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CHAPTER 6: Condensed Phases and Phase
Transitions• Molecules in solid and liquid phases are
much closer to each other than in gas phase.
• Solid and liquid are called “condensed phases” and are harder to describe by simple mathematical equations.
• Can no longer ignore “intermolecular forces” as is done for gases.
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Types of Intermolecular Forces
• Electrostatic: Dipole-dipole, ion-dipole, induced dipole (opposite charges attract)
• Dispersion forces: correlations between electron motions (my area of research!)
• Hydrogen bonding
The strength of these interactions ranges from 0 to 5 kcal/mol - much weaker than
intramolecular covalent bond or ionic bonds!
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Intermolecular Forces and Coulomb’s Law
All of the intermolecular forces can be pictured as manifestations of Coulomb’s law.
• Ion-ion interactions lead to ionic bond.
Strong Attraction!!
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Intermolecular Forces and Coulomb’s Law continued
• Ion – Dipole: You can have non-bonded ion-dipole attraction; these are weaker than ion-ion interactions.
δ −
δ − δ −
δ −
δ +
δ +
δ +
δ +
δ +
δ +
δ +
δ +
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Intermolecular Forces and Coulomb’s Law continued
• Ion-Inducded Dipole: Ions can even be attracted to molecules with no dipole moment – they can create or induce a dipole moment
δ − δ +
Li cation “pulls” electrons in Aratom twoards it, inducing a dipole
This is a weaker attraction than an ion-dipole interaction
The strength of the interaction depends on how polariziable(how easily the electron density deforms) the atom or molecule is.
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Intermolecular Forces and Coulomb’s Law continued
• Dipole-Dipole Interactions – Two molecules with dipole moments line up to create a favorable interaction
δ −
δ +
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δ −
δ +
δ +
δ −
Two dipoles will line up such that the opposite charges are closer than the like charges, such that the favorable interactions will outweigh the unfavorable repulsions.
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Intermolecular Forces and Coulomb’s Law continued
• Dipole-Induced Dipole: These interactions are weaker than ion-induced dipole.
δ − δ +
δ − δ +
The Ar atom deforms slightly as the partial positive charge of the HCl molecule approaches.
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Intermolecular Forces and Coulomb’s Law continued
• Induced dipole – Induced dipole: Also called London Dispersion forces, these favorable interactions result from temporary fluctuations, which cause fluctuations in other molecules.
δ − δ −δ + δ +
Strength of dispersion interactions: larger atoms are more polarizable
He2 < Ne2 < Ar2 < ……..
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Intermolecular Forces and Coulomb’s Law continued
• Hydrogen Bonding: Interaction which forms between a lone pair on N,O, or F and a hydrogen bonded to N, O, or F
Water forms an extensive network of hydrogen bonds as the lone pairs on oxygen (red atom) interact with hydrogen of other molecules. A hydrogen bond is an intermolecular interaction; it occurs between atoms in different molecules.
Hydrogen bonding can be very strong in the gas phase, but usually only provides a few kcal/mol stabilization in solution.
Hydrogen Bond
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Gas vs. Condensed Phases
• Intermolecular forces make molecules attract each other and stick together in the liquid and solid phases.
• Gas phase results if molecules are moving too fast to get stuck together. (For example, at high temperatures or low pressures.)
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Intermolecular Forces and Boiling Point
• The stronger the intermolecular forces, the higher the boiling point of a liquid.
• Which has a higher boiling point, radon or helium? H20 or H2S?
• Usually it is hardest to boil ionic liquids, then polar liquids, then nonpolar liquids.
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Phase Transitions
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Phase Equilibrium• Even when a substance
is mainly in one phase, a small fraction is sometimes in a different phase. For instance, volatile liquids have some molecules escape as a gas from liquid phase.
• The gas and the liquid molecules are in a dynamic equilibrium.
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Vapor Pressure
• The small amount of gas above a liquid has a pressure, P, called the vapor pressure.
• Vapor pressure generally increases with temperature, until the liquid boils.
• The boiling point of a liquid is the point at which vapor pressure = external pressure.
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Phase Diagrams
• A phase diagram is a plot of P vs. T which can be used to predict what phase (solid, liquid, or gas) is seen for a given temperature and pressure.
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Phase Diagram for CO2
• X is the triple point –solid, liquid, and gas exist simultaneously.
• Z is the critical point –can not maintain a distinction between liquid and gas beyond this point
• Solid/liquid line usually curves to the right (at a given T, an increase in P means the substance freezes); water is an exception.
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Colligative Properties
• Colligative Properties describe how the physical properties (like boiling point) of a solvent change when a solute is added
• For dilute solutions, this will depend only on the number of solute particles, not their type.
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Descriptions of Solutions
• Mass Percent = (Mass of component / Total Mass of Mixture) X 100
Example: What is the mass percentage of NaI in a solution that is 5 g of NaI per 100g of solution?
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Descriptions of Solutions
• Mole Fraction = Number of moles A / Total number of moles
• Molality (m) =moles solute / kilograms solvent
Note that molality is NOT the same as molarity(moles/L). Sometimes they are numerically similar since 1 L of water weights 1 kg at 25 ºC.
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Molality Example
• A solution prepared by mixing 20.00 g of CdCl2 with 80.00 g of water has a density of 1.1988 g cm-3 at 20 ºC. Compute the molarity and molality of this solution.
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Example Continued
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Vapor Pressure and Raoult’s Law
• If a nondissociating, nonvolatile solute is added to a solvent, the solvent’s vapor pressure decreases in an amount proportional to the mole fraction of the solution.
∆Psolvent = -Xsolute Pºsolventor equivalently
Psolvent = Xsolvent Pºsolvent (Raoult’s Law)
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Raoult’s law and boiling point
• If a solute lowers the vapor pressure of a solvent, it’s harder (requires a higher temperature) to bring the solvent’s vapor pressure up to Patm to boil.
• Solutes raise the boiling points.• This is termed “boiling point elevation”.
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Determining Boiling point Elevation
∆Tb = kbmι
∆Tb = change in the boiling pointkb = solvent constantm = molality of soulteι = Van’t Hoff constant – how many particles
a solute breaks into in solution
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Van’t Hoff Constants
What is ι for the following compounds?NaCl?
H2SO4?
C6H12O6?
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Boiling point elevation example
• 4.58 g of (nonvolatile) picnic acid (C6H3N3O7) dissolves in 240.0 g of chloroform, which has a kb = 3.63 K kg mol-1. How much does the boiling point increase?
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Freezing Point Depression
• How are freezing points affected by solutes?
• Solute particles make it difficult to form an orderly solid. The solution must get colder to freeze
• “Freezing point depression”
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Freezing Point Depression
∆Tf = kfmι
Same concept as boiling point elevation but kfis different than kb.
For example, why is salt spread on icy roads?
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Mixes of Volatile Compounds
• What happens if we mix two volatile compounds together?
• If Raoult’s law still applied,P1 = X1 P1ºP2 = X2 P2º
If this is true, then the solution is “ideal”.
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Non-ideal solutions• For a mix of two volatile compounds, if Raoult’s
law still held, then P1=X1P1o, P2=X2P2
o. If this is true, the solution is “ideal”
• Even if the solution is non-ideal, for small X2, a similar equation holds if we replace P2
o with “kH”: P2 = kH X2 (Henry’s Law)
• The greater the vapor pressure of a gas above a liquid, the more the gas will dissolve in the liquid
• What could you do to keep a Coke from going flat?
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