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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.
A solution containing the analyte, A, in the presence of some conductive buffer. If an electrolytic potential is applied to the solution through a working electrode, then the measured current depends (in part) on the concentration of the analyte. Measurement of this current can be used to determine the concentration of the analyte directly; this is a form of amperometry. However, the difficulty is that the measured current depends on several other variables, and it is not always possible to control all of them adequately. This limits the precision of direct amperometry.
If the potential applied to the working electrode is sufficient to reduce the analyte, then the concentration of analyte close to the working electrode will decrease. More of the analyte will slowly diffuse into the volume of solution close to the working electrode, restoring the concentration. If the potential applied to the working electrode is great enough (an overpotential), then the concentration of analyte next to the working electrode will depend entirely on the rate of diffusion. In such a case, the current is said to be diffusion limited. As the analyte is reduced at the working electrode, the concentration of the analyte in the whole solution will very slowly decrease; this depends on the size of the working electrode compared to the volume of the solution.
What happens if some other species which reacts with the analyte (the titrant) is added? (For instance, chromate ions can be added to oxidize lead ions.) After a small quantity of the titrant (chromate) is added, the concentration of the analyte (lead) has decreased due to the reaction with chromate. The current from the reduction of lead ion at the working electrode will decrease. The addition is repeated, and the current decreases again. A plot of the current against volume of added titrant will be a straight line.
After enough titrant has been added to react completely with the analyte, the excess titrant may itself be reduced at the working electrode. Since this is a different species with different diffusion characteristics (and different half-reaction), the slope of current versus added titrant will have a different slope after the equivalence point. This change in slope marks the equivalence point, in the same way that, for instance, the sudden change in pH marks the equivalence point in an acid–base titration.
The electrode potential may also be chosen such that the titrant is reduced, but the analyte is not. In this case, the presence of excess titrant is easily detected by the increase in current above background (charging) current.
The chief advantage over direct amperometry is that the magnitude of the measured current is of interest only as an indicator. Thus, factors that are of critical importance to quantitative amperometry, such as the surface area of the working electrode, completely disappear from amperometric titrations.
The chief advantage over other types of titration is the selectivity offered by the electrode potential, as well as by the choice of titrant. For instance, lead ion is reduced at a potential of -0.60 V (relative to the saturated calomel electrode), while zinc ions are not; this allows the determination of lead in the presence of zinc. Clearly this advantage depends entirely on the other species present in the sample.[ citation needed ]
Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, with the potential difference as an outcome of a particular chemical change, or vice versa. These reactions involve electrons moving via an electronically-conducting phase between electrodes separated by an ionically conducting and electronically insulating electrolyte.
Titration is a common laboratory method of quantitative chemical analysis to determine the concentration of an identified analyte. A reagent, termed the titrant or titrator, is prepared as a standard solution of known concentration and volume. The titrant reacts with a solution of analyte to determine the analyte's concentration. The volume of titrant that reacted with the analyte is termed the titration volume.
Karl Fischer titration is a classic titration method in chemical analysis 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.
An acid–base titration is a method of quantitative analysis for determining the concentration of an acid or base by exactly neutralizing it with a standard solution of base or acid having known concentration. A pH indicator is used to monitor the progress of the acid–base reaction. If the acid dissociation constant (pKa) of the acid or base dissociation constant (pKb) of base in the analyte solution is known, its solution concentration (molarity) can be determined. Alternately, the pKa can be determined if the analyte solution has a known solution concentration by constructing a titration curve.
Cyclic voltammetry (CV) is a type of potentiodynamic electrochemical measurement. In a cyclic voltammetry experiment, the working electrode potential is ramped linearly versus time. Unlike in linear sweep voltammetry, after the set potential is reached in a CV experiment, the working electrode's potential is ramped in the opposite direction to return to the initial potential. These cycles of ramps in potential may be repeated as many times as needed. The current at the working electrode is plotted versus the applied voltage to give the cyclic voltammogram trace. Cyclic voltammetry is generally used to study the electrochemical properties of an analyte in solution or of a molecule that is adsorbed onto the electrode.
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. Coulometry is a group of techniques in analytical chemistry. 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.
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.
Voltammetry is a category of electroanalytical methods used in analytical chemistry and various industrial processes. In voltammetry, information about an analyte is obtained by measuring the current as the potential is varied. The analytical data for a voltammetric experiment comes in the form of a voltammogram which plots the current produced by the analyte versus the potential of the working electrode.
Chronoamperometry is an electrochemical technique in which the potential of the working electrode is stepped and the resulting current from faradaic processes occurring at the electrode is monitored as a function of time. The functional relationship between current response and time is measured after applying single or double potential step to the working electrode of the electrochemical system. Limited information about the identity of the electrolyzed species can be obtained from the ratio of the peak oxidation current versus the peak reduction current. However, as with all pulsed techniques, chronoamperometry generates high charging currents, which decay exponentially with time as any RC circuit. The Faradaic current - which is due to electron transfer events and is most often the current component of interest - decays as described in the Cottrell equation. In most electrochemical cells this decay is much slower than the charging decay-cells with no supporting electrolyte are notable exceptions. Most commonly a three electrode system is used. Since the current is integrated over relatively longer time intervals, chronoamperometry gives a better signal to noise ratio in comparison to other amperometric techniques.
A potentiometric sensor is a type of chemical sensor that may be used to determine the analytical concentration of some components of the analyte gas or solution. These sensors measure the electrical potential of an electrode when no current is present.
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.
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 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.
Electroanalytical methods are a class of techniques in analytical chemistry which study an analyte by measuring the potential (volts) and/or current (amperes) in an electrochemical cell containing the analyte. These methods can be broken down into several categories depending on which aspects of the cell are controlled and which are measured. The three main categories are potentiometry, coulometry, and voltammetry.
A Gran plot is a common means of standardizing a titrate or titrant by estimating the equivalence volume or end point in a strong acid-strong base titration or in a potentiometric titration. Such plots have been also used to calibrate glass electrodes, to estimate the carbonate content of aqueous solutions, and to estimate the Ka values of weak acids and bases from titration data.
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.
Amperometry in chemistry is detection of ions in a solution based on electric current or changes in electric current.
A biotransducer is the recognition-transduction component of a biosensor system. It consists of two intimately coupled parts; a bio-recognition layer and a physicochemical transducer, which acting together converts a biochemical signal to an electronic or optical signal. The bio-recognition layer typically contains an enzyme or another binding protein such as antibody. However, oligonucleotide sequences, sub-cellular fragments such as organelles and receptor carrying fragments, single whole cells, small numbers of cells on synthetic scaffolds, or thin slices of animal or plant tissues, may also comprise the bio-recognition layer. It gives the biosensor selectivity and specificity. The physicochemical transducer is typically in intimate and controlled contact with the recognition layer. As a result of the presence and biochemical action of the analyte, a physico-chemical change is produced within the biorecognition layer that is measured by the physicochemical transducer producing a signal that is proportionate to the concentration of the analyte. The physicochemical transducer may be electrochemical, optical, electronic, gravimetric, pyroelectric or piezoelectric. Based on the type of biotransducer, biosensors can be classified as shown to the right.
Total Base Number (TBN) is a measurement of basicity that is expressed in terms of the number of milligrams of potassium hydroxide per gram of oil sample. TBN is an important measurement in petroleum products, and the value varies depending on its application. TBN 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. TBN is typically higher for marine grade lubricants, approximately 15-80 mg KOH/g, as the higher TBN values are designed to increase the operating period under harsh operating conditions, before the lubricant requires replacement.
Electrochemical stripping analysis is a set of analytical chemistry methods based on voltammetry or potentiometry that are used for quantitative determination of ions in solution. Stripping voltammetry have been employed for analysis of organic molecules as well as metal ions. Carbon paste, glassy carbon paste, and glassy carbon electrodes when modified are termed as chemically modified electrodes and have been employed for the analysis of organic and inorganic compounds.