Volatility (chemistry)

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Bromine liquid readily transitions to vapor at room temperature, indicating high volatility Bromine in a vial.png
Bromine liquid readily transitions to vapor at room temperature, indicating high volatility

In chemistry, volatility is a material quality which describes how readily a substance vaporizes. At a given temperature and pressure, a substance with high volatility is more likely to exist as a vapour, while a substance with low volatility is more likely to be a liquid or solid. Volatility can also describe the tendency of a vapor to condense into a liquid or solid; less volatile substances will more readily condense from a vapor than highly volatile ones. [1] Differences in volatility can be observed by comparing how fast substances within a group evaporate (or sublimate in the case of solids) when exposed to the atmosphere. A highly volatile substance such as rubbing alcohol (isopropyl alcohol) will quickly evaporate, while a substance with low volatility such as vegetable oil will remain condensed. [2] In general, solids are much less volatile than liquids, but there are some exceptions. Solids that sublimate (change directly from solid to vapor) such as dry ice (solid carbon dioxide) or iodine can vaporize at a similar rate as some liquids under standard conditions. [3]

Contents

Description

Volatility itself has no defined numerical value, but it is often described using vapor pressures or boiling points (for liquids). High vapor pressures indicate a high volatility, while high boiling points indicate low volatility. Vapor pressures and boiling points are often presented in tables and charts that can be used to compare chemicals of interest. Volatility data is typically found through experimentation over a range of temperatures and pressures.

Vapor pressure

A log-lin vapor pressure chart for various liquids Vapor pressure chart.svg
A log-lin vapor pressure chart for various liquids

Vapor pressure is a measurement of how readily a condensed phase forms a vapor at a given temperature. A substance enclosed in a sealed vessel initially at vacuum (no air inside) will quickly fill any empty space with vapor. After the system reaches equilibrium and the rate of evaporation matches the rate of condensation, the vapor pressure can be measured. Increasing the temperature increases the amount of vapor that is formed and thus the vapor pressure. In a mixture, each substance contributes to the overall vapor pressure of the mixture, with more volatile compounds making a larger contribution.

Boiling point

Boiling point is the temperature at which the vapor pressure of a liquid is equal to the surrounding pressure, causing the liquid to rapidly evaporate, or boil. It is closely related to vapor pressure, but is dependent on pressure. The normal boiling point is the boiling point at atmospheric pressure, but it can also be reported at higher and lower pressures. [3]

Contributing factors

Intermolecular forces

Normal boiling point (red) and melting point (blue) of linear alkanes vs. number of carbon atoms. AlkaneBoilingMeltingPoint.png
Normal boiling point (red) and melting point (blue) of linear alkanes vs. number of carbon atoms.

An important factor influencing a substance's volatility is the strength of the interactions between its molecules. Attractive forces between molecules are what holds materials together, and materials with stronger intermolecular forces, such as most solids, are typically not very volatile. Ethanol and dimethyl ether, two chemicals with the same formula (C2H6O), have different volatilities due to the different interactions that occur between their molecules in the liquid phase: ethanol molecules are capable of hydrogen bonding while dimethyl ether molecules are not. [4] The result in an overall stronger attractive force between the ethanol molecules, making it the less volatile substance of the two.

Molecular weight

In general, volatility tends to decrease with increasing molecular mass because larger molecules can participate in more intermolecular bonding, [5] although other factors such as structure and polarity play a significant role. The effect of molecular mass can be partially isolated by comparing chemicals of similar structure (i.e. esters, alkanes, etc.). For instance, linear alkanes exhibit decreasing volatility as the number of carbons in the chain increases.

Applications

Distillation

A crude oil distillation column. Crude Oil Distillation-en.svg
A crude oil distillation column.

Knowledge of volatility is often useful in the separation of components from a mixture. When a mixture of condensed substances contains multiple substances with different levels of volatility, its temperature and pressure can be manipulated such that the more volatile components change to a vapor while the less volatile substances remain in the liquid or solid phase. The newly formed vapor can then be discarded or condensed into a separate container. When the vapors are collected, this process is known as distillation. [6]

The process of petroleum refinement utilizes a technique known as fractional distillation, which allows several chemicals of varying volatility to be separated in a single step. Crude oil entering a refinery is composed of many useful chemicals that need to be separated. The crude oil flows into a distillation tower and is heated up, which allows the more volatile components such as butane and kerosene to vaporize. These vapors move up the tower and eventually come in contact with cold surfaces, which causes them to condense and be collected. The most volatile chemical condense at the top of the column while the least volatile chemicals to vaporize condense in the lowest portion. [1] On the right is a picture illustrating the design of a distillation tower.

The difference in volatility between water and ethanol has traditionally been used in the refinement of drinking alcohol. In order to increase the concentration of ethanol in the product, alcohol makers would heat the initial alcohol mixture to a temperature where most of the ethanol vaporizes while most of the water remains liquid. The ethanol vapor is then collected and condensed in a separate container, resulting in a much more concentrated product. [7]

Perfume

Volatility is an important consideration when crafting perfumes. Humans detect odors when aromatic vapors come in contact with receptors in the nose. Ingredients that vaporize quickly after being applied will produce fragrant vapors for a short time before the oils evaporate. Slow-evaporating ingredients can stay on the skin for weeks or even months, but may not produce enough vapors to produce a strong aroma. To prevent these problems, perfume designers carefully consider the volatility of essential oils and other ingredients in their perfumes. Appropriate evaporation rates are achieved by modifying the amount of highly volatile and non-volatile ingredients used. [8]

See also

Related Research Articles

<span class="mw-page-title-main">Boiling point</span> Temperature at which a substance changes from liquid into vapor

The boiling point of a substance is the temperature at which the vapor pressure of a liquid equals the pressure surrounding the liquid and the liquid changes into a vapor.

<span class="mw-page-title-main">Distillation</span> Method of separating mixtures

Distillation, or classical distillation, is the process of separating the components or substances from a liquid mixture by using selective boiling and condensation, usually inside an apparatus known as a still. Dry distillation is the heating of solid materials to produce gaseous products ; this may involve chemical changes such as destructive distillation or cracking. Distillation may result in essentially complete separation, or it may be a partial separation that increases the concentration of selected components; in either case, the process exploits differences in the relative volatility of the mixture's components. In industrial applications, distillation is a unit operation of practically universal importance, but is a physical separation process, not a chemical reaction. An installation used for distillation, especially of distilled beverages, is a distillery. Distillation includes the following applications:

<span class="mw-page-title-main">Evaporation</span> Type of vaporization of a liquid that occurs from its surface; surface phenomenon

Evaporation is a type of vaporization that occurs on the surface of a liquid as it changes into the gas phase. High concentration of the evaporating substance in the surrounding gas significantly slows down evaporation, such as when humidity affects rate of evaporation of water. When the molecules of the liquid collide, they transfer energy to each other based on how they collide. When a molecule near the surface absorbs enough energy to overcome the vapor pressure, it will escape and enter the surrounding air as a gas. When evaporation occurs, the energy removed from the vaporized liquid will reduce the temperature of the liquid, resulting in evaporative cooling.

<span class="mw-page-title-main">Solution (chemistry)</span> Homogeneous mixture of a solute and a solvent

In chemistry, a solution is a special type of homogeneous mixture composed of two or more substances. In such a mixture, a solute is a substance dissolved in another substance, known as a solvent. If the attractive forces between the solvent and solute particles are greater than the attractive forces holding the solute particles together, the solvent particles pull the solute particles apart and surround them. These surrounded solute particles then move away from the solid solute and out into the solution. The mixing process of a solution happens at a scale where the effects of chemical polarity are involved, resulting in interactions that are specific to solvation. The solution usually has the state of the solvent when the solvent is the larger fraction of the mixture, as is commonly the case. One important parameter of a solution is the concentration, which is a measure of the amount of solute in a given amount of solution or solvent. The term "aqueous solution" is used when one of the solvents is water.

<span class="mw-page-title-main">Vapor</span> Substances in the gas phase at a temperature lower than its critical point

In physics, a vapor or vapour is a substance in the gas phase at a temperature lower than its critical temperature, which means that the vapor can be condensed to a liquid by increasing the pressure on it without reducing the temperature of the vapor. A vapor is different from an aerosol. An aerosol is a suspension of tiny particles of liquid, solid, or both within a gas.

<span class="mw-page-title-main">Solvent</span> Substance dissolving a solute resulting in a solution

A solvent is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for polar molecules and the most common solvent used by living things; all the ions and proteins in a cell are dissolved in water within the cell.

<span class="mw-page-title-main">Enthalpy of vaporization</span> Energy to convert a liquid substance to a gas at a given pressure

In thermodynamics, the enthalpy of vaporization, also known as the (latent) heat of vaporization or heat of evaporation, is the amount of energy (enthalpy) that must be added to a liquid substance to transform a quantity of that substance into a gas. The enthalpy of vaporization is a function of the pressure at which the transformation takes place.

<span class="mw-page-title-main">Vapor pressure</span> Pressure exerted by a vapor in thermodynamic equilibrium

Vapor pressure or equilibrium vapor pressure is the pressure exerted by a vapor in thermodynamic equilibrium with its condensed phases 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 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.

<span class="mw-page-title-main">Azeotrope</span> Mixture of two or more liquids whose proportions do not change when the mixture is distilled

An azeotrope or a constant heating point mixture is a mixture of two or more components in fluidic states whose proportions cannot be altered or changed by simple distillation. This happens because when an azeotrope is boiled, the vapour has the same proportions of constituents as the unboiled mixture. Azeotropic mixture behavior is important for fluid separation processes.

Fractional distillation is the separation of a mixture into its component parts, or fractions. Chemical compounds are separated by heating them to a temperature at which one or more fractions of the mixture will vaporize. It uses distillation to fractionate. Generally the component parts have boiling points that differ by less than 25 °C (45 °F) from each other under a pressure of one atmosphere. If the difference in boiling points is greater than 25 °C, a simple distillation is typically used. It is used to refine crude oil.

<span class="mw-page-title-main">Fractionating column</span> Equipment to separate liquids by distillation

A fractionating column or fractional column is equipment used in the distillation of liquid mixtures to separate the mixture into its component parts, or fractions, based on their differences in volatility. Fractionating columns are used in small-scale laboratory distillations as well as large-scale industrial distillations.

<span class="mw-page-title-main">Still</span> Apparatus used to distill liquid mixtures

A still is an apparatus used to distill liquid mixtures by heating to selectively boil and then cooling to condense the vapor. A still uses the same concepts as a basic distillation apparatus, but on a much larger scale. Stills have been used to produce perfume and medicine, water for injection (WFI) for pharmaceutical use, generally to separate and purify different chemicals, and to produce distilled beverages containing ethanol.

<span class="mw-page-title-main">Sublimation (phase transition)</span> Transition of a substance directly from the solid to the gas state

Sublimation is the transition of a substance directly from the solid to the gas state, without passing through the liquid state. Sublimation is an endothermic process that occurs at temperatures and pressures below a substance's triple point in its phase diagram, which corresponds to the lowest pressure at which the substance can exist as a liquid. The reverse process of sublimation is deposition or desublimation, in which a substance passes directly from a gas to a solid phase. Sublimation has also been used as a generic term to describe a solid-to-gas transition (sublimation) followed by a gas-to-solid transition (deposition). While vaporization from liquid to gas occurs as evaporation from the surface if it occurs below the boiling point of the liquid, and as boiling with formation of bubbles in the interior of the liquid if it occurs at the boiling point, there is no such distinction for the solid-to-gas transition which always occurs as sublimation from the surface.

<span class="mw-page-title-main">Rotary evaporator</span> Device used in chemical laboratories

A rotary evaporator (rotavap) is a device used in chemical laboratories for the efficient and gentle removal of solvents from samples by evaporation. When referenced in the chemistry research literature, description of the use of this technique and equipment may include the phrase "rotary evaporator", though use is often rather signaled by other language.

<span class="mw-page-title-main">Steam distillation</span> Method of separation in organic chemistry

Steam distillation is a separation process that consists in distilling water together with other volatile and non-volatile components. The steam from the boiling water carries the vapor of the volatiles to a condenser; both are cooled and return to the liquid or solid state, while the non-volatile residues remain behind in the boiling container.

<span class="mw-page-title-main">Continuous distillation</span> Form of distillation

Continuous distillation, a form of distillation, is an ongoing separation in which a mixture is continuously fed into the process and separated fractions are removed continuously as output streams. Distillation is the separation or partial separation of a liquid feed mixture into components or fractions by selective boiling and condensation. The process produces at least two output fractions. These fractions include at least one volatile distillate fraction, which has boiled and been separately captured as a vapor condensed to a liquid, and practically always a bottoms fraction, which is the least volatile residue that has not been separately captured as a condensed vapor.

<span class="mw-page-title-main">Evaporator</span> Machine transforming a liquid into a gas

An evaporator is a device used to turn a liquid into a gas.

<span class="mw-page-title-main">Condenser (laboratory)</span> Laboratory apparatus used to condense vapors

In chemistry, a condenser is laboratory apparatus used to condense vapors – that is, turn them into liquids – by cooling them down.

This glossary of chemistry terms is a list of terms and definitions relevant to chemistry, including chemical laws, diagrams and formulae, laboratory tools, glassware, and equipment. Chemistry is a physical science concerned with the composition, structure, and properties of matter, as well as the changes it undergoes during chemical reactions; it features an extensive vocabulary and a significant amount of jargon.

<span class="mw-page-title-main">Reflux</span> Condensation of vapors and their return to where they originated

Reflux is a technique involving the condensation of vapors and the return of this condensate to the system from which it originated. It is used in industrial and laboratory distillations. It is also used in chemistry to supply energy to reactions over a long period of time.

References

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