intermolecular forces

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intermolecular forces,

forces that are exerted by molecules on each other and that, in general, affect the macroscopic properties of the material of which the molecules are a part. Such forces may be either attractive or repulsive in nature. They are conveniently divided into two classes: short-range forces, which operate when the centers of the molecules are separated by 3 angstromsangstrom
, abbr. Å, unit of length equal to 10−10 meter (0.0000000001 meter); it is used to measure the wavelengths of visible light and of other forms of electromagnetic radiation, such as ultraviolet radiation and X rays.
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 or less, and long-range forces, which operate at greater distances. Generally, if molecules do not tend to interact chemically, the short-range forces between them are repulsive. These forces arise from interactions of the electrons associated with the molecules and are also known as exchange forces. Molecules that interact chemically have attractive exchange forces; these are also known as valence forces. Mechanical rigidity of molecules and effects such as limited compressibility of matter arise from repulsive exchange forces. Long-range forces, or van der Waals forces as they are also called, are attractive and account for a wide range of physical phenomena, such as frictionfriction,
resistance offered to the movement of one body past another body with which it is in contact. In certain situations friction is desired. Without friction the wheels of a locomotive could not "grip" the rails nor could power be transmitted by belts.
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, surface tensionsurface tension,
tendency of liquids to reduce their exposed surface to the smallest possible area. A drop of water, for example, tends to assume the shape of a sphere. The phenomenon is attributed to cohesion, the attractive forces acting between the molecules of the liquid
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, adhesion and cohesionadhesion and cohesion,
attractive forces between material bodies. A distinction is usually made between an adhesive force, which acts to hold two separate bodies together (or to stick one body to another) and a cohesive force, which acts to hold together the like or unlike
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 of liquids and solids, viscosityviscosity,
resistance of a fluid to flow. This resistance acts against the motion of any solid object through the fluid and also against motion of the fluid itself past stationary obstacles.
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, and the discrepancies between the actual behavior of gases and that predicted by the ideal gas lawgas laws,
physical laws describing the behavior of a gas under various conditions of pressure, volume, and temperature. Experimental results indicate that all real gases behave in approximately the same manner, having their volume reduced by about the same proportion of the
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. Van der Waals forces arise in a number of ways, one being the tendency of electrically polarized molecules to become aligned. Quantum theory indicates also that in some cases the electrostatic fields associated with electrons in neighboring molecules constrain the electrons to move more or less in phase.

Intermolecular forces

Attractive or repulsive interactions that occur between all atoms and molecules. Intermolecular forces become significant at molecular separations of about 1 nanometer or less, but are much weaker than the forces associated with chemical bonding. They are important, however, because they are responsible for many of the physical properties of solids, liquids, and gases. These forces are also largely responsible for the three-dimensional arrangements of biological molecules and polymers.

Intermolecular forces can be classified into several types, of which two are universal. The attractive force known as dispersion arises from the quantum-mechanical fluctuation of the electron density around the nucleus of each atom. At distances greater than 1 nm or so, the electrons of each atom move independently of the other, and the charge distribution is spherically symmetric. At shorter distances, an instantaneous fluctuation of the charge density in one atom can affect the other. If the electrons of one atom move briefly to the side nearer the other, the electrons of the other atom are repelled to the far side. In this configuration, both atoms have a small dipole moment, and they attract each other electrostatically. At another moment, the electrons may move the other way, but their motions are correlated so that an attractive force is maintained on average. Molecular orbital theory shows that the electrons of each atom are slightly more likely to be on the side nearer to the other atom, so that each atomic nucleus is attracted by its own electrons in the direction of the other atom.

At small separations the electron clouds can overlap, and repulsive forces arise. These forces are described as exchange-repulsion, and are a consequence of the Pauli exclusion principle, a quantum-mechanical effect which prevents electrons from occupying the same region of space simultaneously. To accommodate it, electrons are squeezed out from the region between the nuclei, which repel each other as a result. Each element can be assigned, approximately, a characteristic van der Waals radius; that is, when atoms in different molecules approach more closely than the sum of their radii, the repulsion ennergy increases sharply. It is this effect that gives molecules their characteristic shape, leading to steric effects in chemical reactions. See Exclusion principle

The other important source of intermolecular forces is the electrostatic interaction. When molecules are formed from atoms, electrons flow from electropositive atoms to electronegative ones, so that the atoms become somewhat positively or negatively charged. In addition, the charge distribution of each atom may be distorted by the process of bond formation, leading to atomic dipole and quadrupole moments. The electrostatic interaction between these is an important source of intermolecular forces, especially in polar molecules, but also in molecules that are not normally thought of as highly polar. The electrostatic field of a molecule may cause polarization of its neighbors, and this leads to a further induction contribution to the intermolecular interaction. An induction interaction can often polarize both molecules in such a way as to favor interactions with further molecules, leading to a cooperative network of intermolecular attractions. This effect is important in the network structure of water and ice.

Intermolecular forces are responsible for many of the bulk properties of matter in all its phases. A realistic description of the relationship between pressure, volume, and temperature of a gas must include the effects of attractive and repulsive forces between molecules. The viscosity, diffusion, and surface tension of liquids are examples of physical properties which depend strongly on intermolecular forces. Intermolecular forces are also responsible for the ordered arrangement of molecules in solids, and account for their elasticity and properties (such as the velocity of sound in materials).

References in periodicals archive ?
Signal-response analyses of the limiting cases of a non-slipping film on an inclined plane (b [right arrow] 0) and of plane viscous liquid sheets (b [right arrow] [infinity]), both in absence of intermolecular forces ([PHI] = 0), have been investigated by Alleborn and Raszillier (2004a,b) and Raszillier (2005), repectively, where also details of the derivation of velocity, pressure and interface perturbations are given.
So our task would have to be that of relating the experimental stress to whatever we can discover as a rational average of the intermolecular forces in a solid.
A detailed description of the hydrogenbonding patterns in a given system must be derived from analysis of specific experimental data, and as such, a sound knowledge and understanding of the role that intermolecular forces play in supramolecular assembly is generally obtained from systematic crystallographic studies.
Intermolecular forces also influence these properties.
Uses in life sciences Many biological processes are governed by intermolecular forces, making them candidates for measurement by AFM force curves.
Nonreactive silicones are based on polydimethylsiloxanes (PDMS), which impart desirable properties as a result of their flexible polymer backbone, stable bonds and low intermolecular forces.
The book provides a thorough foundation in theories and concepts of intermolecular forces, allowing researchers and students to recognize which forces are important in any particular system, as well as how to control these forces.
The individual chains are not covalently bonded to each other, but instead rely on intermolecular forces, such as Van der Waals forces, hydrogen bonding, and dipole interactions, to keep the chains from disentangling.
The substitution of polar hydroxyl groups with less polar acrylate groups led to a decreased viscosity, that can be explained by the reduction of intermolecular forces.
She provides an overview of pharmaceutics, covering dosage form design; intermolecular forces and the physical and pharmaceutical properties of drugs; dispersed systems; the properties of solutions and manipulation of solubility; chemical stability; drug travel from dosage form to receptor; bioavailability, bioequivalence, and the Biopharmaceutical Classification System; parenteral drug delivery; delivery of biopharmaceuticals and the use of novel carrier systems; oral delivery of immediate release dosage forms and modified release solid dosage forms; and drug delivery by various routes of administration.
The results reveal a new physical insight called Critical Intermolecular Forces (CIF), which is responsible for the transition phenomenon from three to one-dimensional shape of aggregate.
p], is an inverse function of intermolecular forces and of how well molecules are packed in supramolecular lattices [5]:

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