Enthalpy Concentration Diagram

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Enthalpy Concentration Diagram

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CONCENTRATION

DIAGRAMS

BMS College of Engineering

Department of Chemical Engineering

Self Study Presentation

Mass Transfer - 2

Anas Zainuddin Assistant Professor

Aman Bhuwania BMS College of

Akshay B.V Engineering1

INTRODUCTION:

• In general in a distillation calculation we

assume constant molal over flow for our

distillation column design, but in a H-x-y

there is variation of liquid and vapor flow

rates which depends on the enthalpies of the

liquid and vapor mixtures. So, this

limitation can be eliminated, if we use

enthalpy balance with the material balance.

2

Contd.

• So, this is a typical enthalpy concentration diagram shown over here, and as we know

during distillation, the change of phase occurs which changes the composition in turn

changing the enthalpy. So, this is the vapor liquid equilibria plots for binary system.

• So, the enthalpy concentration diagram is plotted at constant pressure, and each point on

this enthalpy concentration diagram represents different temperature. The upper curve is

HV versus y which is a plot of saturated vapor enthalpy versus vapor composition. And

the lower curve is the saturated liquid composition curve HL versus x where HL is the

saturated liquid enthalpy and x is the liquid composition. Now, for any given composition

the difference between these two curves at a given composition is the latent heat of

vaporization.

• Now, inside these two curves is a two phase mixture, and between these two curves

constant temperature tie lines are provided. AB is one such tie line.

3

HO DO WE GET AN ENTHALPY

CONCENTRATION DIAGRAM?

• Binary vapour-liquid equilibria can also be plotted on coordinate of enthalpy vs

concentration at constant pressure. Liquid-solution enthalpy includes both sensible heat

and the heat of mixing the components.

H L CL tL t M av H S

*

• Where CL is the heat capacity of the solution, energy/(mol) (degree), and is the heat of

solution at to and the prevailing concentration referred to the pure liquid components,

energy/mol solution. For saturated liquids, tL is the bubble point corresponding to the

liquid concentration at the prevailing pressure. If the heat evolved on mixing, will be

negative, and for ideal solution it is zero. For ideal solutions, the heat capacity is the

weighted average of those for the pure components.

4

Contd.

assuming that the unmixed liquids are heated separately as liquids to the gas temperature

tG ,the dew point , each vaporized at this temperature, and the vapours mixed.

• Where λA and λB are the latent heat of the vaporization of pure substances at tG in the

energy per mole and CL,A and CL,B are the heat capacities of pure liquids,

energy/(mole)(degree).

5

Contd.

• In the fig. 2 which represents a typical binary mixture, the enthalpies of saturated vapours

at their dew points have been plotted vs y and those of the saturated liquids at their bubble

point vs x. The vertical distances between the two curves at x=0 and 1 represents ,

respectively, the molar latent heats of B and A. The heat required for the complete

vaporization of solution C is HD – HC energy/mole solution. Equilibrium liquids and

vapours may be joined by the tie lines, of which line EF is typical.

6

HOW TO OBTAIN x-y DIAGRAM FROM H-x-y

DIAGRAM? (Fig.2)

• Now, the mixture beyond these two points; one which is above this HV vs. y curve is the

super heated vapor, and below HL vs x curve is the subcooled liquid. Now there is a direct

relations between the H-x-y curve with the x-y curve equilibrium diagram.

• So, if we have enthalpy concentration relationship, we can have direct relation between

H-x-y and x-y diagrams, now if we have tie lines which connects the equilibrium liquid

and vapor composition for H-x-y diagram, then it will be easy to construct x-y diagram.

So, only the end points of the tie lines is required to obtain x-y diagram.

7

Contd.

• Now, let us see we have the equilibrium curve of H-x-y diagram. We will just place the x-

y diagram below the H-x-y diagram.

• Now, start at the liquid composition at point E and draw a vertical line . So, it will give

the composition on the x axis will be xE, and then draw a vertical line from the HV vs.y

curve draw a vertical line from point F, it will intersect the diagonal line , and from this

point draw a horizontal line. So, it will cross at point G. So, the composition of these will

be yF. So, this is the equilibrium point, similarly we have other tie lines through which we

will obtain the equilibrium curves.

8

CHARACTERISTICS OF H-x-y DIAGRAMS:

Let point M on figure (2) represents M mole of a mixture of enthalpy HM and concentrations zM,

and similarly N is the N mole of a mixture of properties of HN, zN. Adiabatic mixing of M and N

produce P moles of a mixture of enthalpy Hp and concentrations zP.

M + N = P………………………………… (1)

MzM + NzN =PzP………………………………………… (2)

MHM + NHN = PHP………………………. (3)

9

Contd.

Elimination of P between Equations (1) and (2) and between (1) and (3) yields

M zN zP HN HP

……………………. ( 4 )

N zP zM H P H M

This is the equation of a straight line on the enthalpy-concentration plot, passing through

points (HM , zM ), (HN , zN ) and (HP ,zP ). Point P is therefore on the straight line M N, located

so that M / N =line N P /line PM. Similarly if mixture N were removed adiabatically from

mixture P, the mixture M would result.

Consider now mixture C (Hc , zc ) in fig. 2. It will be useful to describe such in terms of

saturated vapours and liquids, since distillation is mostly concerned with such mixtures. C can

be considered the result of adiabatically removing saturated liquid D from saturated vapour E

(DE is not a tie line).

10

Contd.

They are then projected to the lower diagram, from the curve shown there. Thus any point C

on the H-x-y diagram can be represented by the difference between saturated vapours and

liquids and in turn also by a curve on the x-y plot. For the combination E-D=C, a material

balance shows

D zC y E lineCE

E zC xD lineCD ……………… ( 5 )

This is the equation on the xy diagram of the chord of slope D / E drawn between point (yE,

xD ) and y = x = zC on the 45˚ line. Similarly, the ratios of F / G and J/ K would be shown by

the slope of chords drawn from these points to y = x = zC.

11

Figure 2. H-x-y and x-y Diagram 12

CONCLUSION:

• Consideration of the geometry of the diagram will readily show the following;

1. If the HGy and HLx curves are straight parallel lines (which will occur if the molar

latent heat of A and B are equal, if the heat capacities are constant over a prevailing

temperature range, and if there is no heat of solution), then D / E = F / G = J / K for

adiabatic subtraction, since the line-segment ratios are then equal, and the curve on

x-y representing C becomes a straight line. ( Fig 3.)

2. If the point C is moved upward, the curve on xy becomes steeper, ultimately

coinciding with the 45˚ line when C is at infinity enthalpy.

3. If the point C is on HGy curve, the curve on xy becomes a horizontal straight line; if

C is on the HLx curve, the curve on xy becomes a vertical straight

13

Figure 3.

14

APPLICATIONS:

• The drawbacks of the McCabe Thiele Method led to the invention of a more accurate

method called Ponchon Savarit method with the following advantages:

1. Rigorous and capable of handling all distillations, but requires detailed enthalpy data

for its application

2. Simultaneous material and energy balance calculations

3. Detailed calculations of equilibrium conditions

4. More accurate, but difficult to use

5. Largely superseded by rigorous computer simulation calculations

15

References:

1. Mass Transfer Operation, Robert T. Treybal, 3rd Edition, McGraw Hill International

Editions.

2. http://nptel.ac.in/courses/103103034/28

3. http://www.separationprocesses.com/Distillation/DT_Chp04-2.htm

16

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