Vapor pressure

Vapor pressure or equilibrium vapor pressure is the pressure exerted by a vapor in thermodynamic equilibrium with its condensed phases (solid or liquid) at a given temperature in a closed system. The equilibrium vapor pressure is an indication of a liquid's thermodynamic tendency to evaporate. It relates to the balance of particles escaping from the liquid (or solid) in equilibrium with those in a coexisting vapor phase. A substance with a high vapor pressure at normal temperatures is often referred to as volatile. The pressure exhibited by vapor present above a liquid surface is known as vapor pressure. As the temperature of a liquid increases, the attractive interactions between liquid molecules become less significant in comparison to the entropy of those molecules in the gas phase, increasing the vapor pressure. Thus, liquids with strong intermolecular interactions are likely to have smaller vapor pressures, with the reverse true for weaker interactions.

The vapor pressure of any substance increases non-linearly with temperature, often described by the Clausius–Clapeyron relation. The atmospheric pressure boiling point of a liquid (also known as the normal boiling point) is the temperature at which the vapor pressure equals the ambient atmospheric pressure. With any incremental increase in that temperature, the vapor pressure becomes sufficient to overcome atmospheric pressure and cause the liquid to form vapor bubbles. Bubble formation in greater depths of liquid requires a slightly higher temperature due to the higher fluid pressure, due to hydrostatic pressure of the fluid mass above. More important at shallow depths is the higher temperature required to start bubble formation. The surface tension of the bubble wall leads to an overpressure in the very small initial bubbles.

Vapor pressure is measured in the standard units of pressure. The International System of Units (SI) recognizes pressure as a derived unit with the dimension of force per area and designates the pascal (Pa) as its standard unit. One pascal is one newton per square meter (N·m⁻² or kg·m⁻¹·s⁻²).

Experimental measurement of vapor pressure is a simple procedure for common pressures between 1 and 200 kPa. The most accurate results are obtained near the boiling point of the substance; measurements smaller than 1kPa are subject to major errors. Procedures often consist of purifying the test substance, isolating it in a container, evacuating any foreign gas, then measuring the equilibrium pressure of the gaseous phase of the substance in the container at different temperatures. Better accuracy is achieved when care is taken to ensure that the entire substance and its vapor are both at the prescribed temperature. This is often done, as with the use of an isoteniscope, by submerging the containment area in a liquid bath.

Very low vapor pressures of solids can be measured using the Knudsen effusion cell method.

In a medical context, vapor pressure is sometimes expressed in other units, specifically millimeters of mercury (mmHg). Accurate knowledge of the vapor pressure is important for volatile inhalational anesthetics, most of which are liquids at body temperature but have a relatively high vapor pressure.

The Antoine equation is a pragmatic mathematical expression of the relation between the vapor pressure and the temperature of pure liquid or solid substances. It is obtained by curve-fitting and is adapted to the fact that vapor pressure is usually increasing and concave as a function of temperature. The basic form of the equation is:

and it can be transformed into this temperature-explicit form: