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ENTHALPY

CONCENTRATION
DIAGRAMS
BMS College of Engineering
Department of Chemical Engineering
Self Study Presentation
Mass Transfer - 2

Presented by: Faculty in charge:

Angel Baranwal Mrs. D Srilakshmi


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.

Figure. 1 : Enthalpy Concentration Diagram


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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.

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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.

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Contd.

• For the present purposes, saturated-vapour enthalpies can be calculated adequately by


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).

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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.

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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.

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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.

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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.

A total material balance is


M + N = P………………………………… (1)

And solute balance for component A is


MzM + NzN =PzP………………………………………… (2)

As the enthalpy balance is


MHM + NHN = PHP………………………. (3)

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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).

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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.

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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

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Figure 3.
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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

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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

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