Permanganometry

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Permanganometry is one of the techniques used in chemical quantitative analysis. It is a redox titration that involves the use of permanganates to measure the amount of analyte present in unknown chemical samples. [1] It involves two steps, namely the titration of the analyte with potassium permanganate solution and then the standardization of potassium permanganate solution with standard sodium oxalate solution. The titration involves volumetric manipulations to prepare the analyte solutions. [2]

Permanganometry allows the detection and estimation of the quantitative presence of various chemical species, such as iron(II), manganese(II), oxalate, nitrite, and hydrogen peroxide.

Reaction

Depending on the conditions in which the titration is performed, the manganese is reduced from an oxidation of +7 to +2, +4, or +6.

In most cases, permanganometry is performed in a very acidic solution in which the following electrochemical reaction occurs: [3]

MnO
4
+ 8 H+ + 5 e → Mn2+ + 4 H2O; E° = +1.51 V [4]

which shows that KMnO4 (in an acidic medium) is a very strong oxidizing agent, able to oxidize Fe 2+ (E°Fe3+/Fe2+ = +0.77 V), Sn 2+ (E°Sn4+/Sn2+ = +0.2 V), and even Cl (E°Cl2/Cl = +1.36 V).

In weak acidic medium MnO
4
can not accept 5 electrons to form Mn2+. Instead, it accepts only 3 electrons and forms solid MnO2 by the following reaction:

MnO
4
+ 4 H+ + 3 e → MnO2 + 2 H2O; E° = +1.69 V

In a strongly basic solution, with the concentration c(NaOH) >1 mol dm−3, only one electron is accepted to produce manganate:

MnO
4
+ eMnO2−
4
; E° = +0.56 V [5]

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Electrochemistry is the branch of physical chemistry that studies the relationship between electricity, as a measurable and quantitative phenomenon, and identifiable chemical change, with either electricity considered an outcome of a particular chemical change or vice versa. These reactions involve electric charges moving between electrodes and an electrolyte. Thus electrochemistry deals with the interaction between electrical energy and chemical change.

Titration 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.

Redox chemical reaction in which oxidation states of atoms are changed

Redox is a type of chemical reaction in which the oxidation states of atoms are changed. Redox reactions are characterized by the actual or formal transfer of electrons between chemical species, most often with one species undergoing oxidation while another species undergoes reduction. The chemical species from which the electron is removed is said to have been oxidized, while the chemical species to which the electron is added is said to have been reduced. In other words:

A reducing agent is an element or compound that loses an electron to an electron recipient in a redox chemical reaction.

Oxidizing agent Chemical compound used to oxidize another substance in a chemical reaction

In chemistry, an oxidizing agent, or oxidising agent (oxidiser) is a substance that has the ability to oxidize other substances — in other words to accept their electrons. Common oxidizing agents are oxygen, hydrogen peroxide and the halogens.

Manganese dioxide

Manganese(IV) oxide is the inorganic compound with the formula MnO
2
. This blackish or brown solid occurs naturally as the mineral pyrolusite, which is the main ore of manganese and a component of manganese nodules. The principal use for MnO
2
is for dry-cell batteries, such as the alkaline battery and the zinc-carbon battery. MnO
2
is also used as a pigment and as a precursor to other manganese compounds, such as KMnO
4
. It is used as a reagent in organic synthesis, for example, for the oxidation of allylic alcohols. MnO
2
is α polymorph that can incorporate a variety of atoms in the "tunnels" or "channels" between the manganese oxide octahedra. There is considerable interest in α-MnO
2
as a possible cathode for lithium ion batteries.

Potassium permanganate

Potassium permanganate is an inorganic compound with the chemical formula KMnO4 and composed of K+ and MnO
4
. It is a purplish-black crystalline salt, that dissolves in water to give intensely pink or purple solutions.

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).

Potassium ferrate

Potassium ferrate is the chemical compound with the formula K2FeO4. This purple salt is paramagnetic, and is a rare example of an iron(VI) compound. In most of its compounds, iron has the oxidation state +2 or +3 (Fe2+ or Fe3+). Reflecting its high oxidation state, FeO42− is a powerful oxidizing agent.

Permanganate

A permanganate is the general name for a chemical compound containing the manganate(VII) ion, (MnO
4
). Because manganese is in the +7 oxidation state, the permanganate(VII) ion is a strong oxidizing agent. The ion has tetrahedral geometry. Permanganate solutions are purple in color and are stable in neutral or slightly alkaline media. The exact chemical reaction is dependent upon the organic contaminants present and the oxidant utilized. For example, trichloroethane (C2H3Cl3) is oxidized by permanganate ions to form carbon dioxide (CO2), manganese dioxide (MnO2), hydrogen ions (H+), and chloride ions (Cl).

In chemistry, disproportionation, sometimes called dismutation, is a redox reaction in which one compound of intermediate oxidation state converts to two compounds, one of higher and one of lower oxidation states. More generally, the term can be applied to any desymmetrizing reaction of the following type: 2 A → A' + A", regardless of whether it is a redox or some other type of process.

Manganate

In inorganic nomenclature, a manganate is any negatively charged molecular entity with manganese as the central atom. However, the name is usually used to refer to the tetraoxidomanganate(2−) anion, MnO2−
4
, also known as manganate(VI) because it contains manganese in the +6 oxidation state. Manganates are the only known manganese(VI) compounds.

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.

Sodium oxalate

Sodium oxalate, or disodium oxalate, is the sodium salt of oxalic acid with the formula Na2C2O4. It is a white, crystalline, odorless solid, that decomposes above 290 °C.

Potassium manganate

Potassium manganate is the inorganic compound with the formula K2MnO4. This green-colored salt is an intermediate in the industrial synthesis of potassium permanganate (KMnO4), a common chemical. Occasionally, potassium manganate and potassium permanganate are confused, but they are different compounds with distinctly different properties.

Ferrate(VI)

Ferrate(VI) is the inorganic anion with the chemical formula [FeO4]2−. It is photosensitive, contributes a pale violet colour to compounds and solutions containing it and is one of the strongest water-stable oxidizing species known. Although it is classified as a weak base, concentrated solutions containing ferrate(VI) are corrosive and attack the skin and are only stable at high pH.

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.

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.

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.

Chemical chameleon

The chemical chameleon is a redox reaction, well known from classroom demonstrations, that exploits the dramatic color changes associated with the various oxidation states of manganese.

References

  1. Redox titrations: Permanganometry. In: University Chemistry, Vol. 1. C. Parameshwara Murthy. New Age International, 2008. ISBN   81-224-0742-0. p.632
  2. Louis Rosenfeld. Four Centuries of Clinical Chemistry. CRC Press, 1999, p. 130-175.
  3. https://books.google.com/books?id=XQIIAQAAIAAJ Volumetric analysis, Vol 2. Izaak Maurits Kolthoff, Heinrich Menzel, Nathaniel Howell Furman. J. Wiley & Sons, inc., 1929. page 297
  4. Table of standard reduction potentials. In: Chemistry and chemical reactivity. John C. Kotz, Paul Treichel, John R. Townsend. Cengage Learning, 2008. ISBN   0-495-38703-7. p. 920
  5. Louis Rosenfeld. Four Centuries of Clinical Chemistry. CRC Press, 1999, p. 72-75.