Inchemistry, thedispersity is a measure of the heterogeneity of sizes of molecules or particles in a mixture. A collection of objects is calleduniform if the objects have the same size, shape, or mass. A sample of objects that have an inconsistent size, shape and mass distribution is callednon-uniform. The objects can be in any form ofchemical dispersion, such as particles in acolloid, droplets in a cloud,^[1] crystals in a rock,^[2]or polymer macromolecules in a solution or a solid polymer mass.^[3] Polymers can be described bymolecular mass distribution; a population of particles can be described by size, surface area, and/or mass distribution; and thin films can be described by film thickness distribution.^{[citation needed]}

IUPAC hasdeprecated the use of the termpolydispersity index, having replaced it with the termdispersity, represented by the symbolĐ (pronounced D-stroke^[4]) which can refer to either molecular mass or degree of polymerization. It can be calculated using the equationĐ_M =M_w/M_n, whereM_w is the weight-average molar mass andM_n is the number-average molar mass. It can also be calculated according to degree of polymerization, whereĐ_X =X_w/X_n, whereX_w is the weight-average degree of polymerization andX_n is the number-average degree of polymerization. In certain limiting cases whereĐ_M =Đ_X, it is simply referred to asĐ. IUPAC has also deprecated the termsmonodisperse, which is considered to be self-contradictory, andpolydisperse, which is considered redundant, preferring the termsuniform andnon-uniform instead. The terms monodisperse and polydisperse are however still preferentially used to describe particles in anaerosol.

A uniformpolymer (often referred to as a monodisperse polymer) is composed of molecules of the same mass.^[5] Nearly all natural polymers are uniform.^[6] Synthetic near-uniform polymer chains can be made by processes such asanionic polymerization, a method using an anioniccatalyst to produce chains that are similar in length. This technique is also known asliving polymerization. It is used commercially for the production ofblock copolymers. Uniform collections can be easily created through the use of template-based synthesis, a common method of synthesis innanotechnology.^{[citation needed]}

A polymer material is denoted by the term disperse, or non-uniform, if its chain lengths vary over a wide range of molecular masses. This is characteristic of man-made polymers.^[7]Natural organic matter produced by the decomposition of plants and wood debris in soils (humic substances) also has a pronounced polydispersed character. It is the case ofhumic acids andfulvic acids, naturalpolyelectrolyte substances having respectively higher and lower molecular weights. Another interpretation of dispersity is explained in the articleDynamic light scattering (cumulant method subheading). In this sense, the dispersity values are in the range from 0 to 1.

Thedispersity (Đ), also known as the polydispersity index (PDI) or heterogeneity index, is a measure of the distribution ofmolecular mass in a givenpolymer sample.Đ (PDI) of a polymer is calculated:

${\displaystyle PDI=M_{\mathrm{w}}/M_{\mathrm{n}}}$,

where${\displaystyle M_{\mathrm{w}}}$ is theweight average molecular weight and${\displaystyle M_{\mathrm{n}}}$ is thenumber average molecular weight.${\displaystyle M_{\mathrm{n}}}$ is more sensitive to molecules of low molecular mass, while${\displaystyle M_{\mathrm{w}}}$ is more sensitive to molecules of high molecular mass. The dispersity indicates the distribution of individualmolecular masses in a batch ofpolymers.Đ has a value equal to or greater than 1, but as the polymer chains approach uniform chain length,Đ approaches unity (1).^[8] For some natural polymersĐ is almost taken as unity.

Typical dispersities vary based on the mechanism of polymerization and can be affected by a variety of reaction conditions. In synthetic polymers, it can vary greatly due toreactant ratio, how close thepolymerization went to completion, etc. For typical additionpolymerization,Đ can range around 5 to 20. For typical step polymerization, most probable values ofĐ are around 2 —Carothers' equation limits Đ to values of 2 and below.

Living polymerization, a special case of addition polymerization, leads to values very close to 1. Such is the case also in biological polymers, where the dispersity can be very close or equal to 1, indicating only one length of polymer is present.

The reactor polymerization reactions take place in can also affect the dispersity of the resulting polymer. For bulk radical polymerization with low (<10%) conversion, anionic polymerization, and step growth polymerization to high conversion (>99%), typical dispersities are in the table below.^[9]

With respect to batch andplug flow reactors (PFRs), the dispersities for the different polymerization methods are the same. This is largely because while batch reactors depend entirely on time of reaction, plug flow reactors depend on distance traveled in the reactor and its length. Since time and distance are related by velocity, plug flow reactors can be designed to mirror batch reactors by controlling the velocity and length of the reactor.Continuously stirred-tank reactors (CSTRs) however have a residence time distribution and cannot mirror batch or plug flow reactors, which can cause a difference in the dispersity of final polymer.

The effects of reactor type on dispersity depend largely on the relative timescales associated with the reactor, and with the polymerization type. In conventional bulk free radical polymerization, the dispersity is often controlled by the proportion of chains that terminate via combination or disproportionation.^[10] The rate of reaction for free radical polymerization is exceedingly quick, due to the reactivity of the radical intermediates. When these radicals react in any reactor, their lifetimes, and as a result, the time needed for reaction are much shorter than any reactor residence time. For FRPs that have a constant monomer and initiator concentration, such that theDP_n is constant, the dispersity of the resulting monomer is between 1.5 and 2.0. As a result, reactor type does not affect dispersity for free radical polymerization reactions in any noticeable amount as long as conversion is low.

For anionic polymerization, a form ofliving polymerization, the reactive anion intermediates have the ability to remain reactive for a very long time. In batch reactors or PFRs, well-controlled anionic polymerization can result in almost uniform polymer. When introduced into a CSTR however, the residence time distribution for reactants in the CSTR affects the dispersity of the anionic polymer due to the anion lifetime. For a homogeneous CSTR, the residence time distribution is themost probable distribution.^[11] Since the anionic polymerization dispersity for a batch reactor or PFR is basically uniform, the molecular weight distribution takes on the distribution of the CSTR residence times, resulting in a dispersity of 2. Heterogeneous CSTRs are similar to homogeneous CSTRs, but the mixing within the reactor is not as good as in a homogeneous CSTR. As a result, there are small sections within the reactor that act as smaller batch reactors within the CSTR and end up with different concentrations of reactants. As a result, the dispersity of the reactor lies between that of a batch and that of a homogeneous CSTR.^[9]

Step growth polymerization is most affected by reactor type. To achieve any high molecular weight polymer, the fractional conversion must exceed 0.99, and the dispersity of this reaction mechanism in a batch or PFR is 2.0. Running a step-growth polymerization in a CSTR will allow some polymer chains out of the reactor before achieving high molecular weight, while others stay in the reactor for a long time and continue to react. The result is a much more broad molecular weight distribution, which leads to much larger dispersities. For a homogeneous CSTR, the dispersity is proportional to the square root of theDamköhler number, but for a heterogeneous CSTR, dispersity is proportional to the natural log of theDamköhler number.^[9] Thus, for the similar reasons as anionic polymerization, the dispersity for heterogeneous CSTRs lies between that of a batch and a homogeneous CSTR.

• Gel permeation chromatography (also known assize-exclusion chromatography)
• Light scattering measurements such asdynamic light scattering
• Direct measurement viamass spectrometry, usingmatrix-assisted laser desorption/ionization (MALDI) orelectrospray ionization withtandem mass spectrometry (ESI-MS/MS)

• Polyelectrolyte – Polymers whose repeating units bear an electrolyte group

• Introduction to Polymers

• Copolymers
• Polymer chemistry
• Colloidal chemistry
• Colloids

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