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Homework 27 and Homework 27 answers will be available on Blackboard after lecture. Quiz IX next time. Exam V will be returned at the end of lecture. Your course-to-date percentage will be available on Blackboard under the heading 3rd% after lecture.
Recap
The forces of attraction that give liquids and solids their fixed volumes are called intermolecular forces. Intermolecular forces are forces of attraction between molecules or between molecules and ions. There are four types of intermolecular forces, also known as van der Waals forces:
Ion-dipole forces Dipole-dipole forces Hydrogen bonds London dispersion forces
The relative strengths of the intermolecular forces: Ion-dipole > H-bond > dipole-dipole > London dispersion A substances boiling point is a measure of the strength of its intermolecular forces.
All atoms and molecules exhibit London dispersion forces. Because they arise from induced dipoles, London dispersion forces are the weakest intermolecular forces.
Rank Br2, F2, and I2 according to increasing London dispersion force strength. a. b. c. d. I2 < F2 < Br2 I2 < Br2 < F2 F2 < I2 < Br2 F2 < Br2 < I2
I2 < F 2 < B r2
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I2 < B r2 < F 2
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< I2 < B r2
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< B r2 < I2 F 2
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F 2
As intermolecular force strength increases, boiling point increases. This same trend is observed in melting points.
Rank the following compounds according to increasing boiling point: CO2, H2O, and SO2.
a. b. c. d. CO2 < SO2 < H2O SO2 < H2O < CO2 H2O < CO2 < SO2 CO2 < H2O < SO2
H 2O < SO 2 < C O 2
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C O 2 <
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<
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SO 2 < C O 2 < H 2O
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SO 2
H 2O
<
H 2O
S O 2
<
C O 2
Viscosity
Viscosity is a measure of a liquids resistance to flow.
Van der Waals force strength: glycerol > water > ethanol > benzene > pentane Viscosity van der Waals force strength Viscosity particle size
Types of Solids
At their broadest level, solids can be classified as either crystalline or amorphous. Crystalline solids are those whose atoms, ions, or molecules have an ordered arrangement
extending over a long range. E.g., iron, table salt, ice, and diamond.
Amorphous solids are those whose constituent parts are randomly arranged and have no longrange order.
Rubber
The different subtypes of crystalline solids have different forces of attraction between the particles. Because they have different forces of attraction, different subtypes of crystalline solids have different physical properties.
Metallic Solids
Metallic solids are the simplest examples of crystalline solids because their constituent particles are atoms, which can be approximated as spheres. How can spheres be packed together in an ordered arrangement that extends over a long range? There are four typically observed results:
Simple cubic packing Body-centered cubic packing Hexagonal closest packing Cubic closest packing
Unit Cells
Because these crystalline solids exhibit long-range order, it isnt necessary to know what the extended solid looks like. Knowing the arrangement of the fundamental unit that is repeated to compose the overall solid is enough. The unit cell is the fundamental repeating unit that makes up the overall solid. There are three cubic unit cells:
Primitive cubic Body-centered cubic Face-centered cubic
Packing Type Simple cubic Body-centered cubic Hexagonal closest Cubic closest
Conclusion: Particles pack together in solids as closely as possible, maximizing their interparticle attractions.
Metallic bonds cant be localized or metals wouldnt be malleable (capable of being beaten into shapes). At the atomic level, being beaten into new shapes means moving atoms around, distorting the packing arrangement. If metallic bonds were localized, distorting the packing arrangement would amount to breaking bonds, which requires an enormous amount of energy.
(Conduction band)
(Valence band)
Ionic Solids
Like metallic solids, the particles that compose ionic solids can be approximated as spheres. Unlike metallic solids, the particles that compose ionic solids (cations and anions) have charges and different sizes. Because of their charges, the nearest neighbors of each cation will be anions, and vice versa.
Molecular Solids
Molecular solids are held together by van der Waals forces. Because van der Waals forces are typically weaker than metallic or ionic bonds, molecular solids tend to be soft, easily deformed, and possessed of low melting points. Because there are no charged species and the attractions are between molecules, molecular solids are typically nonconductors.
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Io n -i o n fo Io r n c -d e s ip o le fo H rc y d e ro s g e D n ip b o o le n -d d s ip L o o n le d fo o n rc d e is p e r s io n ..
M e ta lli c b o C n o d v s a le n tb o n d s
Phase Changes
Phase changes, or changes of state, are changes in the physical form of a substance that leave its chemical identity intact.
E.g., boiling water converts liquid water into gaseous water.
Evaporation
Why will a glass of water left out on a table eventually evaporate completely, without being heated? At a given temperature, the molecules in the water have a distribution of speeds, some of which are great enough to allow the molecules to escape the liquid phase.
Vapor Pressure
Vapor pressure (Pvap) is the pressure exerted by a vapor over its liquid. What factors affect vapor pressure?
Clausius-Clapeyron Equation
The relationship between vapor pressure and temperature is given by the Clausius-Clapeyron equation: lnPvap = -(Hvap/R)(1/T) + C The Clausisus-Clapeyron equation has the form of a straight line. y = mx + b
ln(P2/P1) = -(Hvap/R)(1/T2 1/T1) Butane lighters typically contain a mixture of liquid and vapor. At 25 oC the vapor pressure of butane is 2.3 atm. What is the pressure in the container at 150 oC? (The Hvap of butane is 24.3 kJ/mol.)
a. b. c. d.
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6 .6 6 a tm
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1 8 .1 a tm
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4 1 .6 a tm
Summary
Viscosity van der Waals force strength; viscosity particle size Most metallic solids exhibit hexagonal closest or cubic closest packing because doing so packs the atoms as closely together as possible, maximizing interparticle attractions. Metallic bonds involve delocalized sharing of electrons, which is best described as bands of MOs. Ionic solids pack similarly to metals, except that the particles that compose ionic solids (cations and anions) have charges and different sizes. Molecular solids are held together by van der Waals forces. Covalent network solids are held together by covalent bonds. Phase changes, or changes of state, are changes in the physical form of a substance that leave its chemical identity intact. Vapor pressure is the pressure exerted by a vapor over its liquid. The relationship between vapor pressure and temperature is given by the Clausius-Clapeyron equation: lnPvap = -(Hvap/R)(1/T) + C