1. Physical Chemistry I (TKK-2246)
14/15 Semester 2
Physical Chemistry I (TKK-2246)
Instructor: Rama Oktavian
Office Hr.: M – F.13-15

2. Outlines 1. Solid-liquid equilibrium 2. Liquid-solid phase diagram
3. Eutectic point
4. Salting out

3. Liquid-solid equilibria

4. Liquid-solid equilibria
the manufacture of liquid crystal displays and semiconductors
in the food industry, the phase behavior and crystalline habit influences the characteristics of consumer products
(Costa, et al., 2009)
crystallization process

5. Liquid-solid equilibria

6. Liquid-solid phase diagram
a1→a2, The system enters the two-phase region labelled ‘Liquid +B’
a2→a3, More of the solid forms, The liquid phase is richer in A than before
a3→a4, At the end of this step, there is less liquid than at a3, and its composition
is given by e

7. Liquid-solid phase diagram
the eutectic composition, the mixture
with the lowest melting point
the solution having the eutectic composition xe is in equilibrium with both pure solid A and pure solid B.
Eutectics point
F' = P = = 0
the eutectic mixture solidifies at a single definite temperature

8. Liquid-solid phase diagram
The Lead (Pb)-Antimony (Sb) System
The eutectic temperature is 246 °C ; the eutectic composition is 87 mass percent lead

9. Liquid-solid phase diagram
The Lead (Pb)-Antimony (Sb) System
The point a represents pure solid antimony at 300 °C
Point b lies in the region Sb + L
Point c represents equilibrium composition between solid antimony and liquid solution
Point g represents pure lead (Pb) solid
Point d represents equilibrium composition between solid lead and liquid solution
Point b and f represents two phase region

10. Liquid-solid phase diagram
The Lead (Pb)-Antimony (Sb) System
At h, the system is entirely liquid
As the system cools, solid antimony appears at i
as the antimony crystallizes out, the saturated liquid becomes richer in lead and the liquid composition moves along the curve
At j the solution has the eutectic composition e and is saturated with respect to lead also, so lead begins to precipitate

11. Liquid-solid phase diagram
Reacting system
A + B  AB2
there are two eutectics: one of the A-AB2-liquid ; the other of AB2 -B -liquid

12. Liquid-solid phase diagram
H2O-Fe2Cl6 system

13. Liquid-solid phase diagram
Incongruent system
the alloy Na2K

14. Liquid-solid phase diagram
a1→a2 - Some solid Na is deposited, and the remaining liquid is richer in K
a2→just below a3, The sample is now entirely solid, and consists of solid Na and solid Na2K

15. Liquid-solid phase diagram
b1→b2, No obvious change occurs until the phase boundary is reached at b2
when solid Na begins to deposit
b2→b3, Solid Na deposits, but at b3 a reaction occurs to form Na2K. At b3, three phases are in mutual equilibrium
b3→b4, As cooling continues, the amount of solid compound increases until at b4
Peritectic line

16. Salting out
A common procedure to separate a mixture of an organic liquid in water by adding salt
Example: Potassium carbonate added to a solution of methanol in water produces 2 liquid phases
Source: Shakhashiri, B.Z. Chemical Demonstrations: A Handbook for Teachers of Chemistry

17. Salting out
K2CO3-H2O-CH3OH

18. Salting out Example researches on salting out effect
Salting-out effect of sodium, potassium, carbonate, sulfite, tartrate and thiosulfate ions on aqueous mixtures of acetonitrile or 1-methyl-2-pyrrolidone: A liquid–liquid equilibrium study
(Fluid Phase Equilibria Volume 360, 25 December 2013, Pages 357–366)
Recovery of Aniline from Wastewater by Nitrobenzene Extraction Enhanced with Salting-Out Effect
(Biomedical and Environmental Sciences Volume 23, Issue 3, June 2010, Pages 208–212)
Effect of salting out on the desorption-resistance of polycyclic aromatic hydrocarbons (PAHs) in coastal sediment
(Chemical Engineering Journal Volume 225, 1 June 2013, Pages 84–92)

19. Buffering out Example researches on buffering out effect
Mohamed Taha, Han-Lan Teng, Ming-Jer Lee, Buffering-out: Separation of tetrahydrofuran, 1,3-dioxolane, or 1,4-dioxane from their aqueous solutions using EPPS buffer at  K
(Separation and Purification Technology Volume 105, 5 February 2013, Pages 33–40)
Mohamed Taha, Han-Lan Teng, Ming-Jer Lee, The buffering-out effect and phase separation in aqueous solutions of EPPS buffer with 1-propanol, 2-propanol, or 2-methyl-2-propanol at T = 298.15 K
(The Journal of Chemical Thermodynamics Volume 47, April 2012, Pages 154–161)
Mohamed Taha, Ming-Jer Lee, Solubility and phase separation of 4-morpholinepropanesulfonic acid (MOPS), and 3-morpholino-2-hydroxypropanesulfonic acid (MOPSO) in aqueous 1,4-dioxane and ethanol solutions
(The Journal of Chemical Thermodynamics Volume 43, Issue 11, November 2011, Pages 1723–1730)

20. Thank You !