Basic concepts in distillationVapor pressure + + vapor pressure * + Vapor pressure is an important property of liquids. a . a It indicates how easily the liquid is evaporating. ee . - Vapor pressure is strongly dependent on the temperature. The weaker the intermolecular forces are, the higher is the vapor pressure. The amount of liquid does not affect the vapor pressure. » When the vapor pressure is equal to the pressure surrounding the liquid, the liquid boils. + Vapor pressures can be found in databases, or they can be calculated by Antoine’s equation. Picture: HalfTchi CCBY-SA 3.0Antoine equation The Antoine equation is a class of semi- empirical correlations describing the relation between vapor pressure and temperature for pure substances. Example: Find out the vapor pressure cof benzene at the temperature of 50 °C. Coefficents for benzene at 50 °C are A = 4.01814, B = 1203.835, C = -53.226 Units: temperature K and pressure bar. 1203,835 P= 10*91814~333.15-53.226 = 0.362 bar = 36,2 kPa P} = vapor pressure of pure i T= temperature A, Band € are coefficients of a specific substance. They can be found in literature. It is eructal to check the units used and use the correct units in temperature, tao. Parameters can be found eg, from here: ‘webbook.nist.gov/cherDalton's law + Inthe mixture of gases, the pressure of each component is called a partial pressure (p)). In the ideal gases p, = y;P + Dalton’s law says that the total pressure is the sum of partial pressures. Picture Andrew Jarvis CC BY-SA 4.0 n P= Pat Ppt wt Pn =) i P = total pressure P; = partial pressure of component i p= iP Yi = mole fraction of component i Ideal gas law can also be used with one component: PaV = n4RT Pa = partial pressure of component A y= amount of substance A (mol)Raoult's law * Raoult's law 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. p; = x; p' When you combine the Dalton’s law and the Raoult's law, you will get useful expressions for total pressure and the mole fraction in vapor. Raoult's law has many limitations. It only applies to ideal solutions and the vapor should act like ideal gas. ' Pi = iP i p; = partial pressure of component i p'; = vapor pressure of pure i at the same temperature x; = mole fraction of component i in liquid Combination of Raoult’s law and Dalton’s law:Relative volatility Relative volatility is a measure comparing the vapor pressures of two components in a liquid mixture of chemicals. Common symbol for relative volatility is a. It is a unitless quantity. vapor pressure of more volatile component ~ ‘Vapor pressure of less volatile component + When a = 1, separation by distillation would be impossible. The greater the value, the easier is the separation by distillation. + In ideal solutions, the relative volatility can be expressed in different forms by using Raoult's law and Dalton’s law. Pa _ PalXa _PaXe _ YaPXp _ YaCl — Xa) Pe PalXn Pata YaPXa X4(1— Ya)Vapor-liquid equilibrium (VLE) + Vapor-liquid equilibrium (VLE) describes the distribution of a chemical species between the vapor phase and a liquid phase under a given set of conditions. A binary system has two degrees of freedom. In distillation, the pressure is usually fixed. If we fix also the liquid composition, the temperature and vapor composition will be automatically fixed. + VLE data can be expressed in tables or in " i VLE diagram of ethanol and water at diagrams. These are discussed more 4 atm, (http:/worw.vle- detailed in next chapters. cale.comiphase_diagrarn him!)Te References Dutta, B. K. 2007. Principles of mass transfer and separation processes. New Delhi: Prentice-Hall, pp. 321-322 Hipple, Jack. 2017. Chemical Engineering for Non-Chemical Engineers. American Institute of Chemical Engineers, pp. 146-147. Vapor-Liquid Equilibrium calculator. Available at: http://www. vie-calc.com/phase_diagram.htm! [Assessed: 14 June, 2021]. Videos: + Partial pressure vs. vapor pressure: https://youtu.be/QVKOyKJx6FM (3:56) a + Distillation, vapor pressure and volatility: https://youtu,be/sNUYWvXGhig (4:03) e ~! + Vapor Liquid equilibrium for binary systems: htips://yvoutu.be/hl_zqt2Minoc (7:08) poate rongton Eon ene 2) *e