The transport of matter from one point to another by random molecular motions. It occurs in gases, liquids, and solids.
Diffusion plays a key role in processes as diverse as permeation through membranes, evaporation of liquids, dyeing textile fibers, drying timber, doping silicon wafers to make semiconductors, and transporting of thermal neutrons in nuclear power reactors. Rates of important chemical reactions are limited by how fast diffusion can bring reactants together or deliver them to reaction sites on enzymes or catalysts. The forces between molecules and molecular sizes and shapes can be studied by making diffusion measurements. See also Evaporation.
Molecules in fluids (gases and liquids) are constantly moving. Even in still air, for example, nitrogen and oxygen molecules ricochet off each other at bullet speeds. Molecular diffusion is easily demonstrated by pouring a layer of water over a layer of ink in a narrow glass tube. The boundary between the ink and water is sharp at first, but it slowly blurs as the ink diffuses upward into the clear water. Eventually, the ink spreads evenly along the tube without any help from stirring.
Gases
A number of techniques are used to measure diffusion in gases. In a two-bulb experiment, two vessels of gas are connected by a narrow tube through which diffusion occurs. Diffusion is followed by measuring the subsequent changes in the composition of gas in each vessel. Excellent results are also obtained by placing a lighter gas mixture on top of a denser gas mixture in a vertical tube and then measuring the composition along the tube after a timed interval.
Rates of diffusion in gases increase with the temperature (T) approximately as T3/2 and are inversely proportional to the pressure. The interdiffusion coefficients of gas mixtures are almost independent of the composition.
Kinetic theory shows that the self-diffusion coefficient of a pure gas is inversely proportional to both the square root of the molecular weight and the square of the molecular diameter. Interdiffusion coefficients for pairs of gases can be estimated by taking averages of the molecular weights and collision diameters. Kinetic-theory predictions are accurate to about 5% at pressures up to 10 atm (1 megapascal). Theories which take into account the forces between molecules are more accurate, especially for dense gases.
Liquids
The most accurate diffusion measurements on liquids are made by layering a solution over a denser solution and then using optical methods to follow the changes in refractive index along the column of solution. Excellent results are also obtained with cells in which diffusion occurs between two solution compartments through a porous diaphragm. Many other reliable experimental techniques have been devised.
Room-temperature liquids usually have diffusion coefficients in the range 0.5–5 × 10−5 cm2 s−1. Diffusion in liquids, unlike diffusion in gases, is sensitive to changes in composition but relatively insensitive to changes in pressure. Diffusion of high-viscosity, syrupy liquids and macromolecules is slower. The diffusion coefficient of aqueous serum albumin, a protein of molecular weight 60,000 atomic mass units, is only 0.06 × 10−5 cm2 s−1 at 25°C (77°F).
When solute molecules diffuse through a solution, solvent molecules must be pushed out of the way. For this reason, liquid-phase interdiffusion coefficients are inversely proportional to both the viscosity of the solvent and the effective radius of the solute molecules. Accurate theories of diffusion in liquids are still under development.
Solids
Diffusion in solids is an important topic of physical metallurgy and materials science since diffusion processes are ubiquitous in solid matter at elevated temperatures. They play a key role in the kinetics of many microstructural changes that occur during the processing of metals, alloys, ceramics, semiconductors, glasses, and polymers. Typical examples of such changes include nucleation of new phases, diffusive phase transformations, precipitation and dissolution of a second phase, recrystallization, high-temperature creep, and thermal oxidation. Direct technological applications concern diffusion doping during the fabrication of microelectronic devices, solid electrolytes for battery and fuel cells, surface hardening of steels through carburization or nitridation, diffusion bonding, and sintering. See also Fuel cell; Phase transitions.
The atomic mechanisms of diffusion are closely connected with defects in solids. Point defects such as vacancies and interstitials are the simplest defects and often mediate diffusion in an otherwise perfect crystal. Dislocations, grain boundaries, phase boundaries, and free surfaces are other types of defects in a crystalline solid. They can act as diffusion short circuits because the mobility of atoms along such defects is usually much higher than in the lattice.