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Molecular Weight Distribution
The molar mass distribution (or molecular weight distribution) describes the relationship between the number of moles of each polymer species (Ni) and the molar mass (Mi) of that species. In linear polymers, the individual polymer chains rarely have exactly the same degree of polymerization and molar mass, and there is always a distribution around an average value. The molar mass distribution of a polymer may be modified by polymer fractionation. Definitions of molar mass average Different average values can be defined, depending on the statistical method applied. In practice, four averages are used, representing the weighted mean taken with the mole fraction, the weight fraction, and two other functions which can be related to measured quantities: *''Number average molar mass'' (Mn), also loosely referred to as ''number average molecular weight'' (NAMW). *''Mass average molar mass'' (Mw), where ''w'' stands for weight; also commonly referred to as ''weight average'' or ''weight ...
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Mole (unit)
The mole, symbol mol, is the unit of amount of substance in the International System of Units (SI). The quantity amount of substance is a measure of how many elementary entities of a given substance are in an object or sample. The mole is defined as containing exactly elementary entities. Depending on what the substance is, an elementary entity may be an atom, a molecule, an ion, an ion pair, or a subatomic particle such as an electron. For example, 10 moles of water (a chemical compound) and 10 moles of mercury (a chemical element), contain equal amounts of substance and the mercury contains exactly one atom for each molecule of the water, despite the two having different volumes and different masses. The number of elementary entities in one mole is known as the Avogadro number, which is the approximate number of nucleons (protons or neutrons) in one gram of ordinary matter. The previous definition of a mole was simply the number of elementary entities equal to that of 12 gram ...
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Gel Permeation Chromatography
Gel permeation chromatography (GPC) is a type of size-exclusion chromatography (SEC), that separates analytes on the basis of size, typically in organic solvents. The technique is often used for the analysis of polymers. As a technique, SEC was first developed in 1955 by Lathe and Ruthven.Lathe, G.H.; Ruthven, C.R.J. The Separation of Substance and '1956', ''62'', 665–674. The term ''gel permeation chromatography'' can be traced back to J.C. Moore of the Dow Chemical Company who investigated the technique in 1964. The proprietary column technology was licensed to Waters Corporation, who subsequently commercialized this technology in 1964.Moore, J.C. Gel permeation chromatography. I. A new method for molecular weight distribution of high polymers. ''J. Polym. Sci.'', 1964, ''2'', 835-84 GPC systems and consumables are now also available from a number of manufacturers. It is often necessary to separate polymers, both to analyze them as well as to purify the desired product. When cha ...
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Proton NMR
Proton nuclear magnetic resonance (proton NMR, hydrogen-1 NMR, or 1H NMR) is the application of nuclear magnetic resonance in NMR spectroscopy with respect to hydrogen-1 nuclei within the molecules of a substance, in order to determine the structure of its molecules. In samples where natural hydrogen (H) is used, practically all the hydrogen consists of the isotope 1H (hydrogen-1; i.e. having a proton for a nucleus). Simple NMR spectra are recorded in solution, and solvent protons must not be allowed to interfere. Deuterated (deuterium = 2H, often symbolized as D) solvents especially for use in NMR are preferred, e.g. deuterated water, D2O, deuterated acetone, (CD3)2CO, deuterated methanol, CD3OD, deuterated dimethyl sulfoxide, (CD3)2SO, and deuterated chloroform, CDCl3. However, a solvent without hydrogen, such as carbon tetrachloride, CCl4 or carbon disulfide, CS2, may also be used. Historically, deuterated solvents were supplied with a small amount (typically 0.1%) of tet ...
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End-group
End groups are an important aspect of polymer synthesis and characterization. In polymer chemistry, they are functional groups that are at the very ends of a macromolecule or oligomer (IUPAC). In polymer synthesis, like condensation polymerization and free-radical types of polymerization, end-groups are commonly used and can be analyzed by nuclear magnetic resonance (NMR) to determine the average length of the polymer. Other methods for characterization of polymers where end-groups are used are mass spectrometry and vibrational spectrometry, like infrared and raman spectroscopy. These groups are important for the analysis of polymers and for grafting to and from a polymer chain to create a new copolymer. One example of an end group is in the polymer poly(ethylene glycol) diacrylate where the end-groups are circled. End groups in polymer synthesis End groups are seen on all polymers and the functionality of those end groups can be important in determining the application of p ...
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Vapor Pressure Osmometry
Vapor phase osmometry (VPO), also known as vapor-pressure osmometry, is an experimental technique for the determination of a polymer's number average molecular weight The molar mass distribution (or molecular weight distribution) describes the relationship between the number of moles of each polymer species (Ni) and the molar mass (Mi) of that species. In linear polymers, the individual polymer chains rarely have ..., Mn. It works by taking advantage of the decrease in vapor pressure that occurs when solutes are added to pure solvent. This technique can be used for polymers with a molecular weight of up to 20,000 though accuracy is best for those below 10,000. Although membrane osmometry is also based on the measurement of colligative properties, it has a lower bound of 25,000 for sample molecular weight that can be measured owing to problems with membrane permeation. Experiment A typical vapor phase osmometer consists of: (1) two thermistors, one with a polymer-solvent solution dr ...
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Colligative Properties
In chemistry, colligative properties are those properties of solutions that depend on the ratio of the number of solute particles to the number of solvent particles in a solution, and not on the nature of the chemical species present. The number ratio can be related to the various units for concentration of a solution such as molarity, molality, normality (chemistry), etc. The assumption that solution properties are independent of nature of solute particles is exact only for ideal solutions, which are solutions that exhibit thermodynamic properties analogous to those of an ideal gas, and is approximate for dilute real solutions. In other words, colligative properties are a set of solution properties that can be reasonably approximated by the assumption that the solution is ideal. Only properties which result from the dissolution of a nonvolatile solute in a volatile liquid solvent are considered.KL Kapoor ''Applications of Thermodynamics'' Volume 3 They are essentially solvent pr ...
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Viscometry
A viscometer (also called viscosimeter) is an instrument used to measure the viscosity of a fluid. For liquids with viscosities which vary with flow conditions, an instrument called a rheometer is used. Thus, a rheometer can be considered as a special type of viscometer. Viscometers only measure under one flow condition. In general, either the fluid remains stationary and an object moves through it, or the object is stationary and the fluid moves past it. The drag caused by relative motion of the fluid and a surface is a measure of the viscosity. The flow conditions must have a sufficiently small value of Reynolds number for there to be laminar flow. At 20°C, the dynamic viscosity (kinematic viscosity × density) of water is 1.0038 mPa·s and its kinematic viscosity (product of flow time × factor) is 1.0022mm2/s. These values are used for calibrating certain types of viscometers. Standard laboratory viscometers for liquids U-tube viscometers These devices are also known as gl ...
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Arithmetic Mean
In mathematics and statistics, the arithmetic mean ( ) or arithmetic average, or just the ''mean'' or the ''average'' (when the context is clear), is the sum of a collection of numbers divided by the count of numbers in the collection. The collection is often a set of results of an experiment or an observational study, or frequently a set of results from a survey. The term "arithmetic mean" is preferred in some contexts in mathematics and statistics, because it helps distinguish it from other means, such as the geometric mean and the harmonic mean. In addition to mathematics and statistics, the arithmetic mean is used frequently in many diverse fields such as economics, anthropology and history, and it is used in almost every academic field to some extent. For example, per capita income is the arithmetic average income of a nation's population. While the arithmetic mean is often used to report central tendencies, it is not a robust statistic, meaning that it is greatly influe ...
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Molecular Mass
The molecular mass (''m'') is the mass of a given molecule: it is measured in daltons (Da or u). Different molecules of the same compound may have different molecular masses because they contain different isotopes of an element. The related quantity relative molecular mass, as defined by IUPAC, is the ratio of the mass of a molecule to the unified atomic mass unit (also known as the dalton) and is unitless. The molecular mass and relative molecular mass are distinct from but related to the molar mass. The molar mass is defined as the mass of a given substance divided by the amount of a substance and is expressed in g/mol. That makes the molar mass an average of many particles or molecules, and the molecular mass the mass of one specific particle or molecule. The molar mass is usually the more appropriate figure when dealing with macroscopic (weigh-able) quantities of a substance. The definition of molecular weight is most authoritatively synonymous with relative molecular mass; ho ...
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Living Polymerization
In polymer chemistry, living polymerization is a form of chain growth polymerization where the ability of a growing polymer chain to terminate has been removed. This can be accomplished in a variety of ways. Chain termination and chain transfer reactions are absent and the rate of chain initiation is also much larger than the rate of chain propagation. The result is that the polymer chains grow at a more constant rate than seen in traditional chain polymerization and their lengths remain very similar (i.e. they have a very low polydispersity index). Living polymerization is a popular method for synthesizing block copolymers since the polymer can be synthesized in stages, each stage containing a different monomer. Additional advantages are predetermined molar mass and control over end-groups. Living polymerization is desirable because it offers precision and control in macromolecular synthesis. This is important since many of the novel/useful properties of polymers result from t ...
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Step-growth Polymerization
Step-growth polymerization refers to a type of polymerization mechanism in which bi-functional or multifunctional monomers react to form first dimers, then trimers, longer oligomers and eventually long chain polymers. Many naturally occurring and some synthetic polymers are produced by step-growth polymerization, e.g. polyesters, polyamides, polyurethanes, etc. Due to the nature of the polymerization mechanism, a high extent of reaction is required to achieve high molecular weight. The easiest way to visualize the mechanism of a step-growth polymerization is a group of people reaching out to hold their hands to form a human chain—each person has two hands (= reactive sites). There also is the possibility to have more than two reactive sites on a monomer: In this case branched polymers production take place. IUPAC deprecates the term step-growth polymerization and recommends use of the terms polyaddition, when the propagation steps are addition reactions and no molecules are ev ...
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Chemical Kinetics
Chemical kinetics, also known as reaction kinetics, is the branch of physical chemistry that is concerned with understanding the rates of chemical reactions. It is to be contrasted with chemical thermodynamics, which deals with the direction in which a reaction occurs but in itself tells nothing about its rate. Chemical kinetics includes investigations of how experimental conditions influence the speed of a chemical reaction and yield information about the reaction's mechanism and transition states, as well as the construction of mathematical models that also can describe the characteristics of a chemical reaction. History In 1864, Peter Waage and Cato Guldberg pioneered the development of chemical kinetics by formulating the law of mass action, which states that the speed of a chemical reaction is proportional to the quantity of the reacting substances.C.M. Guldberg and P. Waage,"Studies Concerning Affinity" ''Forhandlinger i Videnskabs-Selskabet i Christiania'' (1864), 35P. W ...
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