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FKKSA, UMP

Multiphase Systems

FKKSA, UMP

Objectives

At the end of this chapter, the students will have: ! Ability to describe physical properties and laws that govern the behavior of two-phase systems. ! Ability to show that these laws must be included in the formulation of material balances on separation process units. ! Ability to describe the concept of phase rules. ! Ability to predict physical properties for multi-component systems, solutions of solids in liquids, and systems containing two immiscible or partially miscible liquids.

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Introduction

! Complete chemical plants normally will be comprised of two important sections: 1. Chemical reaction, followed by 2. Separation of chemical species ! Separation of chemical species can be done physically. ! How to separate physically?

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Separation Processes

! Multiphase systems Mainly involved in separation process ! Distillation !"vapor-liquid ! Driving force of separation : Vapor pressure ! Crystallization !"liquid solid ! Driving force of separation : solubility ! Extraction !"liquid liquid ! Driving force of separation : distribution co efficient.

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A phase diagram of a pure substance is a plot of pressure vs temperature that shows the conditions at which the substance exists as solid, liquid and gas.

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Phase Diagram

! Phase diagram shows that equilibrium not only exist between liquid and gas phase, but also between the solid and liquid phases, and the solid and gas phases of a substance. ! If T and P correspond to a point on the vapor-liquid equilibrium curve for a substance, P is the vapor pressure of the substance at temperature T, and T is the boiling point temperature of the substance at pressure P. ! The boiling point of a substance at P = 1 atm is the normal boiling point of that substance.

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Phase Diagram

! If (T, P) falls on the solid-vapor equilibrium curve, then P is the vapor pressure of the solid at temperature T, and T is the sublimation point at pressure P. ! If (T, P) falls on the solid-liquid equilibrium curve, then T is the melting point or freezing point at pressure P. ! The point (T, P) at which solid, liquid and vapor phases can all coexist is called the triple point of the substance

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! Volatility- degree a to which the species tends to transfer from the liquids 9or solid) state to the vapor state. ! Source of Vapor Pressure Data ! Experimental Data from Literature ! Perrys Handbook ! Journals ( J.Chem.Eng.Data, Fluid Phase Equilibria, ) ! Equations and Coefficients : Antoine Equation, ! Perrys Handbook ! Data Books, Databases , ! From Cox chart (Fig. 6.1-4) ! Estimation from Clausius Clapeyron Equation

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Clausius-Clapeyron Equation

! Clausius-Clapeyron Equation is derived from Clapeyron Eqn by assuming that the specific volume of liquid is negligible relative to that of vapor and heat of vaporization is independent of temperature. Heat of Vaporization

Constant ! ! According to this equation, a plot of ln p* vs 1/T should be a straight line, with slope !Hv/R and intercept B. If you know !Hv/R and p* at a single temperature To, you can solve the constant in Clausius-Clapeyron Eqn. and thereafter use this equation to estimate p* at any temperature close to To. If you have p* vs T data, you can plot ln p* vs 1/T and determine !Hv/R and B graphically or by method of least squares

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! Cox Chart is a straight line graph of logarithm of the vapor pressure plotted against a non uniform temperature scale. (* Refer to textbook for a glimpse on Cox Chart)

! Antoine Equation is a relatively simple empirical equation that correlates very well vapor pressure-temperature.

! A, B and C are Antoine constants (Table B.4) and have specific values for each substances. Antoine Eqn. only applicable in certain temperature limits.

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F = 2 + m -!"

! = the number of phases in a system m = the number of chemical species present F = the number of degrees of freedom

For a reactive system, if r independent reactions occur among the system components and the reactions proceed to equilibrium, then the value of m in this equation must be reduced by r.

Why Gibbs Phase Rule is important? So that we will be able to know the degree of freedom for that particular system and hence the number of intensive variables that can be specified independently for a system that remains at phase equilibrium. ! Extensive variables: Depend on the size of system (e.g. mass and volume) ! Intensive variables: Independent of size (e.g. T, P, y, x) the number of degrees of freedom (the number of intensive variables such as temp, pres, or mol frac that can be changed without disturbing the number of phases in equilibrium) The number of intensive parameters that must be specified in order to completely determine the system

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1. Pure liquid water (F = 2) T & P 2. A mixture of liquid, solid and vapor water (F = 0)- no further information about the system may be specified, triple point at only one temperature and pressure 3. A vapor liquid mixture of acetone and methyl ethyl ketone (F = 2)- set T&P, then mole frac will be fixed; or set T & mole frac, then P will be fixed

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! Processes involving gas-liquid systems ! Evaporation, drying, humidification ! Condensation, dehumidification ! Example

Gas (Water + Nitrogen) Liquid (Water)

! The gas in GLE is called noncondensable . ! The gas phase is saturated with water

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! For this type of system which has water and gas components coexist in 2 phases, Gibbs Rule follows that

F = 2 + 2 -2 = 2

! Only two of three intensive variable, T, P and yH2O can be specified arbitrarily and that some relationship must exist that uniquely determines the value of the third variable once the first two have been fixed.

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! The behavior of gas-liquid systems can be described by following the following Law: ! If a gas at temperature T and pressure P contains a saturated vapor whose mole fraction is yv (moles vapor/ mole total gas), and if this vapor is the only species that would condense if the temperature were slightly lowered, then the partial pressure of the vapor in the gas equals the pure component vapor pressure pv* (T) at the system temperature.

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! A gas in equilibrium with a liquid must be saturated with that liquid. ! The partial pressure of a vapor at equilibrium in a gas mixture containing a single condensable component cannot exceed the vapor pressure of the pure component at the system temperature. If pv = pv*, the vapor is saturated; any attempt to increase pv must instead lead to condensation (pi>p*(T)) ! A vapor present in a gas in less than its saturation amount is referred to as a superheated vapor.

! If a gas containing a single superheated vapor is cooled at constant pressure, the temperature at which the vapor becomes saturated is referred to as the dew point of the gas. ! The difference between the temperature of a gas and its dew point is called the degrees of superheat of the gas.

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Example 6.3-1

Air and liquid water are contained at equilibrium in a closed chamber at 75C and 760mmHg. Calculate the molar composition of the gas phase

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Example 6.3-2

A stream of air at 100C and 5260mmHg contains 10% water by volume. 1. Calculate the dew point and degrees of superheat of the air 2. Calculate the percentage of the vapor that condenses and the final composition of the gas phase if the air is cooled to80C at constant pressure 3. Calculate the percentage condensation and the final gas phase composition if instead of being cooled, the air is compressed isothermally to 8500 mmHg.

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! Saturation refers to any gas-vapor combination. ! Humidity refers specifically to an air-water system ! Relative Saturation (Relative Humidity):

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! Absolute Saturation (Absolute Humidity):

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Example 6.3-3

Humid air at 75C, 1.1 bar and 30% relative humidity is fed into a process unit at rate of 1000 m3/h. Determine 1. Molar flow rate of water, dry air and oxygen entering the process unit 2. The molal humidity, absolute humidity and percentage humidity of air 3. The dew point

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! There are several ways to evaluate equilibrium compositions for multicomponent gas-liquid systems: ! ! ! ! ! From tabulated VLE data Raoults Law and Henrys Law VLE calculation assuming ideal solution Graphical Representations of VLE Rigorous VLE calculation using model equations

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Example 6.4-1

A gas stream consisting of 100 lbmole/h of an SO2-air mixture containing 45mole% SO2 in contacted with liquid water in a continuous absorber at 30C. The liquid leaving the absorber analyzed and found to contain 2 g of SO2 per 100g of H2O. Assuming that the gas and liquid streams leaving the absorber in equilibrium at 30C and 1 atm, calculate the fraction of the entering SO2 absorbed in the water and the required water feed rate.

From Perrys Handbook, the partial pressure of SO2 and H2O at 45 mole% SO2 are: pH2O = 31.6 mmHg pSO2 = 176n mmHg

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pA = yAP = xA p*

A(T)

pA is partial pressure of A in gas phase xA is the mole fraction of A in liquid phase yA is the mole fraction of A in gas phase

! Raoults Law is an approximation that is generally valid when xA is close to 1 that is when the liquid phase is almost pure A. Sometimes, it is valid over the entire range of compositions for mixtures of similar substances, such as straight-chain hydrocarbons of similar molecular weights. HA(T) is the Henrys Law constant for A in specific solvent. Look up from Tables.

pA = yAP = xA HA(T)

! Henrys Law is valid for solutions in which xA is close to 0 (dilute solutions of A) provided that A does not dissociate, ionize, or react in the liquid phase. The law is often applied to solutions of noncondensable gases.

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Example 6.4-2

Use either Raoults law or Henry law to solve the following problems 1. A gas containing 1 mole% ethane is in contact with water at 20C and 20 atm. Estimate the mole fraction of dissolved ethane. 2. An equimolar liquid mixture benzene and toluene is in equilibrium with vapor at 30C. What is the system pressure and composition of vapor?

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! Consider a multi-component mixture in liquid phase with different boiling points. ! As heat being applied, a temperature is reached at which the first bubble of vapor forms. The composition of vapor generated, yA will generally have a composition different from that of the liquid mixture, xA. ! As vaporization proceeds, therefore, the composition of remaining liquid mixture continuously changes as a result of different volatility, and hence so does its vaporization temperature. ! A similar phenomenon occurs if a mixture of vapors is subjected to a condensation process at constant pressure. At some temperature the first droplet of liquid forms, and thereafter the composition of the vapor and the condensation temperature both changes.

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! The temperature at which the first bubble of vapor forms when a liquid is heated slowly at constant pressure is the bubble point of the liquid at the given pressure. ! If a gas-vapor mixture is slowly cooled at constant pressure, the temperature at which the first droplet of liquid forms is the dew point of the gas at the given pressure. How to calculate bubble point and dew point for a mixture? ! If the liquid phase mixture behaves as an ideal solution, we can employ Raoults Law and Henrys Law

i = A, B, .. P = Total pressure

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! Bubble Point temperature calculation ! Given P,x " calculate T,y VLE Calculation ! ! ! ! Bubble T Bubble P Dew T Dew P : : : : P,x T,x P,y T,y " " " " T,y P,y T,x P,x

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HINT: To choose a BASE TEMPERATURE, you can check the main component in the mixture and use the boiling point of that component

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# xi = 1 ???

COMPLY ! xi=yiP/pi*(Tdp)

Contradict

Contradict

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Example 6.4-3

1. Calculate the temperature and composition of a vapor in equilibrium with a liquid that is 40 mole% benzene-60 mole% toluene at 1 atm. Is the calculated temperature a bubble point or dew point temperature? 2. Calculate the temperature and composition of liquid in equilibrium with a gas mixture containing 10 mole% benzene, 10 mole% toluene and balance nitrogen (which may be considered noncondensable) at 1 atm. Is the calculated temperature a bubble point or dew point temperature? 3. A gas mixture consisting of 15 mole% benzene, 10 mole% toluene and 75 mole% nitrogen is compressed isothermally at 80C untill condensation occurs. At what pressure will condensation begin? What will be the composition of the initial condensate?

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! A mixture of two different solution is termed miscible if a single phase results from the mixing at all concentrations. ! A system is partially miscible if the two different liquids form a single phase at certain composition and form two liquid phases at other concentrations. ! A system is immiscible if it forms two liquid phases even at lean concentration of other component. ! If a third substance is added to a two-phase liquid mixture, it distributes itself according to its relative solubility in each phase. ! What is distribution coefficient? ! Liquid extraction is a common chemical separation process employed in industry that is based on miscibility concept.

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Distribution Coefficient

Water Rich Phase

Acetone

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Ternary Diagram

! A system which contains 3 components with different solubility affinity is termed as Ternary System. ! In a system composed of A and S that are nearly immiscible liquids, and B is a solute distributed between the phases of an A-S mixture, the distribution coefficient for component B is the ratio of the mass fraction of B in the S phase to that in the A phase. ! The behavior of this partially miscible ternary system systems is frequently represented on a Triangular Phase Diagram (TPD). ! Lever rule is needed to perform mass balance calculation based on this TPD.

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Ternary Diagram

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Example 6.6-2

1000 kg of a 30 wt% solution of acetone in water and a second stream of pure methyl isobutyl ketone (MIBK) id fed to a mixer. The mixture is then fed to a settler where two phases form and are withdrawn separately at 25C. How much MIBK must be fed to the process to reduce the acetone concentration in the water-rich phase to 5 wt%, assuming that the fluids remain in the settler long enough for equilibrium to be achieved?

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