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[[Image:Monodisperse Collection.jpg|thumb|A uniform (monodisperse) collection]]
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[[Image:Polydisperse Collection.jpg|thumb|A non-uniform (polydisperse) collection]]


In [[physical chemistry|physical]] and [[organic chemistry]], the '''dispersity''' is a measure of the heterogeneity of sizes of molecules or particles in a mixture. A collection of objects is called '''uniform''' if the objects have the same size, shape, or mass.  A sample of objects that have an inconsistent size, shape and mass distribution is called '''non-uniform'''. The objects can be in any form of [[Dispersion (chemistry)|chemical dispersion]], such as particles in a [[colloid]], droplets in a cloud,<ref>{{Cite doi|10.1088/1748-9326/4/1/015002}}</ref> crystals in a rock,<ref>{{cite journal
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|url=http://wwwdsa.uqac.ca/~mhiggins/am_min_2000.pdf
|title= Measurement of crystal size distributions
|last= Higgins
|first= Michael D.
|journal= American Mineralogist
|volume=85
|year=2000
|pages=1105–1116}}</ref>
or polymer molecules in a solvent.<ref>{{Cite doi|10.1021/j100847a053}}</ref> Polymers can possess a distribution of [[molecular mass]]; particles often possess a wide distribution of size, surface area and mass; and thin films can possess a varied distribution of film thickness.{{Citation needed|date=February 2012}}
 
[[IUPAC]] has [[deprecation|deprecated]] the use of the term ''polydispersity index'' having replaced it with the term ''dispersity'', represented by the symbol ''Đ'' (pronounced D-stroke<ref name=Stepto/>) which can refer to either molecular mass or degree of polymerization. It can be calculated using the equation ''Đ''<sub>M</sub> = ''M''<sub>w</sub>/''M''<sub>n</sub>, where ''M''<sub>w</sub> is the weight-average molar mass and ''M''<sub>n</sub> is the number-average molar massIt can also be calculated according to degree of polymerization, where ''Đ''<sub>X</sub> = ''X''<sub>w</sub>/''X''<sub>n</sub>, where ''X''<sub>w</sub> is the weight-average degree of polymerization and ''X''<sub>n</sub> is the number-average degree of polymerization. In certain limiting cases where ''Đ''<sub>M</sub> = ''Đ''<sub>X</sub>, it is simply referred to as ''Đ''. IUPAC has also deprecated the terms ''monodisperse'', which is considered to be self-contradictory, and ''polydisperse'', which is considered redundant, preferring the terms ''uniform'' and ''non-uniform'' instead.<ref name=Stepto>Stepto, R. F. T.; Gilbert, R. G.; Hess, M.; Jenkins, A. D.; Jones, R. G.; Kratochvíl P. (2009). "[http://media.iupac.org/publications/pac/2009/pdf/8102x0351.pdf Dispersity in Polymer Science]" ''Pure Appl. Chem.'' '''81''' (2): 351–353. DOI:10.1351/PAC-REC-08-05-02.</ref>
 
==Overview==
{{Quote box
|title = IUPAC definition
|quote = <big>''Đ''<sub>M</sub> = ''M''<sub>w</sub>/''M''<sub>n</sub></big><br/>where ''M''<sub>w</sub> is the weight-average molar mass and<br/>''M''<sub>n</sub> is the number-average molar mass.
|source = [http://www.iupac.org/publications/pac/81/2/0351/ ''Pure Appl. Chem.'', '''2009''', 81(2), 351-353]
|align = right
}}
A uniform [[polymer]] (formerly described as a monodisperse polymer) is composed of molecules of the same mass.<ref>{{cite web
|url=http://goldbook.iupac.org/M04012.html
|title= monodisperse polymer (See: uniform polymer)
|work= IUPAC Gold Book
|publisher= International Union of Pure and Applied Chemistry
|accessdate=25 January 2012}}</ref> Natural polymers are typically uniform.<ref>{{ cite book
|last1 = Brown
|first1 = William H.
|last2 = Foote
|first2 = Christopher S.
|last3 = Iverson
|first3 = Brent L.
|last4 = Anslyn
|first4 = Eric V.
|url = http://books.google.ca/books?id=rxRHzOS-3xoC&pg=PT1193
|title = Organic chemistry
|edition = 6
|publisher = Cengage Learning
|year = 2012
|isbn = 978-0-8400-5498-2
|page = 1161 }}</ref> Synthetic uniform polymer chains can be made by processes such as [[anionic]] polymerization, a method using an anionic [[catalyst]] to produce chains that are similar in length. This technique is also known as [[living polymerization]]. It is used commercially for the production of [[block copolymer]]s.  Uniform collections can be easily created through the use of template-based synthesis, a common method of synthesis in [[nanotechnology]].{{Citation needed|date=February 2012}}
 
A polymer material is denoted by the term  non-uniform (formerly 'polydisperse') if its chain lengths vary over a wide range of molecular masses. This is characteristic of man-made polymers.[http://www.chemicool.com/definition/polydisperse.html]. [[Natural organic matter]] produced by the decomposition of plants and wood debris in soils ([[humic substances]]) also has a pronounced non-uniform character. It is the case of [[humic acid]]s and [[fulvic acid]]s, natural [[polyelectrolyte]] substances having respectively higher and lower molecular masses.  A rather different meaning of polydispersity index is explained in the article [[Dynamic light scattering]] (cumulant method subheading). In this sense, the PDI values are in the range from 0 to 1.
 
The dispersity (''Đ'', formerly known as '''polydispersity index''', '''PDI''', or heterogeneity index), is a measure of the distribution of [[molecular mass]] in a given [[polymer]] sample.  The dispersity calculated is the [[weight average molecular weight]] (<math> M_w </math>) divided by the [[number average molecular weight]] (<math> M_n </math>). It indicates the distribution of individual [[molecular mass]]es in a batch of [[polymer]]s.  The dispersity has a value equal to or greater than 1, but as the polymer chains approach uniform chain length, ''Đ'' approaches unity (1).<ref>Peter Atkins and Julio De Paula, ''Atkins' Physical Chemistry'', 9th edition (Oxford University Press, 2010, ISBN 978-0-19-954337-3)</ref> For some natural polymers, ''Đ'' is almost taken as unity.  
The dispersity from polymerization is often denoted as ''Đ'' <math> = M_w/M_n</math>,
where <math> M_w </math> is the [[weight average molecular weight]]  and  <math> M_n </math> is the [[number average molecular weight]]. <math> M_n </math> is more sensitive to molecules of low molecular mass, while <math> M_w </math> is more sensitive to molecules of high molecular mass.
 
== Effect of polymerization mechanism ==
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 to [[reactant]] ratio, how close the [[polymerization]] went to completion, etc. For typical addition [[polymerization]], ''Đ'' can range around 10 to 20.  For typical step polymerization, most probable values of ''Đ'' are around 2 &mdash;[[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.
 
==Determination methods ==
 
* [[Gel permeation chromatography]] (also known as [[size exclusion chromatography]])
* [[Light scattering]] measurements such as [[dynamic light scattering]]
* Direct measurement via [[mass spectrometry]] using [[MALDI]] or [[ESI-MS]]
 
==References==
{{reflist}}
 
==External links==
*[http://openlearn.open.ac.uk/mod/resource/view.php?id=196629 Polymer structure]
 
[[Category:Copolymers]]
[[Category:Polymer chemistry]]
 
[[ru:Дисперсность]]

Revision as of 07:30, 10 February 2014

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