excess thermodynamic properties ppt
DESCRIPTION
Excess Thermodynamic Properties . Excess volume of mixing, Heat of mixing, deviation in adiabatic compressiblitgies of liquid mixtures (homogeneous and non-reacting)TRANSCRIPT
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Excess Thermodynamic Properties
X. Rosario Rajkumar Department of Humanities and Science
Oxford Engineering College Tiruchirappalli – 620 009
at Cauvery College for Women, Tiruchirappalli
December 16, 2011 (Friday)
Innovation is our strength
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Like dissolves like
Sugar in Water --- Dissolves
Sugar in Kerosene --- Does not dissolve
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NaCl in Water
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Ion-Dipole Interactions
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Liquid water
O H
H
O
H
H
O
H
H
O
H
H
O
HH
OH H
Water molecules in vapour
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Dipole-Dipole Interactions(Keesom Forces)
Edip-dip = 2mA2mB
2/3RAB2kT
Alcohol and water
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London Forces
Polarized molecule
Neighbouringmolecue
BenzeneIodine
EABdisp = [3aAaBIAIB/2(IA+IB)] /
(1/R6)
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Hydrogen Bonding
H F H F H F
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Parameters
Excess volume of mixing, Heat of mixing
Internal Pressure usingDensity and viscosity
Adiabatic compressibility
Ks =1 / (U2 x d )
Gibbs Free Energy of Mixing using vapour pressures of liquids andLiquid mixtures
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Force ModelEnergy, KJmol-1
Example
Ionic 400-4000 NaCl
Covalent 150-1100 H-H
Metallic 75-1000 Au
+
+
-
-
+ electrons +
+ + + +
+
+
+ + +
+ + +
e e e
e e e
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Force ModelEnergy, kJmol-1 Example
Ion-dipole 40-600Na+ & H2O
Dipole-dipole 5-25
HCl and HCl
H-bond O-H ------F-H 10-40 H2O & HF
London dispersion 0.05-40
Xenon & Xenon
+ d- d+
d- d+ d- d+
d- d+ d- d+
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Ideal gas?
• No intermolecular interaction
• Obeys ideal gas equation, PV = nRT
• At low P and at high T, a real gas tends to to ideal gas
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Thermodynamics of SolutionsProperties of Ideal Solutions:1. There is no volume change when an
ideal solution is formed from its pure components
2. There is no evolution or absorption of heat during the formation of an ideal solution
3. An ideal solution obeys Raoult’s law
pi = xi pio
pi = partial vapour pressure of ixi = mole fraction of I in the solution
pio = vapour pressure of pure component i
4. In an ideal solution the intermolecular interactions between like molecules is equal to that of unlike molecules
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Consider a binary solution containing liquid A and liquid B:
Interaction between A & A (like moleules)
--- A-AInteraction between B & B (like moleules)
--- B-BInteraction between A & B (unlike moleules)
--- A-BIn an ideal solution,
A-A or B-B = A-B
In a non-ideal solution,A-A or B-B not equal to A-B
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100mL of alcohol + 100mL of water = ----- mL of solution
Why?•Rupture of H-bonds in alcohol by the addition of water• Breaking up of H-bonds in water by the addition of alcohol• Formation of H-bonds between alcohol and water• Dipole-dipole interactions
VE = (volume after mixing) – (volume before mixing)
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Excess volume of mixing Ethanol + Water
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VE ={ [XA MA + XB MB ] / dAB}- [ XA MA / dA] + [ XB M B / dB ]
VE = Excess Volume of Mixing of two liquids A and B (non- reacting, homogeneous)XA = Mole fraction of liquid A in the solution of A and BXB = Mole fraction of liquid BMA and MB = respective molar masses of A and BdA = density of AdB = density of BdAB = density of the liquid mixture
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PYKNOMETER
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R D BOTTLE
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Experimental Methods
Measurement of Density of liquid and Liquid mixtures using Pyknometer or RD Bottle or Densimeter.Measurement of Heat of Mixing by Calorimetry.Measurement of ultrasonic velocity in
liquids and liquid mixtures by interferometry.
Vapour pressure by Isoteniscope
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Deviation in isentropic copressibility (Ks)
• Ks = Ks,mix – ( x1Ks1 + x2Ks2)• Ks,mix = isentrpic compressiblity of the liquid • mixture• Ks1 and Ks2 are respective isentropic
comressibilities of liquid 1 and 2• X1 and X2 are respective mole fractions
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ULTRSONIC INTERFEROMETER
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Dewar Flask
• Dewar Flask
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Q = m s T + w T
H = Heat of solution
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Density of liquids/liquid mixtures
• Density = (m/m0)xdo at T• m = mass of certain volume of liquid• m0 = mass of same volume of water
• d0 = density of water at T (from Tables)
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Thermodynamic parameters
• I. Prigogine 1977 Nobel Prize winner
• Best low priced Calorimeter ? Dewar flask * Most accurate thermometer to readthe difference in temperatures
? Beckmann thermo-meter
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ISOTENISCOPE
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Repulsive Inter-Human Interactions
• Anger• Hatred • Jealousy• Back-biting• Disobedience• EGO (Evading God-Out)• Arrogance• Greediness
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Attractive Inter-Human Interactions
• Affection• Friendship• Sharing• Helping • Kindness• Respectfulness • Obedience • Gratitude
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?
கற்க கசடற கற்பவை கற்றபன் நி�ற்க அதற்கு தக
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Thank You