A static condition whereby no changes occur in the macroscopic
properties of a system with time is referred to as equilibrium. The assumption of equilibrium is justified when it leads to the results of satisfactory accuracy.
A system that is isolated consisting of liquid and vapor phases in
intimate contact will eventually reaches a final state where no tendency exist for change to take place within the system.
Macroscopic properties (temperature, pressure, and phase
compositions) reaches a final values which thereafter remain fixed, such system has attained equilibrium. Nature of Equilibrium
Conditions are not static at microscopic level as compared to
macroscopic level. The molecules comprising a phase at a given instant are not the same molecules that later occupy the same phase.
Molecules that are near the interface having sufficiently high
velocities overcome surface forces and pass into the other phase.
The average rate of passage of molecules is the same in both
directions, and no net interphase transfer of material occur. Measure of Composition Just like we have shown in mixture compositions, three most common measures of composition are mass fraction, mole fraction, and molar concentration.
Mass or mole fraction is defined as the ratio of mass or the
number of moles of a particular chemical species in a mixture or solution to the total or number of moles of the mixture or solution. 𝑚𝑖 𝑚ሶ 𝑖 𝑛𝑖 𝑛ሶ 𝑖 𝑥𝑖 ≡ = 𝑥𝑖 ≡ = 𝑚 𝑚ሶ 𝑛 𝑛ሶ
Molar concentration is defined as the ratio of the mole fraction of
a particular chemical species in a mixture or solution to its molar volume.
𝑥𝑖 𝐶𝑖 ≡ 𝑉 Measure of Composition The molar concentration has units of mole of i per unit volume. For flow processes convenience suggest its expression as a ratio of rates. Multiplying and dividing by molar flow rate gives
𝑛ሶ 𝑖 𝐶𝑖 = 𝑞 Where 𝑛ሶ 𝑖 is molar flow rate of species i, and q is the volumetric flowrate. The molar mass of a mixture or solution is by definition the mole fraction weighted sum of the molar masses of all species present.
𝑀 = σ𝑖 𝑥𝑖 𝑀𝑖 Vapor Liquid Equilibrium (VLE)
Vapor/liquid equilibrium (VLE) is the state of coexistence of liquid
and vapor phases When thermodynamics is applied to VLE, the goal is to find by calculations the temperature, pressure, and compositions of the phases in equilibrium. Such is accomplished by the use of models that represents the behaviour of the system in vapor/liquid equilibrium. The two simplest models are Raoult’s law Henry’s law Raoult’s Law Two major assumptions are required to reduce VLE calculations to Raoult’s law. The vapor phase is an ideal gas The liquid phase is an ideal solution
The first assumption means that Raoult’s law can apply to low to moderate pressures. The second implies that it can have approximate validity only when the species that comprise the system are chemically similar. The mathematical expression which reflects the above two listed assumptions, and which therefore gives quantitative expression to Raoult’s law is 𝑦𝑖 𝑃 = 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡 1 Raoult’s Law
Where 𝑥𝑖 is a liquid phase mole fraction, 𝑦𝑖 is a vapor phase
mole fraction, and 𝑃𝑖𝑠𝑎𝑡 is the vapor pressure of pure species i at the temperature of the system. The product 𝑦𝑖 𝑃 on the left side of equation 1 is known as the partial pressure of species i.
The simple model for VLE represented by equation 1 provides a
realistic description of actual behaviour for a relatively small class of systems. Raoult’s Law
A limitation of Raoult’s law is that it can be applied only to
species for which a vapor pressure is known, and this requires that the species be subcritical (the temperature of application be below the critical temperature of the species).
Application of Raoult’s law is valid for any species present at a
mole fraction approaching unity, provided only that the vapor phase is an ideal gas. Dew-Point and Bubble-Point Calculations with Raoult’s Law Although VLE problems with other combinations of variables are possible, engineering interest centres on dew-point and bubble- point calculations. For bubble pressure: calculate 𝑦𝑖 and P, given 𝑥𝑖 and T.
For bubble temperature: calculate 𝑦𝑖 and T, given 𝑥𝑖 and P.
For dew pressure: calculate 𝑥𝑖 and P, given 𝑦𝑖 and T.
For dew temperature: calculate 𝑥𝑖 and T, given 𝑦𝑖 and P.
Dew-Point and Bubble-Point Calculations with Raoult’s Law Calculations are made for conditions where simplifying assumption prevail. The general procedures for solutions of VLE problems thus become evident through calculations of relative simplicity. From equation 1, noting that σ𝑖 𝑦𝑖 = 1
𝑃= 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡 2 𝑖
The above equation finds application in bubble-point
calculations, where the vapor-phase composition in unknown. For binary system with 𝑥2 = 1 − 𝑥1 𝑃 = 𝑃2𝑠𝑎𝑡 + 𝑃1𝑠𝑎𝑡 − 𝑃2𝑠𝑎𝑡 𝑥1 3
A plot of P vs 𝑥1 at constant temperature is a straight line
connecting 𝑃2𝑠𝑎𝑡 at 𝑥1 = 0 with 𝑃1𝑠𝑎𝑡 at 𝑥1 = 1. Dew-Point and Bubble-Point Calculations with Raoult’s Law Equation 1 may also be solved for 𝑥𝑖 and assumed over all species. With σ𝑖 𝑥𝑖 = 1, which yields
1 𝑃= 𝑦𝑖 4 σ𝑖 ൘ 𝑠𝑎𝑡 𝑃 𝑖
Equation 4 apply in dew point calculations, where liquid phase
compositions are not known. Vapor Liquid Equilibrium (VLE) The plots of vapor fraction vs liquid fraction for either the constant pressure is shown in Figure 1a or the constant temperature as shown in Figure 1b for a binary system.
The upper surface is the bubble line in both plots and the under surface is the dew line. Tutorial Question 1 Calculate the vapor and liquid compositions in equilibrium at 95oC for benzene-toluene using the vapor pressure from the table below at 101.32 kPa. Question 2
Binary system acetonitrile(1)/nitromethane(2) conforms closely to
Raoult’s law. Vapor pressure for the pure species are given by the following Antoine equations
𝑙𝑛𝑃1𝑠𝑎𝑡ൗ 2945.47 𝑘𝑃𝑎 = 14.2724 − 𝑇−49.15
𝑙𝑛𝑃2𝑠𝑎𝑡ൗ 2972.64 𝑘𝑃𝑎 = 14.2043 − 𝑇−64.15
Prepare a graph showing P vs xi and P vs yi for a temperature of
348.15 K Ans: P = 41.98 kPa for x1 = 0.0 P = 66.72 kPa for x1 = 0.6 Henry’s Law
The application of Raoult’s law to species i requires a value for
𝑃𝑖𝑠𝑎𝑡 at the temperature of application.
Thus, it is not appropriate for a species whose critical
temperature is less than the temperature of application.
If a system of air in contact with liquid water is presumed at
equilibrium, then the air is saturated with water.
The mole fraction of water vapor in the air is usually found from Raoult’s law applied to the water with the assumption that no air dissolves in the liquid phase. Henry’s Law The liquid water is regarded as pure and Raoult’s law for the water (species 2) becomes 𝑦2 𝑃 = 𝑃2𝑠𝑎𝑡 5 At 298.15 K and atmospheric pressure, equation 5
𝑃2𝑠𝑎𝑡 3.166 𝑦2 = = = 0.0312 𝑃 101.33
Where the pressures are in kPa, and 𝑃2𝑠𝑎𝑡 comes from the steam tables. If one wishes to calculate the mole fraction of air dissolved in the water, then Raoult’s law cannot be applied, because the critical temperature of air is much lower than 298.15 K. Henry’s Law Tutorial Question 3
Assuming that carbonated water contains only CO2 and H2O,
determine the compositions of the vapor and liquid phases in a sealed can of soda and the pressure exerted on the can at 283.15 K. Henry’s constant for CO2 in water at 283.15 K is about 990 bar. VLE by Modified Raoult’s Law For low to moderate pressures a much realistic equation for VLE results when the second major Raoult’s law assumption is abandoned, and account is taken of deviations from solution ideality in the liquid phase by a factor inserted into Raoult’s law, modified to read 𝑦𝑖 𝑃 = 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 (i = 1,2,….N) 6 Where 𝛾𝑖 is called an activity coefficient. Bubble-point and dew-point calculations made with this equation are only a bit more complex than the same calculations made with Raoult’s law. From equation 6, with σ𝑖 𝑦𝑖 = 1
𝑃= 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 7 VLE by Modified Raoult’s Law Equation 6 may be solved for 𝑥𝑖 , in which case summing over all species yields. 1 𝑃= σ𝑖 𝑦𝑖ൗ 𝑠𝑎𝑡 8 𝛾𝑖 𝑃𝑖 Tutorial Question 4 For the system methanol(1)/methyl acetate(2), the following equations provide a reasonable correlation for the activity coefficients.
ln 𝛾1 = 𝐴 𝑥22 ln 𝛾2 = 𝐴 𝑥12, where A = 2.771 – 0.00523T
In addition, the following Antoine equations provide vapor pressures:
Where the vapor pressures is in kPa and T is in kelvins. Assuming the validity of modified Raoult’s law, calculate
a) P and (𝑦𝑖 ), for T = 318.15 K and 𝑥𝑖 = 0.25
b) T and (𝑦𝑖 ), for P = 101.33 kPa and 𝑥𝑖 = 0.85
Ans: (a) 73.50 kPa; y1 = 0.282; y2 = 0.282
(b) 62. 89 kPa; x1 = 0.8169; x2 = 0.1831
VLE from K-Value Correlations The tendency of a given chemical species to partition itself preferentially between liquid and vapor is the equilibrium ratio Ki, defined as 𝑦𝑖 𝐾𝑖 = 9 𝑥𝑖 This quantity 𝐾𝑖 serves as a measure of the lightness of a constituent species, i.e., of its tendency to favor the vapor phase.
When 𝐾𝑖 is greater than unity, species i exhibits a higher
concentration in the vapor phase. When less, a higher concentration in the liquid phase, and is considered a heavy constituent.
The use of K-values allows the elimination of one set of mole
fractions 𝑦𝑖 or 𝑥𝑖 in favor of the other. VLE from K-Value Correlations From Raoult’s law, it shows that K-values is 𝑃𝑖𝑠𝑎𝑡 𝐾𝑖 = 10 𝑃 Introducing the modified Raoult’s law shows that 𝑦𝑖 𝑃𝑖𝑠𝑎𝑡 𝐾𝑖 = 11 𝑃
According to equation 9, 𝑦𝑖 = 𝐾𝑖 𝑥𝑖 ; because σ𝑖 𝑦𝑖 = 1, then
σ𝑖 𝐾𝑖 𝑥𝑖 = 1 12 For bubble-point calculations, where 𝑥𝑖 are known, the problem is to find the set of K-values that satisfies equation 12. Alternatively, equation 9 can be written 𝑥𝑖 = 𝑦𝑖 /𝐾𝑖 because σ𝑖 𝑥𝑖 = 1, then 𝑦 σ𝑖 𝑖 = 1 13 𝐾𝑖 For dew-point calculations, where 𝑦𝑖 are known, the problem is to find the set of K-values that satisfies equation 13. Tutorial Question 5 For a mixture of 10 mol-% methane, 20 mol % ethane and 70 mol % propane at 283 K, determine The dew point pressure The bubble point pressure Flash Calculations Flash calculation is an important application of VLE. A liquid at a pressure equal to or greater than its bubble-point pressure flashes or partially evaporates when the pressure is reduced, producing a two phase system of vapor and liquid in equilibrium.
It will be considered here only the P, T-flash which refers to any
calculation of the quantities and compositions of the vapor and liquid phase making up a two-phase system in equilibrium at known T, P and overall composition. Flash Calculations A system containing one mole of non-reacting chemical species with an overall compositions represented by the set of mole fractions zi. Let L be the moles of liquid, with mole fractions xi, F the moles of initial feed, and let V be the moles of vapor, with mole fractions yi. The material balance equations becomes
F=L+V 1 Component balance Fzi = xiL + yiV 2
Introducing yi = xiK from K-value correlation and solving for yi
𝐹𝑧𝑖 𝐹 𝑧𝑖 𝑥𝑖 = = 𝐿 3 𝐾𝑖 𝑉+𝐿 𝑉 𝐾𝑖 +( ) 𝑉
Since sum of 𝑥𝑖 = 1, equation 3 is summed over all species
𝑧𝑖 𝑉 σ𝑖 = 4 𝐾𝑖 +(𝐿/𝑉) 𝐹 Flash Calculations Equation 4 can be used for the calculation of T, P or fractional vaporization in an iterative procedure. Eliminating xi from equation 2, leads to
Fzi = xiL + yiV 2
𝐹𝑧𝑖 𝐹 𝑧𝑖 𝑦𝑖 = 𝐿 = 5 𝑉+( ) 𝑉 1+( 𝐿 ) 𝐾𝑖 𝑉𝐾𝑖
Since sum of 𝑦𝑖 = 1, equation 5 is summed over all species
𝑧𝑖 𝑉 σ𝑖 𝐿 = 6 1+( ) 𝐹 𝑉𝐾𝑖
Equation 6 can also be utilized in an iterative procedure to
estimate T, P or the fraction of the initial mixture that is vaporised. Tutorial Question 6
The system acetone(1)/acetoneitrate(2)/nitromethane(3) at 353.15
K and 110 kPa has the overall composition z1 = 0.45, z2 = 0.35 z3 = 0.20. Assuming that Raoult’s law is appropriate to the system, determine L, V and xi and yi. The vapor pressures of the pure species at 353.15 K are
Question 7 A hydrocarbon mixture contains 25% (mol) propane, 40% (mol) n-butane and 35% (mol) n-pentane at 1447.14 kPa. Assume ideal solution behavior and calculate a) The bubble-point temperature and composition of the vapor b) The dew-point temperature and the composition of the liquid c) The temperature and the composition of the liquid and vapor in equilibrium when 45% (mol) of the initial mixture is vaporized.
