Boiling point

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Boiling water Kochendes wasser02.jpg
Boiling water

The boiling point of a substance is the temperature at which the vapor pressure of a liquid equals the pressure surrounding the liquid [1] [2] and the liquid changes into a vapor.

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The boiling point of a liquid varies depending upon the surrounding environmental pressure. A liquid in a partial vacuum has a lower boiling point than when that liquid is at atmospheric pressure. A liquid at low pressure has a lower boiling point than when that liquid is at atmospheric pressure. Because of this, water boils at 99.97 °C (211.95 °F) under standard pressure at sea level, but at 93.4 °C (200.1 °F) at 1,905 metres (6,250 ft) [3] altitude. For a given pressure, different liquids will boil at different temperatures.

The normal boiling point (also called the atmospheric boiling point or the atmospheric pressure boiling point) of a liquid is the special case in which the vapor pressure of the liquid equals the defined atmospheric pressure at sea level, one atmosphere. [4] [5] At that temperature, the vapor pressure of the liquid becomes sufficient to overcome atmospheric pressure and allow bubbles of vapor to form inside the bulk of the liquid. The standard boiling point has been defined by IUPAC since 1982 as the temperature at which boiling occurs under a pressure of one bar. [6]

The heat of vaporization is the energy required to transform a given quantity (a mol, kg, pound, etc.) of a substance from a liquid into a gas at a given pressure (often atmospheric pressure).

Liquids may change to a vapor at temperatures below their boiling points through the process of evaporation. Evaporation is a surface phenomenon in which molecules located near the liquid's edge, not contained by enough liquid pressure on that side, escape into the surroundings as vapor. On the other hand, boiling is a process in which molecules anywhere in the liquid escape, resulting in the formation of vapor bubbles within the liquid.

Saturation temperature and pressure

Demonstration of the lower boiling point of water at lower pressure, achieved by using a vacuum pump.

A saturated liquid contains as much thermal energy as it can without boiling (or conversely a saturated vapor contains as little thermal energy as it can without condensing).

Saturation temperature means boiling point. The saturation temperature is the temperature for a corresponding saturation pressure at which a liquid boils into its vapor phase. The liquid can be said to be saturated with thermal energy. Any addition of thermal energy results in a phase transition.

If the pressure in a system remains constant (isobaric), a vapor at saturation temperature will begin to condense into its liquid phase as thermal energy (heat) is removed. Similarly, a liquid at saturation temperature and pressure will boil into its vapor phase as additional thermal energy is applied.

The boiling point corresponds to the temperature at which the vapor pressure of the liquid equals the surrounding environmental pressure. Thus, the boiling point is dependent on the pressure. Boiling points may be published with respect to the NIST, USA standard pressure of 101.325 kPa (or 1 atm), or the IUPAC standard pressure of 100.000 kPa. At higher elevations, where the atmospheric pressure is much lower, the boiling point is also lower. The boiling point increases with increased pressure up to the critical point, where the gas and liquid properties become identical. The boiling point cannot be increased beyond the critical point. Likewise, the boiling point decreases with decreasing pressure until the triple point is reached. The boiling point cannot be reduced below the triple point.

If the heat of vaporization and the vapor pressure of a liquid at a certain temperature are known, the boiling point can be calculated by using the Clausius–Clapeyron equation, thus:

where:

is the boiling point at the pressure of interest,
is the ideal gas constant,
is the vapor pressure of the liquid,
is some pressure where the corresponding is known (usually data available at 1 atm or 100 kPa),
is the heat of vaporization of the liquid,
is the boiling temperature,
is the natural logarithm.

Saturation pressure is the pressure for a corresponding saturation temperature at which a liquid boils into its vapor phase. Saturation pressure and saturation temperature have a direct relationship: as saturation pressure is increased, so is saturation temperature.

If the temperature in a system remains constant (an isothermal system), vapor at saturation pressure and temperature will begin to condense into its liquid phase as the system pressure is increased. Similarly, a liquid at saturation pressure and temperature will tend to flash into its vapor phase as system pressure is decreased.

There are two conventions regarding the standard boiling point of water: The normal boiling point is 99.97  °C (211.9  °F ) at a pressure of 1 atm (i.e., 101.325 kPa). The IUPAC-recommended standard boiling point of water at a standard pressure of 100 kPa (1 bar) [7] is 99.61  °C (211.3  °F ). [6] [8] For comparison, on top of Mount Everest, at 8,848 m (29,029 ft) elevation, the pressure is about 34  kPa (255  Torr ) [9] and the boiling point of water is 71  °C (160  °F ). The Celsius temperature scale was defined until 1954 by two points: 0 °C being defined by the water freezing point and 100 °C being defined by the water boiling point at standard atmospheric pressure.

Relation between the normal boiling point and the vapor pressure of liquids

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

The higher the vapor pressure of a liquid at a given temperature, the lower the normal boiling point (i.e., the boiling point at atmospheric pressure) of the liquid.

The vapor pressure chart to the right has graphs of the vapor pressures versus temperatures for a variety of liquids. [10] As can be seen in the chart, the liquids with the highest vapor pressures have the lowest normal boiling points.

For example, at any given temperature, methyl chloride has the highest vapor pressure of any of the liquids in the chart. It also has the lowest normal boiling point (−24.2 °C), which is where the vapor pressure curve of methyl chloride (the blue line) intersects the horizontal pressure line of one atmosphere (atm) of absolute vapor pressure.

The critical point of a liquid is the highest temperature (and pressure) it will actually boil at.

See also Vapour pressure of water.

Boiling point of chemical elements

The element with the lowest boiling point is helium. Both the boiling points of rhenium and tungsten exceed 5000 K at standard pressure; because it is difficult to measure extreme temperatures precisely without bias, both have been cited in the literature as having the higher boiling point. [11]

Boiling point as a reference property of a pure compound

As can be seen from the above plot of the logarithm of the vapor pressure vs. the temperature for any given pure chemical compound, its normal boiling point can serve as an indication of that compound's overall volatility. A given pure compound has only one normal boiling point, if any, and a compound's normal boiling point and melting point can serve as characteristic physical properties for that compound, listed in reference books. The higher a compound's normal boiling point, the less volatile that compound is overall, and conversely, the lower a compound's normal boiling point, the more volatile that compound is overall. Some compounds decompose at higher temperatures before reaching their normal boiling point, or sometimes even their melting point. For a stable compound, the boiling point ranges from its triple point to its critical point, depending on the external pressure. Beyond its triple point, a compound's normal boiling point, if any, is higher than its melting point. Beyond the critical point, a compound's liquid and vapor phases merge into one phase, which may be called a superheated gas. At any given temperature, if a compound's normal boiling point is lower, then that compound will generally exist as a gas at atmospheric external pressure. If the compound's normal boiling point is higher, then that compound can exist as a liquid or solid at that given temperature at atmospheric external pressure, and will so exist in equilibrium with its vapor (if volatile) if its vapors are contained. If a compound's vapors are not contained, then some volatile compounds can eventually evaporate away in spite of their higher boiling points.

Boiling points of alkanes, alkenes, ethers, halogenoalkanes, aldehydes, ketones, alcohols and carboxylic acids as a function of molar mass Boiling point vs molar mass graph.png
Boiling points of alkanes, alkenes, ethers, halogenoalkanes, aldehydes, ketones, alcohols and carboxylic acids as a function of molar mass

In general, compounds with ionic bonds have high normal boiling points, if they do not decompose before reaching such high temperatures. Many metals have high boiling points, but not all. Very generally—with other factors being equal—in compounds with covalently bonded molecules, as the size of the molecule (or molecular mass) increases, the normal boiling point increases. When the molecular size becomes that of a macromolecule, polymer, or otherwise very large, the compound often decomposes at high temperature before the boiling point is reached. Another factor that affects the normal boiling point of a compound is the polarity of its molecules. As the polarity of a compound's molecules increases, its normal boiling point increases, other factors being equal. Closely related is the ability of a molecule to form hydrogen bonds (in the liquid state), which makes it harder for molecules to leave the liquid state and thus increases the normal boiling point of the compound. Simple carboxylic acids dimerize by forming hydrogen bonds between molecules. A minor factor affecting boiling points is the shape of a molecule. Making the shape of a molecule more compact tends to lower the normal boiling point slightly compared to an equivalent molecule with more surface area.

Comparison of butane (C4H10) isomer boiling points
Common namen-butane isobutane
IUPAC name butane2-methylpropane
Molecular
form
Butane-3D-balls.png Isobutane-3D-balls.png
Boiling
point (°C)
−0.5−11.7
Comparison of pentane isomer boiling points
Common namen-pentane isopentane neopentane
IUPAC name pentane2-methylbutane2,2-dimethylpropane
Molecular
form
Pentane-3D-balls.png Isopentane-3D-balls.png Neopentane-3D-balls.png
Boiling
point (°C)
36.027.79.5
Binary boiling point diagram of two hypothetical only weakly interacting components without an azeotrope Binary Boiling Point Diagram new.svg
Binary boiling point diagram of two hypothetical only weakly interacting components without an azeotrope

Most volatile compounds (anywhere near ambient temperatures) go through an intermediate liquid phase while warming up from a solid phase to eventually transform to a vapor phase. By comparison to boiling, a sublimation is a physical transformation in which a solid turns directly into vapor, which happens in a few select cases such as with carbon dioxide at atmospheric pressure. For such compounds, a sublimation point is a temperature at which a solid turning directly into vapor has a vapor pressure equal to the external pressure.

Impurities and mixtures

In the preceding section, boiling points of pure compounds were covered. Vapor pressures and boiling points of substances can be affected by the presence of dissolved impurities (solutes) or other miscible compounds, the degree of effect depending on the concentration of the impurities or other compounds. The presence of non-volatile impurities such as salts or compounds of a volatility far lower than the main component compound decreases its mole fraction and the solution's volatility, and thus raises the normal boiling point in proportion to the concentration of the solutes. This effect is called boiling point elevation . As a common example, salt water boils at a higher temperature than pure water.

In other mixtures of miscible compounds (components), there may be two or more components of varying volatility, each having its own pure component boiling point at any given pressure. The presence of other volatile components in a mixture affects the vapor pressures and thus boiling points and dew points of all the components in the mixture. The dew point is a temperature at which a vapor condenses into a liquid. Furthermore, at any given temperature, the composition of the vapor is different from the composition of the liquid in most such cases. In order to illustrate these effects between the volatile components in a mixture, a boiling point diagram is commonly used. Distillation is a process of boiling and [usually] condensation which takes advantage of these differences in composition between liquid and vapor phases.

Table

See also

Related Research Articles

<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. Dry distillation is the heating of solid materials to produce gaseous products. Dry distillation may involve chemical changes such as destructive distillation or cracking and is not discussed under this article. Distillation may result in essentially complete separation, or it may be a partial separation that increases the concentration of selected components in the mixture. 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 it is a physical separation process, not a chemical reaction.

<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">Pressure</span> Force distributed over an area

Pressure is the force applied perpendicular to the surface of an object per unit area over which that force is distributed. Gauge pressure is the pressure relative to the ambient pressure.

In thermodynamics, the triple point of a substance is the temperature and pressure at which the three phases of that substance coexist in thermodynamic equilibrium. It is that temperature and pressure at which the sublimation curve, fusion curve and the vaporisation curve meet. For example, the triple point of mercury occurs at a temperature of −38.8 °C (−37.8 °F) and a pressure of 0.165 mPa.

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

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 that 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 defined as 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 evaporation rate. It relates to the tendency of particles to escape from the liquid. 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 liquid increases, the kinetic energy of its molecules also increases. As the kinetic energy of the molecules increases, the number of molecules transitioning into a vapor also increases, thereby increasing the vapor pressure.

In a mixture of gases, each constituent gas has a partial pressure which is the notional pressure of that constituent gas as if it alone occupied the entire volume of the original mixture at the same temperature. The total pressure of an ideal gas mixture is the sum of the partial pressures of the gases in the mixture.

Boiling is the rapid vaporization of a liquid, which occurs when a liquid is heated to its boiling point, the temperature at which the vapour pressure of the liquid is equal to the pressure exerted on the liquid by the surrounding atmosphere. There are two main types of boiling: nucleate boiling where small bubbles of vapour form at discrete points, and critical heat flux boiling where the boiling surface is heated above a certain critical temperature and a film of vapor forms on the surface. Transition boiling is an intermediate, unstable form of boiling with elements of both types. The boiling point of water is 100 °C or 212 °F but is lower with the decreased atmospheric pressure found at higher altitudes.

<span class="mw-page-title-main">Humidity</span> Concentration of water vapour present in the air

Humidity is the concentration of water vapor present in the air. Water vapor, the gaseous state of water, is generally invisible to the human eye. Humidity indicates the likelihood for precipitation, dew, or fog to be present.

<span class="mw-page-title-main">Phase diagram</span> Chart used to show conditions at which physical phases of a substance occur

A phase diagram in physical chemistry, engineering, mineralogy, and materials science is a type of chart used to show conditions at which thermodynamically distinct phases occur and coexist at equilibrium.

<span class="mw-page-title-main">Azeotrope</span>

An azeotrope or a constant heating point mixture is a mixture of two or more liquids whose proportions cannot be altered or changed by simple distillation. This happens when an azeotrope is boiled, the vapour has the same proportions of constituents as the unboiled mixture. Because their composition is unchanged by distillation, azeotropes are also called constant boiling point mixtures.

<span class="mw-page-title-main">Water vapor</span> Gaseous phase of water

Water vapor, water vapour or aqueous vapor is the gaseous phase of water. It is one state of water within the hydrosphere. Water vapor can be produced from the evaporation or boiling of liquid water or from the sublimation of ice. Water vapor is transparent, like most constituents of the atmosphere. Under typical atmospheric conditions, water vapor is continuously generated by evaporation and removed by condensation. It is less dense than most of the other constituents of air and triggers convection currents that can lead to clouds.

<span class="mw-page-title-main">Leidenfrost effect</span> Physical phenomenon

The Leidenfrost effect is a physical phenomenon in which a liquid, close to a surface that is significantly hotter than the liquid's boiling point, produces an insulating vapor layer that keeps the liquid from boiling rapidly. Because of this repulsive force, a droplet hovers over the surface, rather than making physical contact with it. The effect is named after the German doctor Johann Gottlob Leidenfrost, who described it in A Tract About Some Qualities of Common Water.

<span class="mw-page-title-main">Heat transfer</span> Transport of thermal energy in physical systems

Heat transfer is a discipline of thermal engineering that concerns the generation, use, conversion, and exchange of thermal energy (heat) between physical systems. Heat transfer is classified into various mechanisms, such as thermal conduction, thermal convection, thermal radiation, and transfer of energy by phase changes. Engineers also consider the transfer of mass of differing chemical species, either cold or hot, to achieve heat transfer. While these mechanisms have distinct characteristics, they often occur simultaneously in the same system.

In chemistry, colligative properties are those properties of solutions that depend on the ratio of the number of solute particles to the number of solvent particles in a solution, and not on the nature of the particles present. The number ratio can be related to the various units for concentration of a solution such as molarity, molality, normality (chemistry), etc. The assumption that solution properties are independent of nature of solute particles is exact only for ideal solutions, which are solutions that exhibit thermodynamic properties analogous to those of an ideal gas and is approximate for dilute real solutions. In other words, colligative properties are a set of solution properties that can be reasonably approximated by the assumption that the solution is ideal.

<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.

This page provides supplementary data to the article properties of water.

<span class="mw-page-title-main">Volatility (chemistry)</span> Tendency of a substance to vaporize

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. Differences in volatility can be observed by comparing how fast substances within a group evaporate when exposed to the atmosphere. A highly volatile substance such as rubbing alcohol will quickly evaporate, while a substance with low volatility such as vegetable oil will remain condensed. In general, solids are much less volatile than liquids, but there are some exceptions. Solids that sublimate such as dry ice or iodine can vaporize at a similar rate as some liquids under standard conditions.

In thermodynamics and chemical engineering, the vapor–liquid equilibrium (VLE) describes the distribution of a chemical species between the vapor phase and a liquid phase.

<span class="mw-page-title-main">Liquid</span> State of matter

A liquid is a nearly incompressible fluid that conforms to the shape of its container but retains a (nearly) constant volume independent of pressure. As such, it is one of the four fundamental states of matter, and is the only state with a definite volume but no fixed shape. A liquid is made up of tiny vibrating particles of matter, such as atoms, held together by intermolecular bonds. Like a gas, a liquid is able to flow and take the shape of a container. Most liquids resist compression, although others can be compressed. Unlike a gas, a liquid does not disperse to fill every space of a container, and maintains a fairly constant density. A distinctive property of the liquid state is surface tension, leading to wetting phenomena. Water is by far the most common liquid on Earth.

References

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