Boiling-point elevation is the phenomenon whereby the boiling point of a liquid (a solvent) will be higher when another compound is added, meaning that a solution has a higher boiling point than a pure solvent. This happens whenever a non-volatile solute, such as a salt, is added to a pure solvent, such as water. The boiling point can be measured accurately using an ebullioscope.
The boiling point elevation is a colligative property, which means that boiling point elevation is dependent on the number of dissolved particles but not their identity. [1] It is an effect of the dilution of the solvent in the presence of a solute. It is a phenomenon that happens for all solutes in all solutions, even in ideal solutions, and does not depend on any specific solute–solvent interactions. The boiling point elevation happens both when the solute is an electrolyte, such as various salts, and a nonelectrolyte. In thermodynamic terms, the origin of the boiling point elevation is entropic and can be explained in terms of the vapor pressure or chemical potential of the solvent. In both cases, the explanation depends on the fact that many solutes are only present in the liquid phase and do not enter into the gas phase (except at extremely high temperatures).
The vapor pressure affects the solute shown by Raoult's Law while the free energy change and chemical potential are shown by Gibbs free energy. Most solutes remain in the liquid phase and do not enter the gas phase, except at very high temperatures.
In terms of vapor pressure, a liquid boils when its vapor pressure equals the surrounding pressure. A nonvolatile solute lowers the solvent’s vapor pressure, meaning a higher temperature is needed for the vapor pressure to equalize the surrounding pressure, causing the boiling point to elevate.
In terms of chemical potential, at the boiling point, the liquid and gas phases have the same chemical potential. Adding a nonvolatile solute lowers the solvent’s chemical potential in the liquid phase, but the gas phase remains unaffected. This shifts the equilibrium between phases to a higher temperature, elevating the boiling point.
Freezing-point depression is analogous to boiling point elevation, though the magnitude of freezing-point depression is higher for the same solvent and solute concentration. These phenomena extend the liquid range of a solvent in the presence of a solute.
The extent of boiling-point elevation can be calculated by applying Clausius–Clapeyron relation and Raoult's law together with the assumption of the non-volatility of the solute. The result is that in dilute ideal solutions, the extent of boiling-point elevation is directly proportional to the molal concentration (amount of substance per mass) of the solution according to the equation: [2]
where the boiling point elevation, is defined as Tb (solution) − Tb (pure solvent).
Non integer i factors result from ion pairs in solution, which lower the effective number of particles in the solution.
Equation after including the van 't Hoff factor
The above formula reduces precision at high concentrations, due to nonideality of the solution. If the solute is volatile, one of the key assumptions used in deriving the formula is not true because the equation derived is for solutions of non-volatile solutes in a volatile solvent. In the case of volatile solutes, the equation can represent a mixture of volatile compounds more accurately, and the effect of the solute on the boiling point must be determined from the phase diagram of the mixture. In such cases, the mixture can sometimes have a lower boiling point than either of the pure components; a mixture with a minimum boiling point is a type of azeotrope.
Values of the ebullioscopic constants Kb for selected solvents: [4]
Compound | Boiling point in °C | Ebullioscopic constant Kb in units of [(°C·kg)/mol] or [°C/molal] |
---|---|---|
Acetic acid | 118.1 | 3.07 |
Benzene | 80.1 | 2.53 |
Carbon disulfide | 46.2 | 2.37 |
Carbon tetrachloride | 76.8 | 4.95 |
Naphthalene | 217.9 | 5.8 |
Phenol | 181.75 | 3.04 |
Water | 100 | 0.512 |
Together with the formula above, the boiling-point elevation can be used to measure the degree of dissociation or the molar mass of the solute. This kind of measurement is called ebullioscopy (Latin-Greek "boiling-viewing"). However, superheating is a factor that can affect the precision of the measurement and would be challenging to avoid because of the decrease in molecular mobility. Therefore, ΔTb would be hard to measure precisely even though superheating can be partially overcome by the invention of the Beckmann thermometer. In reality, cryoscopy is used more often because the freezing point is often easier to measure with precision.
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.
In chemistry, a solution is defined by IUPAC as "A liquid or solid phase containing more than one substance, when for convenience one substance, which is called the solvent, is treated differently from the other substances, which are called solutes. When, as is often but not necessarily the case, the sum of the mole fractions of solutes is small compared with unity, the solution is called a dilute solution. A superscript attached to the ∞ symbol for a property of a solution denotes the property in the limit of infinite dilution." 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.
Osmotic pressure is the minimum pressure which needs to be applied to a solution to prevent the inward flow of its pure solvent across a semipermeable membrane. It is also defined as the measure of the tendency of a solution to take in its pure solvent by osmosis. Potential osmotic pressure is the maximum osmotic pressure that could develop in a solution if it were separated from its pure solvent by a semipermeable membrane.
Raoult's law ( law) is a relation of physical chemistry, with implications in thermodynamics. Proposed by French chemist François-Marie Raoult in 1887, it states that the partial pressure of each component of an ideal mixture of liquids is equal to the vapor pressure of the pure component multiplied by its mole fraction in the mixture. In consequence, the relative lowering of vapor pressure of a dilute solution of nonvolatile solute is equal to the mole fraction of solute in the solution.
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.
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.
An azeotrope or a constant heating point mixture is a mixture of two or more liquids whose proportions cannot be changed by simple distillation. This happens because when an azeotrope is boiled, the vapour has the same proportions of constituents as the unboiled mixture. Knowing an azeotrope's behavior is important for distillation.
In chemistry, solubility is the ability of a substance, the solute, to form a solution with another substance, the solvent. Insolubility is the opposite property, the inability of the solute to form such a solution.
In thermodynamics, activity is a measure of the "effective concentration" of a species in a mixture, in the sense that the species' chemical potential depends on the activity of a real solution in the same way that it would depend on concentration for an ideal solution. The term "activity" in this sense was coined by the American chemist Gilbert N. Lewis in 1907.
In physical chemistry, Henry's law is a gas law that states that the amount of dissolved gas in a liquid is directly proportional at equilibrium to its partial pressure above the liquid. The proportionality factor is called Henry's law constant. It was formulated by the English chemist William Henry, who studied the topic in the early 19th century. In simple words, we can say that the partial pressure of a gas in vapour phase is directly proportional to the mole fraction of a gas in solution.
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 chemical species 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.
Freezing-point depression is a drop in the maximum temperature at which a substance freezes, caused when a smaller amount of another, non-volatile substance is added. Examples include adding salt into water, alcohol in water, ethylene or propylene glycol in water, adding copper to molten silver, or the mixing of two solids such as impurities into a finely powdered drug.
The van 't Hoff factor i is a measure of the effect of a solute on colligative properties such as osmotic pressure, relative lowering in vapor pressure, boiling-point elevation and freezing-point depression. The van 't Hoff factor is the ratio between the actual concentration of particles produced when the substance is dissolved and the concentration of a substance as calculated from its mass. For most non-electrolytes dissolved in water, the van 't Hoff factor is essentially 1.
In thermodynamics, the cryoscopic constant, Kf, relates molality to freezing point depression. It is the ratio of the latter to the former:
François-Marie Raoult was a French chemist who conducted research into the behavior of solutions, especially their physical properties.
Osmotic concentration, formerly known as osmolarity, is the measure of solute concentration, defined as the number of osmoles (Osm) of solute per litre (L) of solution. The osmolarity of a solution is usually expressed as Osm/L, in the same way that the molarity of a solution is expressed as "M".
In thermodynamics, the ebullioscopic constantKb relates molality b to boiling point elevation. It is the ratio of the latter to the former:
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.
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.
An osmotic coefficient is a quantity which characterises the deviation of a solvent from ideal behaviour, referenced to Raoult's law. It can be also applied to solutes. Its definition depends on the ways of expressing chemical composition of mixtures.