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Theta Solvent
In a polymer solution, a theta solvent (or θ solvent) is a solvent in which polymer coils act like ideal chains, assuming exactly their random walk coil dimensions. Therefore, the Mark–Houwink equation exponent is 1/2 in a theta solvent. Thermodynamically, the excess chemical potential of mixing between a polymer and a theta solvent is zero. Physical interpretation The conformation assumed by a polymer chain in dilute solution can be modeled as a random walk of monomer subunits using a freely jointed chain model. However, this model does not account for steric effects. Real polymer coils are more closely represented by a self-avoiding walk because conformations in which different chain segments occupy the same space are not physically possible. This excluded volume effect causes the polymer to expand. Chain conformation is also affected by solvent quality. The intermolecular interactions between polymer chain segments and coordinated solvent molecules have an associated ener ...
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Polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part") is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic and natural polymers play essential and ubiquitous roles in everyday life. Polymers range from familiar synthetic plastics such as polystyrene to natural biopolymers such as DNA and proteins that are fundamental to biological structure and function. Polymers, both natural and synthetic, are created via polymerization of many small molecules, known as monomers. Their consequently large molecular mass, relative to small molecule compounds, produces unique physical properties including toughness, high elasticity, viscoelasticity, and a tendency to form amorphous and semicrystalline structures rather than crystals. The term "polymer" derives from the Greek word πολύς (''polus'', meaning "many, much") and μέρος (''meros'' ...
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Ideal Solution
In chemistry, an ideal solution or ideal mixture is a solution that exhibits thermodynamic properties analogous to those of a mixture of ideal gases. The enthalpy of mixing is zero as is the volume change on mixing by definition; the closer to zero the enthalpy of mixing is, the more "ideal" the behavior of the solution becomes. The vapor pressures of the solvent and solute obey Raoult's law and Henry's law, respectively, and the activity coefficient (which measures deviation from ideality) is equal to one for each component. The concept of an ideal solution is fundamental to chemical thermodynamics and its applications, such as the explanation of colligative properties. Physical origin Ideality of solutions is analogous to ideality for gases, with the important difference that intermolecular interactions in liquids are strong and cannot simply be neglected as they can for ideal gases. Instead we assume that the mean strength of the interactions are the same between all the m ...
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Sedimentation Equilibrium
Sedimentation equilibrium in a suspension of different particles, such as molecules, exists when the rate of transport of each material in any one direction due to sedimentation equals the rate of transport in the opposite direction due to diffusion. Sedimentation is due to an external force, such as gravity or centrifugal force in a centrifuge. It was discovered for colloids by Jean Baptiste Perrin for which he received the Nobel Prize in Physics in 1926. Colloid In a colloid, the colloidal particles are said to be in sedimentation equilibrium if the rate of sedimentation is equal to the rate of movement from Brownian motion. For dilute colloids, this is described using the Laplace-Perrin distribution law: \Phi(z) = \Phi_0\exp\biggl(-\fracz\biggr)=\Phi_0e^ where \Phi(z) is the colloidal particle volume fraction as a function of vertical distance z above reference point z=0, \Phi_0 is the colloidal particle volume fraction at reference point z=0, m^* is the buoyant mass of t ...
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Intrinsic Viscosity
Intrinsic viscosity \left \eta \right/math> is a measure of a solute's contribution to the viscosity \eta of a solution. It should not be confused with inherent viscosity, which is the ratio of the natural logarithm of the relative viscosity to the mass concentration of the polymer. Intrinsic viscosity is defined as : \left \eta \right= \lim_ \frac where \eta_0 is the viscosity in the absence of the solute, \eta is (dynamic or kinematic) viscosity of the solution and \phi is the volume fraction of the solute in the solution. As defined here, the intrinsic viscosity \left \eta \right/math> is a dimensionless number. When the solute particles are rigid spheres at infinite dilution, the intrinsic viscosity equals \frac, as shown first by Albert Einstein. In practical settings, \phi is usually solute mass concentration (c, g/dL), and the units of intrinsic viscosity \left \eta \right/math> are deciliters per gram (dL/g), otherwise known as inverse concentration. Formulae for ri ...
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Light Scattering
Scattering is a term used in physics to describe a wide range of physical processes where moving particles or radiation of some form, such as light or sound, are forced to deviate from a straight trajectory by localized non-uniformities (including particles and radiation) in the medium through which they pass. In conventional use, this also includes deviation of reflected radiation from the angle predicted by the law of reflection. Reflections of radiation that undergo scattering are often called ''diffuse reflections'' and unscattered reflections are called ''specular'' (mirror-like) reflections. Originally, the term was confined to light scattering (going back at least as far as Isaac Newton in the 17th century). As more "ray"-like phenomena were discovered, the idea of scattering was extended to them, so that William Herschel could refer to the scattering of "heat rays" (not then recognized as electromagnetic in nature) in 1800. John Tyndall, a pioneer in light scattering resear ...
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Experimental Techniques
The design of experiments (DOE, DOX, or experimental design) is the design of any task that aims to describe and explain the variation of information under conditions that are hypothesized to reflect the variation. The term is generally associated with experiments in which the design introduces conditions that directly affect the variation, but may also refer to the design of quasi-experiments, in which natural conditions that influence the variation are selected for observation. In its simplest form, an experiment aims at predicting the outcome by introducing a change of the preconditions, which is represented by one or more independent variables, also referred to as "input variables" or "predictor variables." The change in one or more independent variables is generally hypothesized to result in a change in one or more dependent variables, also referred to as "output variables" or "response variables." The experimental design may also identify control variables that must be h ...
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Boyle Temperature
The Boyle temperature is formally defined as the temperature for which the second virial coefficient, B_(T), becomes zero. It is at this temperature that the attractive forces and the repulsive forces acting on the gas particles balance out P = RT \left(\frac + \frac + \cdots \right) This is the virial equation of state and describes a real gas. Since higher order virial coefficients are generally much smaller than the second coefficient, the gas tends to behave as an ideal gas over a wider range of pressures when the temperature reaches the Boyle temperature (or when c = \frac or P are minimized). In any case, when the pressures are low, the second virial coefficient will be the only relevant one because the remaining concern terms of higher order on the pressure. Also at Boyle temperature the dip in a PV diagram tends to a straight line over a period of pressure. We then have :\frac = 0 \qquad\mbox~P \to 0 where Z is the compressibility factor. Expanding the van der Waals ...
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Real Gas
Real gases are nonideal gases whose molecules occupy space and have interactions; consequently, they do not adhere to the ideal gas law. To understand the behaviour of real gases, the following must be taken into account: *compressibility effects; *variable specific heat capacity; *van der Waals forces; *non-equilibrium thermodynamic effects; *issues with molecular dissociation and elementary reactions with variable composition For most applications, such a detailed analysis is unnecessary, and the ideal gas approximation can be used with reasonable accuracy. On the other hand, real-gas models have to be used near the condensation point of gases, near critical points, at very high pressures, to explain the Joule–Thomson effect, and in other less usual cases. The deviation from ideality can be described by the compressibility factor Z. Models Van der Waals model Real gases are often modeled by taking into account their molar weight and molar volume :RT = \left(p + \frac\ri ...
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Virial Coefficient
Virial coefficients B_i appear as coefficients in the virial expansion of the pressure of a many-particle system in powers of the density, providing systematic corrections to the ideal gas law. They are characteristic of the interaction potential between the particles and in general depend on the temperature. The second virial coefficient B_2 depends only on the pair interaction between the particles, the third (B_3) depends on 2- and non-additive 3-body interactions, and so on. Derivation The first step in obtaining a closed expression for virial coefficients is a cluster expansion of the grand canonical partition function : \Xi = \sum_ = e^ Here p is the pressure, V is the volume of the vessel containing the particles, k_B is Boltzmann's constant, T is the absolute temperature, \lambda =\exp mu/(k_BT) is the fugacity, with \mu the chemical potential. The quantity Q_n is the canonical partition function of a subsystem of n particles: : Q_n = \operatorname e^ Here H(1,2,\ld ...
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Absolute Temperature
Thermodynamic temperature is a quantity defined in thermodynamics as distinct from kinetic theory or statistical mechanics. Historically, thermodynamic temperature was defined by Kelvin in terms of a macroscopic relation between thermodynamic work and heat transfer as defined in thermodynamics, but the kelvin was redefined by international agreement in 2019 in terms of phenomena that are now understood as manifestations of the kinetic energy of free motion of microscopic particles such as atoms, molecules, and electrons. From the thermodynamic viewpoint, for historical reasons, because of how it is defined and measured, this microscopic kinetic definition is regarded as an "empirical" temperature. It was adopted because in practice it can generally be measured more precisely than can Kelvin's thermodynamic temperature. A thermodynamic temperature reading of zero is of particular importance for the third law of thermodynamics. By convention, it is reported on the ''Kelvin scale'' ...
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Gas Constant
The molar gas constant (also known as the gas constant, universal gas constant, or ideal gas constant) is denoted by the symbol or . It is the molar equivalent to the Boltzmann constant, expressed in units of energy per temperature increment per amount of substance, i.e. the pressure–volume product, rather than energy per temperature increment per ''particle''. The constant is also a combination of the constants from Boyle's law, Charles's law, Avogadro's law, and Gay-Lussac's law. It is a physical constant that is featured in many fundamental equations in the physical sciences, such as the ideal gas law, the Arrhenius equation, and the Nernst equation. The gas constant is the constant of proportionality that relates the energy scale in physics to the temperature scale and the scale used for amount of substance. Thus, the value of the gas constant ultimately derives from historical decisions and accidents in the setting of units of energy, temperature and amount of substa ...
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Molecular Weight
A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and biochemistry, the distinction from ions is dropped and ''molecule'' is often used when referring to polyatomic ions. A molecule may be homonuclear, that is, it consists of atoms of one chemical element, e.g. two atoms in the oxygen molecule (O2); or it may be heteronuclear, a chemical compound composed of more than one element, e.g. water (two hydrogen atoms and one oxygen atom; H2O). In the kinetic theory of gases, the term ''molecule'' is often used for any gaseous particle regardless of its composition. This relaxes the requirement that a molecule contains two or more atoms, since the noble gases are individual atoms. Atoms and complexes connected by non-covalent interactions, such as hydrogen bonds or ionic bonds, are typically not consi ...
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