VAPOUR LIQUID EQUILIBRIA & DEW POINT CALCULATIONS

THERMODYNAMICS II PROJECT CHE - 03

Group Members Afnan Amjad Haseeb Hayat Hassan Raza Malik Zeeshan Tariq Muhammad Irfan Muhammad Salman Mudassir Sultan Muhammad Zubair

Mubashir Khizar Abbasi

Vapor-Liquid Equilibrium Definition Vaporliquid equilibrium (VLE) is a condition where a liquid and its vapor (gas
phase) are in equilibrium with each other, a condition or state where the rate of evaporation (liquid changing to vapor) equals the rate of condensation (vapor changing to liquid) on a molecular level such that there is no net (overall) vapor liquid inter-conversion. A substance at vaporliquid equilibrium is generally referred to as a saturated fluid. For a pure chemical substance this implies that it is at its boiling point. The notion of "saturated fluid" includes saturated liquid (about to vaporize), saturated liquidvapor mixture, and saturated vapor (about to condense).

Explaination
When a liquid such as water or alcohol is exposed to air in an open container, the liquid evaporates. This happens because the distribution of speeds (and hence kinetic energies) among molecules in a liquid is similar to that illustrated for gases, shown again below.

At any given instant a small fraction of the molecules in the liquid phase will be moving quite fast. If one of these is close to the surface and is traveling upward, it can escape the attraction of its fellow molecules entirely and pass into the gas phase. As the higher energy molecules depart, the average energy of the molecules in the liquid decreases and the temperature of the liquid falls. Heat energy will be absorbed from the surroundings. Absorption of heat maintains the average molecular speed in the liquid, so that, given enough time, all the liquid can

evaporate. The heat absorbed during the entire process corresponds to the enthalpy of vaporization. If the liquid is placed in a closed, rather than an open, container, we no longer find that it evaporates completely. Once a certain partial pressure of gas has been built up by the evaporation of liquid, no more change occurs, and the amount of liquid remains constant. The partial pressure attained in this way is called the vapor pressure of the liquid. It is different for different liquids and increases with temperature for a given liquid. So long as some liquid is present, the vapor pressure is always the same, regardless of the size of the container or the quantity of liquid.

Example
We find that any size sample of water held at 25C will produce a vapor pressure of 23.8 mmHg (3.168 kPa) in any closed container, provided only that all the water does not evaporate. On the macroscopic level, once the vapor pressure has been attained in a closed container, evaporation appears to stop.

The

amount of vapor remains the same only because molecules are reentering the liquid just as fast as they are escaping from it. The molecules of the vapor behave like any other gas: They bounce around colliding with each other and the walls of the container. However, one of these walls is the surface of the liquid. In most cases a molecule colliding with the liquid surface will enter the body of the liquid, not have enough energy to escape, and be recaptured. When the liquid is first introduced into the container, there are very few molecules of vapor and the rate of recapture will be quite low, but as more and more molecules evaporate,

The Chances of a recapture will become proportionately larger. Eventually the vapor pressure will be attained, and the rate of recapture will exactly balance the rate of escape. There will then be no net evaporation of liquid or condensation of gas. Once the vapor-liquid system has attained this state, it will appear on the macroscopic level not to be undergoing any change in its properties. The amount, the volume, the pressure, the temperature, the density, etc. of both liquid and gas will all remain constant with time. When this happens to a system, it is said to be in equilibrium state or to have attained equilibrium. Later, we will encounter many other quite different examples of equilibrium, but they all have one property in common. The lack of change on the macroscopic level is always the result of two opposing microscopic processes whose rates are equal. The effect of each process is to nullify the effect of the other. Since both microscopic processes are still in motion, such a situation is often referred to as dynamic equilibrium. The magnitude of the vapor pressure of a liquid depends mainly on two factors: The strength of the forces holding the molecules together The temperature. It is easy to see that if the intermolecular forces is weak, the vapor pressure will be high. Weak intermolecular forces will permit molecules to escape relatively easily from the liquid. The rate at which molecules escape will thus be high. Quite a large concentration of molecules will have to build up in the gas phase before the rate of reentry can balance the escape rate. Consequently the vapor pressure will be large. By contrast, strong intermolecular forces result in a low escape rate, and only a small concentration of molecules in the vapor is needed to balance it. The vapor pressure of a liquid is quite a sensitive indicator of small differences in intermolecular forces The other major factor governing the magnitude of the vapor pressure of a liquid is temperature. At a low temperature only a minute fraction of the molecules have enough energy to escape from the liquid. As the temperature is raised, this fraction increases very rapidly and the vapor pressure increases with it, which makes sense given our previous discussion on temperature and gases. The higher the temperature, the higher will be the increase of the energetic fraction of molecules. The result is a variation of vapor pressure with temperature. Note from this figure how the vapor-pressure increase for a 10C increase in temperature is larger at higher temperatures.

Equilibrium between solid and vapor (Sublimation curve)

At the point B ice is in equilibrium with its Vapor. The pressure at B is the Vapor pressure of ice at the temperature at B. If this temperature at B is gradually raised keeping the volume constant, Vapor pressure of ice also increases. If the Vapor pressure of ice is plotted against temperature, the curve BO, the sublimation curve is obtained. Along the curve BO, ice and water Vapor are in equilibrium with each other. The slope of the curve at any point is given by the Clapeyron. If the system is expanded isothermally, then this will decrease the pressure of the Vapor phase. As at a given temperature, the solid-Vapor system has a fixed Vapor pressure, some ice will sublime to maintain the pressure. If the isothermal expansion is continued, more and more ice will sublime till the solid phase disappeared. If, on the other hand, the system represented by point B is compressed isothermally, then some Vapor will condense to form ice in order to maintain the pressure and prevent its increase. If the isothermal compression is continued, then the entire Vapor phase will disappear leaving only a solid phase in the system.

These show that the regions above and below the curve BO represent solid and Vapor phases, respectively.

Equilibrium between liquid, Vapor and solid water (ice)

The system at point B is gradually heated keeping the volume constant when theVapour pressure of ice increases. A temperature is reached at which the Vapor pressure of ice becomes equal to that of liquid water maintained at the same temperature. Then the solid water starts melting and the system consists of three phases, ice, water and Vapor, in equilibrium with each other. This is an invariant system (F=0) and the temperature and pressure of the system remain unchanged as long as all the three phases are present together, is known as triple point. This point for water lies at 0.0075 and 4.6mmHg.

Equilibrium between liquid and Vapor (Vaporization curve)

The system at the triple point is gradually heated at constant volume; the temperature and pressure do not change till the entire solid melts to give liquid water. There are only 2 phases in the system liquid water and Vapor. If the heating is continued at constant volume, the temperature and Vapor pressure of the system vary along the curve OA. The curve OA is known as the vaporization curve and along the curve OA liquid water and Vapor are in equilibrium with each other. The slope of the curve OA at any point is given by the Clapeyron equation. Mathematically,

If a system is subjected to isothermal expansion, then the pressure of the Vapor phase decreases, a small quantity of water evaporates to raise the pressure to a value which is the Vapor pressure of liquid water at that temperature. As the isothermal expansion is continued, more and more liquid water evaporates till the entire liquid phase disappears and the system is made up of only Vapor.

Data Calculations
Following data are required and we find them by a series of calculations explained later: 1. Partial Pressure 2. Composition of the mixture for which calculations are done

In mixtures containing two or more components where their concentrations are compared in the vapor and liquid phases, concentrations of each component are often expressed as mole fractions. A mole fraction is number of moles of a given component in an amount of mixture in a phase (either vapor or liquid phase) divided by the total number of moles of all components in that amount of mixture in that phase. The equilibrium concentration of each component in the liquid phase is often different from its concentration (or vapor pressure) in the vapor phase, but there is a correlation. Such VLE concentration data is often known or can be determined experimentally for vaporliquid mixtures with various components. In certain cases such VLE data can be determined or approximated with the help of certain theories such as Raoult's Law, Dalton's Law and/or Henry's Law.

Thermodynamics Explanation
For pure systems having single component: ; ; For multi-component systems: ; ; Where P represents pressure, T represents temperature and G represents the partial molar Gibbs free energy. Liq represents liquid state and vap is the vapour state of the given component in the mixture. Gibbs free energy is calculated by:

Where G is the extensive Gibbs free energy, and ni is the amount of substance of component i.

Dew Point Introduction

The dew point is the temperature below which the water
vapor in a volume of humid air at a constant barometric pressure will condense into liquid water. Condensed water is called dew when it forms on a solid surface.

The dew point is a water-to-air saturation temperature. The dew point is associated with relative humidity. A high relative humidity indicates that the dew point is closer to the current air temperature. Relative humidity of 100% indicates the dew point is equal to the current temperature and that the air is maximally saturated with water. When the dew point remains constant and temperature increases, relative humidity decreases. When a liquid mixture begins to boil, the vapor does not normally have the same composition as the liquid. The components with the lowest boiling point (i.e. the more volatile) will preferentially boil off. Thus, as the liquid continues to boil, the concentration of the least volatile component drops. This results in a rise in the boiling point. The temperatures over which boiling occurs set the bubble and dew points of the mixture. The bubble and dew points can be defined as: 1. The bubble point is the point at which the first drop of a liquid mixture begins to vaporize. 2. The dew point is the point at which the first drop of a gaseous mixture begins to condense. For a pure component, the bubble and dew point are both at the same temperature its boiling point. For example, pure water will boil at a single temperature (at atmospheric pressure, this is 100C). For ideal mixtures (i.e. mixtures where there are no significant interactions between the components), vapor-liquid equilibrium is governed by Raoult's Law and Dalton's Law.

Measurements
When the relative humidity is above 50% we can use the following formula:

and

Considering the temperature in Celsius. RH represents the relative humidity.

Methods of Calculations
Calculating Bubble & Dew Points for Ideal Mixtures

Raoult's Law
Raoult's Law states that the partial pressure of a component, PA, is proportional to its concentration in the liquid. So for component A, PA=PoA.XA Where PA=partial pressure of component A PoA= Vapour pressure of component A XA= Liquid mole fraction of component A

Dalton's Law
Dalton's Law states that the total pressure is equal to the sum of the component partial pressures. Thus for component A, its partial pressure, PA, is proportional to its mole fraction in the gas phase PA=YA.PTotal Where PTotal=Total System Pressure yA=vapour mole fraction of component A

Dew Point Calculation

The dew point is the temperature at which a gas mixture will start to condense. For an ideal mixture, we can use Dalton's and Raoult's Laws to calculate the dew point. By combining the two equations, we can calculate the liquid mole fractions for a given vapour composition, i.e. XA=YA.PTotal/PoA The pure component vapour pressures can then be used to calculate the liquid mole fraction for each component, x, using the above equation. The sum of all the liquid mole fractions should add up to 1 at the dew point. If the sum is greater than 1, the temperature guess is too low. If the sum is less than 1, the temperature guess is too high. Adjust the temperature until the liquid mole fractions add up to 1.

Example Calculation Estimating the Dew Point

A gas has the following composition: 75mol% n-pentane, 20mol% n-hexane, 5mol% n-heptane. What is its Dew Point at atmospheric pressure (760 mmHg)? The normal boiling points of pentane, hexane and heptane are 36C, 69C and 98C respectively, so the dew point at atmospheric pressure will lie within this temperature range. As a first guess, take a temperature of 40C.The vapour pressure of each component can be estimated using their Antoine Equation (see our separate article). So at 40C, the vapour pressure of each component is as follows:

Assuming ideal behaviour, the liquid mole fractions at the dew point can be calculated using:

Thus

Adding the vapour mole fractions together gives: 0.857 + 0.074 + 0.006 = 0.937. This is less than 1, meaning that 40C is below the bubble point. Re-guessing the temperature at 50C, 45C, 42C and 41C

Temperature 40oC yPentane yHexane yHeptane Total 0.857 0.074 0.006 0.937

50oC 1.183 0.107 0.009 1.299

45oC 1.011 0.089 0.008 1.108

42oC 0.918 0.080 0.007 1.005

41oC 0.888 0.077 0.006 0.971

Dew point calculation with Raoult's law

We can also find dew point using modified form of Raoult's law which is given as

yAP = xAPA*(T)
Raoult's Law and for each component yAP = xAPA*(T) Raoult's Law for component A yBP = xBPB*(T) Raoult's Law for component B by adding both equations we get yA / PA*(T) + yB / PB*(T) = 1/P We then find the composition from Raoult's Law xA = yAP / PA*

Example
What is the dew point pressure of a mixture containing 40 mol% n-pentane and 60 mol% n-hexane at 121C and what is the composition of the first droplets of liquid that begin to condense?

Solution
The vapor pressures are the same as in the above bubble-point problem because the temperature is still 121C. However, now we want to eliminate x from the two Raoult's Law equations because we know y values. Therefore we can use the expression derived above:

yA / PA*(T) + yB / PB*(T) = 1/P = 0.4/3059 + 0.6/666 = 0.001032 / mm Hg Thus,

P = mm Hg/0.001032 = 969.3 mm Hg We then find the composition from Raoult's Law xA = yAP / PA* = (0.4)(969.3)/3059 = 0.127 Dew point calculation using modified Raoult's law with Gamma & pi: We can also find dew point using modified Raoult's law with Gamma & phi. This is given as P=(Xi.gammai.Pisat)/phii to find gamma,phi,Psat we use other complex equations and then put it in main equation to find dew point pressure.