOH. Weak acids and bases A weak acid or the conjugate acid of a weak base can be treated using the same formalism. The complexity of the procedure depends on the nature of the solution. p[OH] = 2. for practical purposes. Acid: Base: First. that is. For solutions of sodium hydroxide at higher concentrations the self-ionization equilibrium must be taken into account. This is clearly wrong as an acid solution should have a pH of less than 7. Strong acids and bases Strong acids and bases are compounds that. Treating the system as a mixture of hydrochloric acid and the amphoteric substance water.01M solution of NaOH is equal to •log10(0. Under normal circumstances this means that the concentration of hydrogen ions in acidic solution can be taken to be equal to the concentration of the acid. The pH of a solution containing a weak base may require the solution of a cubic equation. a mathematical procedure for calculating the concentrations of all chemical species that are present in the solution. Kw defined as where [H+] stands for the concentration of the aquated hydronium ion and [OH-] represents the concentration of the hydroxide ion. are completely dissociated in water. It dissociates according to the equilibrium with a dissociation constant. Self-ionization must also be considered when concentrations are extremely low. For strong acids and bases no calculations are necessary except in extreme situations. Sodium hydroxide. The pH of blood is usually slightly basic with a value of pH 7.01).PH pH being excessively high.01M solution of HCl is equal to •log10(0. a pH of 6. The simple procedure given above would suggest that it has a pH of 7. Plaque can create a local acidic environment that can result in tooth decay by demineralization. a solution of hydrochloric acid at a concentration of 5„10•8M. is an example of a strong base. pH = 2. The general case requires the solution of a set of non-linear simultaneous equations. Enzymes and other proteins have an optimum pH range and can become inactivated or denatured outside this range. The pH is then equal to minus the logarithm of the concentration value. this means that the pH is equal to about 12.

Solution of this quadratic equation gives the hydrogen ion concentration and hence p[H] or. Two additional equations are needed. write down the mass-balance equations for each reagent Note that there are no approximations involved in these equations. This is satisfactory for simple cases like this one. General method Some systems. the solution of these equations is not straightforward. Much more complicated expressions are required if activities are to be used. When an acid is dissolved in water CA = CH = Ca. Since addition of hydroxide reduces the hydrogen ion concentration. …. there are now three equations in three unknowns. except that each stability constant is defined as a quotient of concentrations. and the hydroxide ion concentration is constrained by the self-ionization equilibrium to be equal to In this case the resulting equation in [H] is a cubic equation. For example. [A]. the concentration of the acid. Next. pH. Together with the equation defining Ka.PH and its value is assumed to have been determined by experiment. are amenable to spreadsheet calculations. With three or more reagents or when many complexes are formed with general formulae such as ApBqHr the following general method can be used to calculate the pH of a solution. pKa = 4. 9 C stands for analytical concentration. After some further algebraic manipulation an equation in the hydrogen ion concentration may be obtained. for details see chemical equilibrium#Computer programs. and because concentrations may range over many powers of 10. pH = 3. each equilibrium is characterized by and equilibrium constant. Step 3: Solve the quadratic equation. The calculation of . . This being so.01M solution of benzoic acid. However.11 For alkaline solutions an additional term is added to the mass-balance equation for hydrogen. [B] and [H]. with three reagents. There may be more than three reagents. One way to provide them is to apply the law of mass conservation in terms of the two "reagents" H and A. Because the equations are non-linear. but is more difficult to apply to more complicated cases as those below. when CA „ CH.19? Step 1: Step 2: Set up the quadratic equation. what is the pH of a 0. that is. This procedure is illustrated in an ICE table which can also be used to calculate the pH when some additional (strong) acid or alkali has been added to the system. [HA]. There are 3 non-linear simultaneous equations in the three unknowns. more loosely. In some texts one mass balance equation is replaced by an equation of charge balance. there are three unknown concentrations. such as with polyprotic acids. many computer programs are available which can be used to perform these calculations. [H+] and [A-] to determine by calculation. so [A] = [H]. For example. not activities.

International Organization for Standardization. (2001) CO2 in seawater: equilibrium.pdf) € Red Cabbage pH Indicator ( [2] Sorensen. S. 1992.. S. Amsterdam. Roger G. Enzymstudien. L. Krossing. Two other publications appeared in 1909 one in French and one in Danisch [3] Quantities and units € Part 8: Physical chemistry and molecular physics. Netherlands ISBN 0-444-50946-1 External links € The pH Scale (http://www. Section 13. "Determination of pH" [5] . P. Annex C (normative): pH. 1909.uwaterloo.. Acid-base Equilibria and Calculations (http://www.. kinetics... using this formalism. c1xacid2. and Wolf-Gladrow. Section 13. Int.html) € Chem1 Virtual Textbook.19 The glass electrode [6] Himmel.PH hydrogen ion concentrations.. 1973. K.html) . isotopes. D. I. 2010. Leito. pp. •ber die Messung und die Bedeutung der Wasserstoffionenkonzentration bei enzymatischen Prozessen. Determination of pH: theory and practice. [4] .htm) € Food and Foodstuff . I. Biochem. 10 References [1] Bates. 49. vol. 131€304. 6885€6888.engineeringtoolbox.about. E.pH Values (http://www.23.chem1. [7] Zeebe. II. "A Unified pH Scale for all Phases" Angew. Elsevier Science is a key element in the determination of equilibrium constants by potentiometric titration. Goll. D. Ed. 21. Zeitschr.

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