Titration

Titration setup: the titrant drops from the burette into the analyte solution in the flask. An indicator present then changes color permanently at the endpoint. Titration is a common laboratory method of quantitative/chemical analysis that can be used to determine the concentration of a known reactant. Because volume measurements play a key role in titration, it is also known as volumetric analysis. A reagent, called the titrant, of known concentration (a standard solution) and volume is used to react with a solution of the analyte, whose concentration is not known in advance. Using a calibrated burette to add the titrant, it is possible to determine the exact amount that has been consumed when the endpoint is reached. The endpoint is the point at which the titration is complete, as determined by an indicator (see below). This is ideally the same volume as the equivalence point - 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). In the classic strong acid-strong base titration, the endpoint of a titration is the point at which the pH of the reactant is just about equal to 7, and often when the solution permanently changes color due to an indicator. There are however many different types of titrations (see below). Many methods can be used to indicate the endpoint of a reaction; titrations often use visual indicators (the reactant mixture changes colour). In simple acid-base titrations a pH indicator may be used, such as phenolphthalein, which becomes pink when a certain pH (about 8.2) is reached or exceeded. Another example is methyl orange, which is red in acids and yellow in alkali solutions. Not every titration requires an indicator. In some cases, either the reactants or the products are strongly coloured and can serve as the "indicator". For example, an oxidation-reduction titration using potassium permanganate (pink/purple) as the titrant

does not require an indicator. When the titrant is reduced, it turns colourless. After the equivalence point, there is excess titrant present. The equivalence point is identified from the first faint pink color that persists in the solution being titrated. Due to the logarithmic nature of the pH curve, the transitions are, in general, extremely sharp; and, thus, a single drop of titrant just before the endpoint can change the pH significantly leading to an immediate colour change in the indicator. There is a slight difference between the change in indicator color and the actual equivalence point of the titration. This error is referred to as an indicator error, and it is indeterminate.

History and etymology

The word "titration" comes from the Latin word titalus, meaning inscription or title. The French word titre, also from this origin, means rank. Titration, by definition, is the determination of rank or concentration of a solution with respect to water with a pH of 7 (which is the pH of pure water). The origins of volumetric analysis are in late-18th-century French chemistry. Francois Antoine Henri Descroizilles developed the first burette (which looked more like a graduated cylinder) in 1791. Joseph Louis Gay-Lussac developed an improved version of the burette that included a side arm, and coined the terms "pipette" and "burette" in an 1824 paper on the standardization of indigo solutions. A major breakthrough in the methodology and popularization of volumetric analysis was due to Karl Friedrich Mohr, who redesigned the burette by placing a clamp and a tip at the bottom, and wrote the first textbook on the topic, Lehrbuch der chemisch-analytischen Titrirmethode (Textbook of analytical-chemical titration methods), published in 1855.[1]

Preparing a sample for titration

In a titration, both titrant and analyte are required to be aqueous, or in a solution form. If the sample is not a liquid or solution, the samples must be dissolved. If the analyte is very concentrated in the sample, it might be useful to dilute the sample. Although the vast majority of titrations are carried out in aqueous solution, other solvents such as glacial acetic acid or ethanol (in petrochemistry) are used for special purposes. A measured amount of the sample can be given in the flask and then be dissolved or diluted. The mathematical result of the titration can be calculated directly with the measured amount. Sometimes the sample is dissolved or diluted beforehand, and a measured amount of the solution is used for titration. In this case the dissolving or diluting must be done accurately with a known coefficient because the mathematical result of the titration must be multiplied with this factor. Many titrations require buffering to maintain a certain pH for the reaction. Therefore, buffer solutions are added to the reactant solution in the flask.

Some titrations require "masking" of a certain ion. This can be necessary when two reactants in the sample would react with the titrant and only one of them must be analysed, or when the reaction would be disturbed or inhibited by this ion. In this case another solution is added to the sample, which "masks" the unwanted ion (for instance by a weak binding with it or even forming a solid insoluble substance with it). Some redox reactions may require heating the solution with the sample and titration while the solution is still hot (to increase the reaction rate).

Procedure
A typical titration begins with a beaker or Erlenmeyer flask containing a precise volume of the reactant and a small amount of indicator, placed underneath a burette containing the reagent. By controlling the amount of reagent added to the reactant, it is possible to detect the point at which the indicator changes colour. As long as the indicator has been chosen correctly, this should also be the point where the reactant and reagent neutralise each other, and, by reading the scale on the burette, the volume of reagent can be measured. As the concentration of the reagent is known, the number of moles of reagent can be calculated (since concentration = moles / volume). Then, from the chemical equation involving the two substances, the number of moles present in the reactant can be found. Finally, by dividing the number of moles of reactant by its volume, the concentration is calculated.

Titration curves

A typical titration curve of a diprotic acid, oxalic acid, titrated with a strong base, sodium hydroxide. Each of the two equivalence points are visible Titrations are often recorded on titration curves, whose compositions are generally identical: the independent variable is the volume of the titrant, while the dependent variable is the pH of the solution (which changes depending on the composition of the two solutions).

The equivalence point is a significant point on the graph (the point at which all of the starting solution, usually an acid, has been neutralized by the titrant, usually a base). It can be calculated precisely by finding the second derivative of the titration curve and computing the points of inflection (where the graph changes concavity); however, in most cases, simple visual inspection of the curve will suffice (in the curve given to the right, both equivalence points are visible, after roughly 15 and 30 mL of NaOH solution has been titrated into the oxalic acid solution.) To calculate the pKa values, one must find the volume at the half-equivalence point, that is where half the amount of titrant has been added to form the next compound (here, sodium hydrogen oxalate, then disodium oxalate). Halfway between each equivalence point, at 7.5 mL and 22.5 mL, the pH observed was about 1.5 and 4, giving the pKa values. In monoprotic acids, the point halfway between the beginning of the curve (before any titrant has been added) and the equivalence point is significant: at that point, the concentrations of the two species (the acid and conjugate base) are equal. Therefore, the Henderson-Hasselbalch equation can be solved in this manner:

Therefore, one can easily find the acid dissociation constant of the monoprotic acid by finding the pH of the point halfway between the beginning of the curve and the equivalence point, and solving the simplified equation. In the case of the sample curve, the Ka would be approximately 1.7810-5 from visual inspection (the actual Ka2 is 1.7105 ) For polyprotic acids, calculating the acid dissociation constants is only marginally more difficult: the first acid dissociation constant can be calculated the same way as it would be calculated in a monoprotic acid. The second acid dissociation constant, however, is the point halfway between the first equivalence point and the second equivalence point (and so on for acids that release more than two protons, such as phosphoric acid).

Types of titrations
Titrations can be classified by the type of reaction. Different types of titration reaction include:

Acid-base titrations are based on the neutralization reaction between the analyte and an acidic or basic titrant. These most commonly use a pH indicator, a pH meter, or a conductance meter to determine the endpoint. Redox titrations are based on an oxidation-reduction reaction between the analyte and titrant. These most commonly use a potentiometer or a redox indicator to determine the endpoint. Frequently either the reactants or the titrant have a colour intense enough that an additional indicator is not needed. Complexometric titrations are based on the formation of a complex between the analyte and the titrant. The chelating agent EDTA is very commonly used to titrate metal ions in solution. These titrations generally require specialized indicators that form weaker complexes with the analyte. A common example is Eriochrome Black T for the titration of calcium and magnesium ions. A form of titration can also be used to determine the concentration of a virus or bacterium. The original sample is diluted (in some 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. This value, the titre, may be based on TCID50, EID50, ELD50, LD50 or pfu. This procedure is more commonly known as an assay.

Measuring the endpoint of a titration

Different methods to determine the endpoint include:

pH indicator: This is a substance that changes colour in response to a chemical change. An acid-base indicator (e.g., phenolphthalein) changes colour depending on the pH. Redox indicators are also frequently used. A drop of indicator solution is added to the titration at the start; when the colour changes the endpoint has been reached. A potentiometer can also be used. This is an instrument that measures the electrode potential of the solution. These are used for titrations based on a redox reaction; the potential of the working electrode will suddenly change as the endpoint is reached. pH meter: This is a potentiometer that uses an electrode whose potential depends on the amount of H+ ion present in the solution. (This is an example of an ionselective electrode. This allows the pH of the solution to be measured throughout the titration. At the endpoint, there will be a sudden change in the measured pH. It can be more accurate than the indicator method, and is very easily automated. Conductance: The conductivity of a solution depends on the ions that are present in it. During many titrations, the conductivity changes significantly. (For instance, during an acid-base titration, the H+ and OH- ions react to form neutral H2O. This changes the conductivity of the solution.) The total conductance of the solution

depends also on the other ions present in the solution (such as counter ions). Not all ions contribute equally to the conductivity; this also depends on the mobility of each ion and on the total concentration of ions (ionic strength). Thus, predicting the change in conductivity is harder than measuring it. Colour change: In some reactions, the solution changes colour without any added indicator. This is often seen in redox titrations, for instance, when the different oxidation states of the product and reactant produce different colours. Precipitation: If the reaction forms a solid, then a precipitate will form during the titration. A classic example is the reaction between Ag+ and Cl- to form the very insoluble salt AgCl. This usually makes it difficult to determine the endpoint precisely. As a result, precipitation titrations often have to be done as "back" titrations (see below). An isothermal titration calorimeter uses the heat produced or consumed by the reaction to determine the endpoint. This is important in biochemical titrations, such as the determination of how substrates bind to enzymes. Thermometric titrimetry is an extraordinarily versatile technique. This is differentiated from calorimetric titrimetry by the fact that the heat of the reaction (as indicated by temperature rise or fall) is not used to determine the amount of analyte in the sample solution. Instead, the endpoint is determined by the rate of temperature change. Spectroscopy can be used to measure the absorption of light by the solution during the titration, if the spectrum of the reactant, titrant or product is known. The relative amounts of the product and reactant can be used to determine the endpoint.

Back Titration
The term back titration is used when a titration is done "backwards": instead of titrating the original analyte, one adds a known excess of a standard reagent to the solution, then titrates the excess. A back titration is useful if the endpoint of the reverse titration is easier to identify than the endpoint of the normal titration. They are also useful if the reaction between the analyte and the titrant is very slow.

Particular uses

Titrations in the petrochemical or food industry to define oils, fats or biodiesel and similar substances. An example procedure for all three can be found here: [1]. o Acid number: an acid-base titration with colour indicator is used to determine the free fatty acid content. See also: pH of fatty acids. o Iodine number: a redox titration with colour indication, which indicates the amount of unsaturated fatty acids. o Saponification value: an acid-base back titration with colour indicator or potentiometric to get a hint about the average chain length of fatty acids in a fat.

References
1. ^ Louis Rosenfeld. Four Centuries of Clinical Chemistry. CRC Press, 1999, p. 72-75.

Titrage

Montage d'un titrage La titrimtrie ou titrage est une technique de dosage utilise en chimie analytique afin de dterminer la concentration d'une espce chimique en solution (ou titre d'une solution). La mthode de titrage la plus utilise est la volumtrie ou titrage volumtrique. Elle consiste utiliser une solution de concentration connue (appele titrant) afin de neutraliser une espce contenue dans la solution inconnue. Les titrages volumtriques les plus rpandus sont les titrages acide-base : L'oprateur fait couler goutte goutte un acide dans un volume dtermin de base. Ainsi les ractifs ragissent mol mol. Le titrage base-acide est aussi possible. Le point de neutralisation est connu grce un indicateur color ajout dans la solution inconnue (Cet indicateur change de couleur au moment de la neutralisation) ou grce une variation du potentiel ou du pH (mesur au moyen d'une lectrode trempant dans la solution inconnue).

Matriel ncessaire [modifier]

Montage pour faire un titrage. La burette contient une solution titrante, et l'erlen la solution titrer On utilise en gnral une burette gradue quand le titrage est manuel ou un titrimtre automatique quand on souhaite amliorer la rptabilit et la traabilit. Le volume de l'chantillon est prlev au moyen d'une pipette de volume dtermin et est plac dans un erlenmeyer. La burette contient toujours la solution de ractif titrante dont on connat la concentration. La burette donne le volume vers de solution titrante et donc nous donnera le point l'quivalence. La solution doser sera toujours dans un becher ou autre rcipient propre, elle sera en volume exactement connu.

Titrage en solution aqueuse [modifier]

Pour raliser un titrage, on ralise une raction chimique o l'espce en solution ragit avec une autre substance. L'espce doser est appele ractif titr et la substance ajoute est appele ractif titrant Il est possible de raliser un titrage conductimtrique (pour une raction acido-basique), un titrage colorimtrique, un titrage pH-mtrique, ...

Les titrages pH-mtrique [modifier]

Dosage d'un acide fort par une base faible en prsence d'un indicateur color. Ce type de titrage est ralisable uniquement avec des acides et des bases, faible ou fort, et sous prsence d'un PH-mtre ou d'un indicateur de pH colore.

Titrage d'un acide fort par une base forte [modifier]

En solution, les acides forts comme l'acide chlorhydrique sont totalement dissocis et donnent des ions des ions . De mme, les bases fortes se dissocient totalement pour librer et ragissent de la faon suivante: (Voici l'quation gnrale de neutralisation) Au volume l'quivalence tous les ions H3O + et OH ont ragit, la seule raction qui se produit est celle de l'autoprotolyse de l'eau. Le pH est alors gal 7. L'quivalence est indique soit par un indicateur de pH, soit indirectement par une courbe reprsentant le pH en fonction du volume de base vers. Vous devez pour cela relever les valeurs du PHmtre pour chaque mL de solution verse. Quand le pH commence augmenter de faon significative, versez alors 0,2 ml de solution entre chaque mesure de pH une fois que le pH sera redevenu relativement stable reprenez une mesure de pH tous les ml En traant la courbe du pH en fonction du volume de base verse, ont obtient la courbe reprsente comme sur le dessin anim. Pour retrouver le volume l'quivalence, vous devez tracer les tangentes aux deux points d'inflexion ( l o la courbe change de direction). Les tangentes doivent tre parallles. Tracer la perpendiculaire ces deux droites, puis grce un compas, tracer la mdiatrice de la perpendiculaire. La mdiatrice doit tre parallle aux tangentes . Le volume l'quivalence est l'endroit o la mdiatrice et la courbe se rencontrent, pour un pH de 7 . . Les ions

Les titrages colorimtriques [modifier]

Article dtaill : titrage colorimtrique.

Les titrages conductimtriques [modifier]

Un titrage conductimtrique utilise la capacit des ions conduire le courant lectrique dans un milieu aqueux, on mesure alors la conductance de la solution grce une lectrode. Comme chaque ion conduit le courant diffremment, la conductance varie pendant le dosage. Cette notion est directement lie avec la concentration des ions prsents. Par exemple : L'ion H3O + conduit mieux le courant que l'ion OH . Si vous faites ragir les ions H3O + , la conductance de la solution va baisser car ces ions disparaissent ( la concentration des ions H3O + diminue ) .Puis si vous continuez le titrage au-del du point a l'quivalence, la conductance va monter, car les ions OH seront de plus en plus nombreux,(la concentration des ions OH augmente). En relevant les valeurs indiques par le conductimtre, on peut tracer la droite de la conductance en fonction du volume vers. Il se dessine alors deux droites adjacentes, en forme de V.Le point adjacent indique le volume l'quivalence.

Calculs [modifier]
Le but d'un titrage est de trouver la concentration en un lment donn. Il existe pour cela deux moyens possibles : par le calcul et par un tableau d'avancement. Dans les deux cas il faut connatre l'quation bilan de la raction.

Mthode mathmatique [modifier]

A l'quivalence, il y a eu autant de moles de ractif A que de ractif B.

donc

Avec :

: concentration de la solution connue (titrant) : volume de titrant coul en ml : concentration de la solution inconnue : volume d'chantillon utilis en ml

Cette formule est gnrale quels que soient les coefficients (ou nombres) stoechiomtriques. En raisonnant avec les concentrations alors les coefficients stoechiomtriques interviennent.

Tableau d'avancement [modifier]

Le bilan de la raction s'crit comme ceci :

Etat initial Etat intermdiaire Etat Final Au dbut du titrage, (quand vous n'avez encore rien vers), vous n'avez que des ractifs et aucun produit de raction. Au fur et mesure que votre raction se droule, une quantit x de ractif disparat, alors qu'en mme temps une quantit x de produit apparat. C'est l'application de la loi de lavoisier. A la fin du titrage, c'est--dire quand un de vos ractifs a totalement disparu (celui se trouvant dans votre erlen) vous avez atteint l'avancement maximal, votre raction ne peut pas aller plus loin. A ce moment l

donc

Ce tableau permet de comprendre ce qui ce passe pendant la raction et de ne pas vous tromper avec les coefficients. En effet vous avez juste les reporter devant le X . Normalement quand vous avez de l'eau dans votre raction vous devez crire "en excs" (vous avez toujours plus d'eau qu'il n'en faut pour que la raction se droule)

Calcul d'un excs [modifier]

Au dpart la solution titre est en excs. Aprs l'quivalence, c'est la solution titrante qui est en excs. Pour une raction acido-basique, l'acide est limitant au dbut et pour une oxydo-rduction, c'est l'oxydant qui est limitant avant l'quivalence. Un excs est une partie des ractifs qui ne ragit pas pendant une raction chimique et qui se retrouve donc dans les produits de la raction. On peut doser l'excs de ractif avec une deuxime raction chimique : c'est un dosage en retour.

Rappels [modifier]

Le nombre de mole correspond la quantit de matire d'une espce chimique. La masse molaire d'un lment est la quantit de matire qu'il faut pour avoir une mole de cet lement. Exemple : pour avoir 1 mole. La masse est la quantit de matire pese. , il faut 12 grammes de carbone

La concentration est la quantit de matire contenue dans un litre de solution. Elle est exprime en mol/L ou en g/L.

C = n / V ou C = m / V