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A burette and Erlenmeyer flask (conical flask) being used for an acid-base titration. Acid and Base Titration.jpg
A burette and Erlenmeyer flask (conical flask) being used for an acid–base titration.

Titration (also known as titrimetry [1] and volumetric analysis) is a common laboratory method of quantitative chemical analysis to determine the concentration of an identified analyte (a substance to be analyzed). A reagent, termed the titrant or titrator, [2] is prepared as a standard solution of known concentration and volume. The titrant reacts with a solution of analyte (which may also be termed the titrand [3] ) to determine the analyte's concentration. The volume of titrant that reacted with the analyte is termed the titration volume.


History and etymology

The word "titration" descends from the French word titrer (1543), meaning the proportion of gold or silver in coins or in works of gold or silver; i.e., a measure of fineness or purity. Tiltre became titre, [4] which thus came to mean the "fineness of alloyed gold", [5] and then the "concentration of a substance in a given sample". [6] In 1828, the French chemist Joseph Louis Gay-Lussac first used titre as a verb (titrer), meaning "to determine the concentration of a substance in a given sample". [7]

Volumetric analysis originated in late 18th-century France. François-Antoine-Henri Descroizilles (fr) developed the first burette (which was similar to a graduated cylinder) in 1791. [8] [9] [10] Gay-Lussac developed an improved version of the burette that included a side arm, and invented the terms "pipette" and "burette" in an 1824 paper on the standardization of indigo solutions. [11] The first true burette was invented in 1845 by the French chemist Étienne Ossian Henry (1798–1873). [12] [13] [14] [15] A major improvement of the method and popularization of volumetric analysis was due to Karl Friedrich Mohr, who redesigned the burette into a simple and convenient form, and who wrote the first textbook on the topic, Lehrbuch der chemisch-analytischen Titrirmethode (Textbook of analytical chemistry titration methods), published in 1855. [16] [17]


Analysis of soil samples by titration. Titration for Soil.JPG
Analysis of soil samples by titration.

A typical titration begins with a beaker or Erlenmeyer flask containing a very precise amount of the analyte and a small amount of indicator (such as phenolphthalein) placed underneath a calibrated burette or chemistry pipetting syringe containing the titrant. [18] Small volumes of the titrant are then added to the analyte and indicator until the indicator changes color in reaction to the titrant saturation threshold, representing arrival at the endpoint of the titration, meaning the amount of titrant balances the amount of analyte present, according to the reaction between the two. Depending on the endpoint desired, single drops or less than a single drop of the titrant can make the difference between a permanent and temporary change in the indicator. [ further explanation needed ]

Preparation techniques

Typical titrations require titrant and analyte to be in a liquid (solution) form. Though solids are usually dissolved into an aqueous solution, other solvents such as glacial acetic acid or ethanol are used for special purposes (as in petrochemistry, which specializes in petroleum.) [19] Concentrated analytes are often diluted to improve accuracy.

Many non-acid–base titrations require a constant pH during the reaction. Therefore, a buffer solution may be added to the titration chamber to maintain the pH. [20]

In instances where two reactants in a sample may react with the titrant and only one is the desired analyte, a separate masking solution may be added to the reaction chamber which eliminates the effect of the unwanted ion. [21]

Some reduction-oxidation (redox) reactions may require heating the sample solution and titrating while the solution is still hot to increase the reaction rate. For instance, the oxidation of some oxalate solutions requires heating to 60 °C (140 °F) to maintain a reasonable rate of reaction. [22]

Titration curves

A typical titration curve of a diprotic acid titrated with a strong base. Shown here is oxalic acid titrated with sodium hydroxide. Both equivalence points are visible. Oxalic acid titration grid.svg
A typical titration curve of a diprotic acid titrated with a strong base. Shown here is oxalic acid titrated with sodium hydroxide. Both equivalence points are visible.

A titration curve is a curve in graph the x-coordinate of which represents the volume of titrant added since the beginning of the titration, and the y-coordinate of which represents the concentration of the analyte at the corresponding stage of the titration (in an acid–base titration, the y-coordinate usually represents the pH of the solution). [23]

In an acidbase titration, the titration curve represents the strength of the corresponding acid and base. For a strong acid and a strong base, the curve will be relatively smooth and very steep near the equivalence point. Because of this, a small change in titrant volume near the equivalence point results in a large pH change and many indicators would be appropriate (for instance litmus, phenolphthalein or bromothymol blue).

If one reagent is a weak acid or base and the other is a strong acid or base, the titration curve is irregular and the pH shifts less with small additions of titrant near the equivalence point. For example, the titration curve for the titration between oxalic acid (a weak acid) and sodium hydroxide (a strong base) is pictured. The equivalence point occurs between pH 8-10, indicating the solution is basic at the equivalence point and an indicator such as phenolphthalein would be appropriate. Titration curves corresponding to weak bases and strong acids are similarly behaved, with the solution being acidic at the equivalence point and indicators such as methyl orange and bromothymol blue being most appropriate.

Titrations between a weak acid and a weak base have titration curves which are very irregular. Because of this, no definite indicator may be appropriate and a pH meter is often used to monitor the reaction. [24]

The type of function that can be used to describe the curve is termed a sigmoid function.

Types of titrations

There are many types of titrations with different procedures and goals. The most common types of qualitative titration are acid–base titrations and redox titrations.

Acid–base titration

Methyl orange Acidobazna titracija 004.jpg
Methyl orange
IndicatorColor on acidic sideRange of color change
Color on basic side
Methyl violet Yellow0.0—1.6Violet
Bromophenol blue Yellow3.0—4.6Blue
Methyl orange Red3.1—4.4Yellow
Methyl red Red4.4—6.3Yellow
Litmus Red5.0—8.0Blue
Bromothymol blue Yellow6.0—7.6Blue
Phenolphthalein Colorless8.3—10.0Pink
Alizarin yellow Yellow10.1—12.0Red

Acid–base titrations depend on the neutralization between an acid and a base when mixed in solution. In addition to the sample, an appropriate pH indicator is added to the titration chamber, representing the pH range of the equivalence point. The acid–base indicator indicates the endpoint of the titration by changing color. The endpoint and the equivalence point are not exactly the same because the equivalence point is determined by the stoichiometry of the reaction while the endpoint is just the color change from the indicator. Thus, a careful selection of the indicator will reduce the indicator error. For example, if the equivalence point is at a pH of 8.4, then the phenolphthalein indicator would be used instead of Alizarin Yellow because phenolphthalein would reduce the indicator error. Common indicators, their colors, and the pH range in which they change color are given in the table above. [25] When more precise results are required, or when the reagents are a weak acid and a weak base, a pH meter or a conductance meter are used.

For very strong bases, such as organolithium reagent, metal amides, and hydrides, water is generally not a suitable solvent and indicators whose pKa are in the range of aqueous pH changes are of little use. Instead, the titrant and indicator used are much weaker acids, and anhydrous solvents such as THF are used. [26] [27]

Phenolphthalein, a commonly used indicator in acid and base titration. Faint pink color of Phenolphthalein.jpg
Phenolphthalein, a commonly used indicator in acid and base titration.

The approximate pH during titration can be approximated by three kinds of calculations. Before beginning of titration, the concentration of is calculated in an aqueous solution of weak acid before adding any base. When the number of moles of bases added equals the number of moles of initial acid or so called equivalence point, one of hydrolysis and the pH is calculated in the same way that the conjugate bases of the acid titrated was calculated. Between starting and end points, is obtained from the Henderson-Hasselbalch equation and titration mixture is considered as buffer. In Henderson-Hasselbalch equation the [acid] and [base] are said to be the molarities that would have been present even with dissociation or hydrolysis. In a buffer, can be calculated exactly but the dissociation of HA, the hydrolysis of and self-ionization of water must be taken into account. [28] Four independent equations must be used: [29]

In the equations, and are the moles of acid (HA) and salt (XA where X is the cation), respectively, used in the buffer, and the volume of solution is V. The law of mass action is applied to the ionization of water and the dissociation of acid to derived the first and second equations. The mass balance is used in the third equation, where the sum of and must equal to the number of moles of dissolved acid and base, respectively. Charge balance is used in the fourth equation, where the left hand side represents the total charge of the cations and the right hand side represents the total charge of the anions: is the molarity of the cation (e.g. sodium, if sodium salt of the acid or sodium hydroxide is used in making the buffer). [30]

Redox titration

Redox titrations are based on a reduction-oxidation reaction between an oxidizing agent and a reducing agent. A potentiometer or a redox indicator is usually used to determine the endpoint of the titration, as when one of the constituents is the oxidizing agent potassium dichromate. The color change of the solution from orange to green is not definite, therefore an indicator such as sodium diphenylamine is used. [31] Analysis of wines for sulfur dioxide requires iodine as an oxidizing agent. In this case, starch is used as an indicator; a blue starch-iodine complex is formed in the presence of excess iodine, signalling the endpoint. [32]

Some redox titrations do not require an indicator, due to the intense color of the constituents. For instance, in permanganometry a slight persisting pink color signals the endpoint of the titration because of the color of the excess oxidizing agent potassium permanganate. [33] In iodometry, at sufficiently large concentrations, the disappearance of the deep red-brown triiodide ion can itself be used as an endpoint, though at lower concentrations sensitivity is improved by adding starch indicator, which forms an intensely blue complex with triiodide.

Color of iodometric titration mixture before (left) and after (right) the end point. Iodometric titration mixture.jpg
Color of iodometric titration mixture before (left) and after (right) the end point.

Gas phase titration

Gas phase titrations are titrations done in the gas phase, specifically as methods for determining reactive species by reaction with an excess of some other gas, acting as the titrant. In one common gas phase titration, gaseous ozone is titrated with nitrogen oxide according to the reaction

O3 + NO → O2 + NO2. [34] [35]

After the reaction is complete, the remaining titrant and product are quantified (e.g., by Fourier transform spectroscopy) (FT-IR); this is used to determine the amount of analyte in the original sample.

Gas phase titration has several advantages over simple spectrophotometry. First, the measurement does not depend on path length, because the same path length is used for the measurement of both the excess titrant and the product. Second, the measurement does not depend on a linear change in absorbance as a function of analyte concentration as defined by the Beer–Lambert law. Third, it is useful for samples containing species which interfere at wavelengths typically used for the analyte. [36]

Complexometric titration

Complexometric titrations rely on the formation of a complex between the analyte and the titrant. In general, they require specialized complexometric indicators that form weak complexes with the analyte. The most common example is the use of starch indicator to increase the sensitivity of iodometric titration, the dark blue complex of starch with iodine and iodide being more visible than iodine alone. Other complexometric indicators are Eriochrome Black T for the titration of calcium and magnesium ions, and the chelating agent EDTA used to titrate metal ions in solution. [37]

Zeta potential titration

Zeta potential titrations are titrations in which the completion is monitored by the zeta potential, rather than by an indicator, in order to characterize heterogeneous systems, such as colloids. [38] One of the uses is to determine the iso-electric point when surface charge becomes zero, achieved by changing the pH or adding surfactant. Another use is to determine the optimum dose for flocculation or stabilization. [39]


An assay is a type of biological titration used to determine the concentration of a virus or bacterium. Serial dilutions are performed on a sample in a fixed ratio (such as 1:1, 1:2, 1:4, 1:8, etc.) until the last dilution does not give a positive test for the presence of the virus. The positive or negative value may be determined by inspecting the infected cells visually under a microscope or by an immunoenzymetric method such as enzyme-linked immunosorbent assay (ELISA). This value is known as the titer. [40]

Measuring the endpoint of a titration

Different methods to determine the endpoint include: [41]

An elementary pH meter that can be used to monitor titration reactions. PHmeter basic.JPG
An elementary pH meter that can be used to monitor titration reactions.

Endpoint and equivalence point

Though the terms equivalence point and endpoint are often used interchangeably, they are different terms. Equivalence point is the theoretical completion of the reaction: the volume of added titrant at which the number of moles of titrant is equal to the number of moles of analyte, or some multiple thereof (as in polyprotic acids). Endpoint is what is actually measured, a physical change in the solution as determined by an indicator or an instrument mentioned above. [42]

There is a slight difference between the endpoint and the equivalence point of the titration. This error is referred to as an indicator error, and it is indeterminate. [43] [ self-published source? ]

Back titration

Back titration is a titration done in reverse; instead of titrating the original sample, a known excess of standard reagent is added to the solution, and the excess is titrated. A back titration is useful if the endpoint of the reverse titration is easier to identify than the endpoint of the normal titration, as with precipitation reactions. Back titrations are also useful if the reaction between the analyte and the titrant is very slow, or when the analyte is in a non-soluble solid. [44]

Graphical methods

The titration process creates solutions with compositions ranging from pure acid to pure base. Identifying the pH associated with any stage in the titration process is relatively simple for monoprotic acids and bases. The presence of more than one acid or base group complicates these computations. Graphical methods, [45] such as the equiligraph, [46] have long been used to account for the interaction of coupled equilibria.

Particular uses

A titration is demonstrated to secondary school students. School level titration demonstration.jpg
A titration is demonstrated to secondary school students.

Acid–base titrations

Redox titrations


See also

Related Research Articles

<span class="mw-page-title-main">Analytical chemistry</span> Study of the separation, identification, and quantification of matter

Analytical chemistry studies and uses instruments and methods to separate, identify, and quantify matter. In practice, separation, identification or quantification may constitute the entire analysis or be combined with another method. Separation isolates analytes. Qualitative analysis identifies analytes, while quantitative analysis determines the numerical amount or concentration.

A pH indicator is a halochromic chemical compound added in small amounts to a solution so the pH (acidity or basicity) of the solution can be determined visually or spectroscopically by changes in absorption and/or emission properties. Hence, a pH indicator is a chemical detector for hydronium ions (H3O+) or hydrogen ions (H+) in the Arrhenius model.

<span class="mw-page-title-main">Karl Fischer titration</span> Chemical method to determine trace amounts of water in a sample

In analytical chemistry, Karl Fischer titration is a classic titration method that uses coulometric or volumetric titration to determine trace amounts of water in a sample. It was invented in 1935 by the German chemist Karl Fischer. Today, the titration is done with an automated Karl Fischer titrator.

In environmental chemistry, the chemical oxygen demand (COD) is an indicative measure of the amount of oxygen that can be consumed by reactions in a measured solution. It is commonly expressed in mass of oxygen consumed over volume of solution which in SI units is milligrams per litre (mg/L). A COD test can be used to easily quantify the amount of organics in water. The most common application of COD is in quantifying the amount of oxidizable pollutants found in surface water or wastewater. COD is useful in terms of water quality by providing a metric to determine the effect an effluent will have on the receiving body, much like biochemical oxygen demand (BOD).

A redox titration is a type of titration based on a redox reaction between the analyte and titrant. It may involve the use of a redox indicator and/or a potentiometer. A common example of a redox titration is treating a solution of iodine with a reducing agent to produce iodide using a starch indicator to help detect the endpoint. Iodine (I2) can be reduced to iodide (I) by, say, thiosulfate (S2O2−3), and when all iodine is spent the blue colour disappears. This is called an iodometric titration.

Complexometric titration is a form of volumetric analysis in which the formation of a colored complex is used to indicate the end point of a titration. Complexometric titrations are particularly useful for the determination of a mixture of different metal ions in solution. An indicator capable of producing an unambiguous color change is usually used to detect the end-point of the titration. Complexometric titration are those reactions where a simple ion is transformed into a complex ion and the equivalence point is determined by using metal indicators or electrometrically.

<span class="mw-page-title-main">Acid–base titration</span> Method of chemical quantitative analysis

An acid–base titration is a method of quantitative analysis for determining the concentration of Brønsted-Lowry acid or base (titrate) by neutralizing it using a solution of known concentration (titrant). A pH indicator is used to monitor the progress of the acid–base reaction and a titration curve can be constructed.

In analytical electrochemistry, coulometry determines the amount of matter transformed during an electrolysis reaction by measuring the amount of electricity consumed or produced. It can be used for precision measurements of charge, and the amperes even used to have a coulometric definition. However, today coulometry is mainly used for analytical applications. It is named after Charles-Augustin de Coulomb.

The equivalence point, or stoichiometric point, of a chemical reaction is the point at which chemically equivalent quantities of reactants have been mixed. For an acid-base reaction the equivalence point is where the moles of acid and the moles of base would neutralize each other according to the chemical reaction. This does not necessarily imply a 1:1 molar ratio of acid:base, merely that the ratio is the same as in the chemical reaction. It can be found by means of an indicator, for example phenolphthalein or methyl orange.

<span class="mw-page-title-main">Iodine–starch test</span> Method to detect presence of polysaccharides

The iodine–starch test is a chemical reaction that is used to test for the presence of starch or for iodine. The combination of starch and iodine is intensely blue-black. The interaction between starch and the triiodide anion is the basis for iodometry.

Amperometric titration refers to a class of titrations in which the equivalence point is determined through measurement of the electric current produced by the titration reaction. It is a form of quantitative analysis.

Iodometry, known as iodometric titration, is a method of volumetric chemical analysis, a redox titration where the appearance or disappearance of elementary iodine indicates the end point.

In analytical chemistry, a standard solution is a solution containing a precisely known concentration of an element or a substance. A known mass of solute is dissolved to make a specific volume. It is prepared using a standard substance, such as a primary standard. Standard solutions are used to determine the concentrations of other substances, such as solutions in titration. The concentrations of standard solutions are normally expressed in units of moles per litre, moles per cubic decimetre (mol/dm3), kilomoles per cubic metre (kmol/m3) or in terms related to those used in particular titrations. A simple standard is obtained by the dilution of a single element or a substance in a soluble solvent with which it reacts. A primary standard is a reagent that is extremely pure, stable, has no waters of hydration, and has high molecular weight. Some primary standards of titration of acids include sodium carbonate.

In analytical chemistry, quantitative analysis is the determination of the absolute or relative abundance of one, several or all particular substance(s) present in a sample.

<span class="mw-page-title-main">Thermometric titration</span>

A thermometric titration is one of a number of instrumental titration techniques where endpoints can be located accurately and precisely without a subjective interpretation on the part of the analyst as to their location. Enthalpy change is arguably the most fundamental and universal property of chemical reactions, so the observation of temperature change is a natural choice in monitoring their progress. It is not a new technique, with possibly the first recognizable thermometric titration method reported early in the 20th century. In spite of its attractive features, and in spite of the considerable research that has been conducted in the field and a large body of applications that have been developed; it has been until now an under-utilized technique in the critical area of industrial process and quality control. Automated potentiometric titration systems have pre-dominated in this area since the 1970s. With the advent of cheap computers able to handle the powerful thermometric titration software, development has now reached the stage where easy to use automated thermometric titration systems can in many cases offer a superior alternative to potentiometric titrimetry.

In analytical chemistry, potentiometric titration is a technique similar to direct titration of a redox reaction. It is a useful means of characterizing an acid. No indicator is used; instead the electric potential is measured across the analyte, typically an electrolyte solution. To do this, two electrodes are used, an indicator electrode and a reference electrode. Reference electrodes generally used are hydrogen electrodes, calomel electrodes, and silver chloride electrodes. The indicator electrode forms an electrochemical half-cell with the interested ions in the test solution. The reference electrode forms the other half-cell.

In analytical chemistry, argentometry is a type of titration involving the silver(I) ion. Typically, it is used to determine the amount of chloride present in a sample. The sample solution is titrated against a solution of silver nitrate of known concentration. Chloride ions react with silver(I) ions to give the insoluble silver chloride:

Conductometry is a measurement of electrolytic conductivity to monitor a progress of chemical reaction. Conductometry has notable application in analytical chemistry, where conductometric titration is a standard technique. In usual analytical chemistry practice, the term conductometry is used as a synonym of conductometric titration while the term conductimetry is used to describe non-titrative applications. Conductometry is often applied to determine the total conductance of a solution or to analyze the end point of titrations that include ions.

Base Number (BN) is a measurement of basicity that is expressed in terms of the number of milligrams of potassium hydroxide per gram of oil sample. BN is an important measurement in petroleum products, and the value varies depending on its application. BN generally ranges from 6–8 mg KOH/g in modern lubricants, 7–10 mg KOH/g for general internal combustion engine use and 10–15 mg KOH/g for diesel engine operations. BN is typically higher for marine grade lubricants, approximately 15-80 mg KOH/g, as the higher BN values are designed to increase the operating period under harsh operating conditions, before the lubricant requires replacement.

<span class="mw-page-title-main">Calconcarboxylic acid</span> Chemical compound

Calconcarboxylic acid is an azo dye that is used as an indicator for complexometric titrations of calcium with ethylenediaminetetraacetic acid (EDTA) in the presence of magnesium. Structurally, it is similar to eriochrome blue black R, which is obtained from calconcarboxylic acid by decarboxylation and reaction with sodium hydroxide.


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