Conductometry

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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. [1] Conductometry is often applied to determine the total conductance of a solution or to analyze the end point of titrations that include ions. [2]

Contents

History

Conductive measurements began as early as the 18th century, when Andreas Baumgartner noticed that salt and mineral waters from Bad Gastein in Austria conducted electricity. [3] [4] As such, using conductometry to determine water purity, which is often used today to test the effectiveness of water purification systems, began in 1776. [2] Friedrich Kohlrausch further developed conductometry in the 1860s when he applied alternating current to water, acids, and other solutions. It was also around this time when Willis Whitney, who was studying the interactions of sulfuric acid and chromium sulfate complexes, found the first conductometric endpoint. [3] These finding culminated into potentiometric titrations and the first instrument for volumetric analysis by Robert Behrend in 1883 while titrating chloride and bromide with HgNO3. This development allowed for testing the solubility of salts and hydrogen ion concentration, as well as acid/base and redox titrations. Conductometry was further improved with the development of the glass electrode, which began in 1909. [3] [4]

Titration

Conductometric titration is a type of titration in which the electrolytic conductivity of the reaction mixture is continuously monitored as one reactant is added. The equivalence point is the point at which the conductivity undergoes a sudden change. Marked increase or decrease in conductance are associated with the changing concentrations of the two most highly conducting ions—the hydrogen and hydroxyl ions. [5] The method can be used for titrating coloured solutions or homogeneous suspension (e.g.: wood pulp suspension [5] ), which cannot be used with normal indicators.

Acid-base titrations and redox titrations are often performed in which common indicators are used to locate the end point e.g., methyl orange, phenolphthalein for acid base titrations and starch solutions for iodometric type redox process. However, electrical conductance measurements can also be used as a tool to locate the end point.

Example: titration of an HCl solution with the strong base NaOH. As the titration progresses, the protons are neutralized to form water by the addition of NaOH. For each amount of NaOH added equivalent amount of hydrogen ions is removed. Effectively, the mobile H+ cation is replaced by the less-mobile Na+ ion, and the conductivity of the titrated solution as well as the measured conductance of the cell fall. This continues until the equivalence point is reached, at which one obtains a solution of sodium chloride, NaCl. If more base is added, an increase in conductivity or conductance is observed, since more ions Na+ and OH are being added and the neutralization reaction no longer removes an appreciable amount of H+. Consequently, in the titration of a strong acid with a strong base, the conductance has a minimum at the equivalence point. This minimum can be used, instead of an indicator dye, to determine the endpoint of the titration. The conductometric titration curve is a plot of the measured conductance or conductivity values as a function of the volume of the NaOH solution added. The titration curve can be used to graphically determine the equivalence point.

For reaction between a weak acid and a weak base in the beginning conductivity decreases a bit as the few available H+ ions are used up. Then conductivity increases slightly up to the equivalence point volume, due to contribution of the salt cation and anion.(This contribution in case of a strong acid-strong base is negligible and is not considered there.) After the equivalence point is achieved the conductivity increases rapidly due to the excess OH ions.

Related Research Articles

<span class="mw-page-title-main">Acid</span> Chemical compound giving a proton or accepting an electron pair

An acid is a molecule or ion capable of either donating a proton (i.e. hydrogen ion, H+), known as a Brønsted–Lowry acid, or forming a covalent bond with an electron pair, known as a Lewis acid.

<span class="mw-page-title-main">Titration</span> Laboratory method for determining the concentration of an analyte

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.

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. Normally, the indicator causes the color of the solution to change depending on the pH. Indicators can also show change in other physical properties; for example, olfactory indicators show change in their odor. The pH value of a neutral solution is 7.0 at 25°C (standard laboratory conditions). Solutions with a pH value below 7.0 are considered acidic and solutions with pH value above 7.0 are basic. Since most naturally occurring organic compounds are weak electrolytes, such as carboxylic acids and amines, pH indicators find many applications in biology and analytical chemistry. Moreover, pH indicators form one of the three main types of indicator compounds used in chemical analysis. For the quantitative analysis of metal cations, the use of complexometric indicators is preferred, whereas the third compound class, the redox indicators, are used in redox titrations (titrations involving one or more redox reactions as the basis of chemical analysis).

<span class="mw-page-title-main">Aqueous solution</span> Solution in which the solvent is water

An aqueous solution is a solution in which the solvent is water. It is mostly shown in chemical equations by appending (aq) to the relevant chemical formula. For example, a solution of table salt, or sodium chloride (NaCl), in water would be represented as Na+(aq) + Cl(aq). The word aqueous means pertaining to, related to, similar to, or dissolved in, water. As water is an excellent solvent and is also naturally abundant, it is a ubiquitous solvent in chemistry. Since water is frequently used as the solvent in experiments, the word solution refers to an aqueous solution, unless the solvent is specified.

<span class="mw-page-title-main">Base (chemistry)</span> Type of chemical substance

In chemistry, there are three definitions in common use of the word base, known as Arrhenius bases, Brønsted bases, and Lewis bases. All definitions agree that bases are substances that react with acids, as originally proposed by G.-F. Rouelle in the mid-18th century.

<span class="mw-page-title-main">Neutralization (chemistry)</span> Chemical reaction in which an acid and a base react quantitatively

In chemistry, neutralization or neutralisation is a chemical reaction in which acid and a base react quantitatively with each other. In a reaction in water, neutralization results in there being no excess of hydrogen or hydroxide ions present in the solution. The pH of the neutralized solution depends on the acid strength of the reactants.

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.

<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 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.

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.

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, 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 chemistry, the equivalent concentration or normality (N) of a solution is defined as the molar concentration ci divided by an equivalence factor feq:

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:

<span class="mw-page-title-main">Conductivity (electrolytic)</span> Measure of the ability of a solution containing electrolytes to conduct electricity

Conductivity of an electrolyte solution is a measure of its ability to conduct electricity. The SI unit of conductivity is Siemens per meter (S/m).

Cerimetry or cerimetric titration, also known as cerate oximetry, is a method of volumetric chemical analysis developed by Ion Atanasiu. It is a redox titration in which an iron(II)–1,10-phenanthroline complex (ferroin) color change indicates the end point. Ferroin can be reversibly discolored in its oxidized form upon titration with a Ce4+ solution. The use of cerium(IV) salts as reagents for volumetric analysis was first proposed in the middle of 19th century, but systematic studies did not start until about 70 years later. Standard solutions can be prepared from different Ce4+ salts, but often cerium sulfate is chosen.

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.

<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.

References

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  4. 1 2 Stock, T., "A Short Course on the History of Analytical Chemistry and the Related Sciences". Journal of Chemical Education, 1977, 54, 635-637.
  5. 1 2 Katz et al., 1984 S. Katz, R.P. Beatson and A.M. Scallan, The determination of strong and weak acidic groups in sulfite pulps, Svensk Paperstidn. 6 (1984), pp. 48–53.