Excess property introduction ▪ Excess volume ▪ Excess gibbs free energy ▪ Entropy of mixing ▪ what is use of Residual property and Excess property in thermodynamics ▪ Case study ▪ Thermo-calc demo ▪ conclusion

1. charitable Trust’s
vishwakarma institute of
technology ,pune
Name Of Students: Rucha Lokhande ,Rucha
Dhavale , Prajakta Kulal , Isha Meshram
Under Guidance Of Dr.Tanushree
Bhattacharjee
1

2. Excess property
determination
Advanced
Thermodynamics

3. contents
▪ Excess property introduction
▪ Excess volume
▪ Excess gibbs free energy
▪ Entropy of mixing
▪ what is use of Residual property and Excess property
in thermodynamics
▪ Case study
▪ Thermo-calc demo
▪ conclusion
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4. Excess properties
▷
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5. ▷
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6. 6

7. ▷
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8. Excess Gibbs free energy
▷
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9. ▷
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10. ▷
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11. Entropy of mixing
▪ Consider that a number of ideal gases are separated which are present in a
vessel. Let ni be the number of moles of each gas and Vi is the volume it
occupies. The total entropy
S1 =∑ni (Cv ln T + R ln(Vi + Si) 1
▪ The increase in entropy in mixture: S 2 – S1 = – ∑ ni R ln Xi
▪ Entropy of mixing of 1 mole of the ideal gas:
∆ S m = – R ∑ ni/n ln Xi = –R ∑ Xi ln X
▪ The fraction Xi is less than unity in all cases, the logarithm is negative and
thus ∆ S m is always positive. Thus mixing of gases, always results in
increase in entropy.
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12. ▷ Entropy and disorder
-The diffusion of initially separated gases
result in an increase in entropy.
- The process has increased the random
distribution of molecules. Spontaneous
conduction of heat results in the random
distribution of kinetic energy of the
atoms.
-Thus spontaneous processes increase
randomness, at the same time increases
entropy
▷ Entropy And Randomness
-This definition of entropy, that it is a
measure of randomness, is one of great
value.
-A measure of entropy changes gives an
indication of structural changes.
-The process of fusion involves
increase in disorder and therefore, the
entropy increase. Greater the disorder,
greater the entropy increase.
-heat of fusion of ice and benzene are
5.26 and 8.27 cal/deg/mol.
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13. “
▪ In Thermodynamics A Residual Property Is Defined As The
Difference Between A Real Gas Property And An Idea
Gas Property, Both Considered At The
Same Pressure, Temperature, And Composition.
▪ Excess Property Is Difference Between The Value Of The Property
In A Real Mixture And The Value That Would Exist In An Ideal
Solution Under The Same Conditions.
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Excess property & residual property relationship

14. what is use of Residual property and Excess property
in thermodynamics ?
❑ Excess properties are
usually used with
liquid solutions, or
when we want to
measure deviations
from a non-ideal
solution.
❑ A Residual property is
measure the deviation
from an ideal gas at the
same conditions.
❑ MR = M – Mig
❑ ME = M - Mid
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15. Excess Chemical Potential
▪ The excess chemical potential is defined as the
difference between the chemical potential of a
given species and that of an ideal gas under the
same conditions.
▪ Ui= U Ideal + U Excess
▪ Useful for homogeneous & non-homogeneous
system 15

16. Experimental method to
determine excess property
• Measurement of density of
liquid & liquid mixture by
densimeter or by RD bottle.
• Measurement of heat of mixture
by calorimeter.
• Ultrasonic velocity by
interferometry.
• Vapor pressure by isoteniscope
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17. Intermolecular Forces
Dipole-Dipole Interaction
❑ Dipole-dipole
interaction occurs
whenever two polar
molecules get near each
other.
❑ The positively charged
portion of one molecule
is attracted to the
negatively charged
portion of another
molecule.
Ion-Dipole Interaction
❑ Ion-dipole interaction
occurs when an ion
encounters a polar
molecule.
❑ A cation or positive
ion would be attracted
to the negative part of
a molecule and
repelled by the
positive part.
London Dispersion Force
❑ The force between two
nonpolar molecules, is
the weakest of the
intermolecular forces.
❑ The electrons of one
molecule are attracted
to the nucleus of the
other molecule, while
repelled by the other
molecule's electrons.
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18. 18
Excess property
behavior
✔ Excess properties
are available is
various signs.
✔ Useful to predict
solution
behavior.
✔ Data available at
ambient
temperature 25
degree c.

19. Excess property & property change of mixing
▷ Observe excess property behavior
▷ Mixing process observe the behavior of enthalpy.
Applications:
✔ Predict the data of temperature & composition.
✔ Predict deviation from non ideal behavior.
✔ It inform about the type molecular interactions
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20. “
0bjective
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21. Experimental Determination
Excess Volume –Dilatometer V^E
Formula
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22. Experimental Determination
Excess Enthalpy- Calorimeter H^E
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23. 23
Thermodynamic Properties of Binary Liquid Mixtures of Cycloalkanol+
nAlkanes

24. • The HE and VE results
for each mixture were
expressed as a function
of the mole fraction x
of cycloalkanol by the
polynomials
• The values of
coefficients A, and the
standard deviations
o(HE) and a( VE)
obtained by the method
of least squares, with
all points weighted
equally 24

25. Molar Excess Enthalpies Of Cyclopentanol Mixtures
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26. 26
Molar Excess Volumes Of Cyclopentanol Mixtures

27. Simulation Simulation
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28. “
▷ DETERMINATION OF
THERMODYNAMIC EXCESS
PROPERTIES OF MIXTURES FROM
COMPUTER SIMULATION
28
example

29. Example
DETERMINATION OF THERMODYNAMIC EXCESS
PROPERTIES OF MIXTURES FROM COMPUTER
SIMULATION
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30. 30
introduction

31. 31

32. Simulation Result
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33. Excess Property Graph
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34. 34
summary

35. 35

36. Overview
BENIFITS
Thermo-Calc can be used to understand
many different phases in the life-cycle of
a material, such as:
• Alloy and materials development
• Metallurgical extraction and refining
• Additive Manufacturing
• Casting
• Forging/Hot rolling
• Heat treatment
• Joining/Welding/Soldering
• Quality control
• Materials selection
• Corrosion
• Underlying causes of failure
• Waste and recycling
APPLICATION
• Reduce costly, time-consuming
experiments and testing.
• Increase the value of experiments
• Optimize and define safe processing
windows.
• Shorten development time Build and
safeguard intellectual knowledge
• Improve the quality and consistency of
products through deeper understanding
• Make predictions that are difficult
CALCULATION
• Stable and meta-stable
• Amounts of phases and
their compositions
• Phase transformation
• Phase diagrams
• Thermochemical data
• Driving force for phase
transformations
• Solidification
• Thermodynamic properties
• Pourbaix diagrams
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37. Phase Daigram
• The term phase diagram
often means a T-x type of
diagram for binary systems
but the term is used here for
any type of diagram with
two or more independent
state variables used as axis
variables.
• Phase diagram gives
information about the state
of a system for any value of
the state variables.
Property Daigram
• A property diagram plots
the value of a dependent
property against an
independent variable, such
as the carbon activity
versus temperature in
steels.
• In multicomponent
systems, property diagrams
are often more useful than
phase diagrams.
Plotting
• A phase diagram is
calculated with the POLY
module using the MAP
command. At least two
axis variables should be
set in the POLY module.
• A property diagram is
calculated with the POLY
module using the STEP
command. Only one axis
variable should be set in
the POLY module. 37

38. Software
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39. 39
Software
Demonstration

40. Conclusion
In Detailed
Theoretical Study of
Excess Property
Determination of excess
property can se done by
both Experimental and
Simulation Method
•• Experimental Method is
bite costly and time
Consumping
•• Simulation is easy to
understand , and time
saving
Overview of
Thermo-Cal is been
Studied
•• Various
Thermodynamic
Property Diagram can
be easily Plotted.
•• Predication which are
difficult can also be
easily Solve
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41. Reference
▷ www.wikipedia.com
▷ Anping Liu & Rakesh Govind (1995) Determination of Thermodynamic Excess Properties of Mixtures
from Computer Simulation, Molecular Simulation, 15:1, 47-55, DOI: 10.1080/08927029508022328
▷ Elliott, J. Richard; Lira, Carl T. (2012). Introductory Chemical Engineering
Thermodynamics. Upper Saddle River, New Jersey: Prentice Hall. ISBN 978-0-13-606854-9.
▷ Frenkel, Daan; Smit, Berend (2001). Understanding Molecular Simulation : from algorithms to
applications. San Diego, California: Academic Press. ISBN 978-0-12-267351-1
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42. Thank you!
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