intermolecular forces
DESCRIPTION
Intermolecular Forces. Intermolecular forces are weak, short-range attractive forces between atoms or molecules. Intermolecular forces ultimately derive from the electrostatic properties of molecules. - PowerPoint PPT PresentationTRANSCRIPT
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Intermolecular Forces
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Intermolecular forces are weak, short-range attractive forces between atoms or molecules.
Intermolecular forces ultimately derive from the electrostatic properties of molecules.
Although intermolecular forces are weak, they result in significant effects on the physical properties of molecules because these forces are additive.
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Intramolecular bonds refer to the covalent bonds holding molecules together and are many-fold stronger than the weaker intermolecular forces of attraction between molecules.
The strength of intermolecular forces between molecules is inversely proportional to the thermal energy of the system.
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Vibrational and Rotational Motion of Ethane
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Relative Motion of Water Molecules
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Summary of Intermolecular Forces
Coulombic interactions
Van der Waals interactions (London dispersion forces)
Hydrogen bonds
Hydrophobic effect
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Coulomb's Law
o is the permittivity of the medium, also known as the dielectric constant
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Dielectric constants are related to the polarity and polarizability of the medium, that is the ability of the medium to diminish the force between two point charges at a constant distance d.
Vacuum (o = 1) has little effect on Coulombic
interactions
Water (o = 80) significantly dampens Coulombic
interactions
Dielectric constants of common mediaVacuum 1
Mylar 3
Glass 5-10
Benzene 4
Water 80Air (1 atm) 1.0006Air (102 atm)1.0548
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Van der Waals interactions arise from weak electrostatic forces that act over a short distance, generally near the point of physical contact. These forces ultimately rely on the inherent repulsive force of the outer electron clouds of molecules and its inherent polarizability.
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Infinite distance– no interaction
The London-Jones Thought Experiment
++ - -Attraction due to induced dipoles in outer electron shells
Strong repulsion as outer electron shells begin to overlap
Atomic radius
Van der Waals radius
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Induced Dipole-Induced Dipole Interactions
Induced Dipole-Dipole Interactions
Dipole-Dipole Interactions
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Ion-Dipole Interaction
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The Structure of Water
Conventional viewVan der Waals representation
Electron density (side view)
Electron density (end view)
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R = 2.976 (+0.000, -0.030) Å, α = 6 ± 20°, β = 57 ± 10°; α is the donor angle and β is the acceptor angle. The dimer (with slightly different geometry) dipole moment is 2.6 D. Although β is close to as expected if the lone pair electrons were tetrahedrallly placed (109.47°/2), the energy minimum (~21 kJ mol-1) is broad and extends towards β = 0°.
Geometry of the Hydrogen Bond
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Extended Hydrogen Bonding Structures
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Flicker clusters are short-lived local areas of order water within an otherwise disordered bulk solution.
Flicker Clusters
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Relative Motion of Water Molecules
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Structure of Ice
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Liquid water Solid water
Space Filling Model of Liquid and Solid Water
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Hydration Spheres Surrounding Ions
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Hydrophobic Effect
The hydrophobic effect is an entropically-driven association of hydrophobic molecules that is a direct consequence of the polar nature of water and it propensity for hydrogen bonding.
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Bennion and Daggett (2003) Proc. Natl. Acad. Sci. USA 100, 5142-5147.
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1YPC rendered in PyMol
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Average Root Mean Square Deviation of the ca positions for the protein vs. time (a measure of overall protein structure)
Nonpolar Surface Accessible Surface Area vs. time (a measure of protein “openness”
Bennion and Daggett (2003) Proc. Natl. Acad. Sci. USA 100, 5142-5147.
Figure 1
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Figure 3
Bennion and Daggett (2003) Proc. Natl. Acad. Sci. USA 100, 5142-5147.
water
urea
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Bennion and Daggett (2003) Proc. Natl. Acad. Sci. USA 100, 5142-5147.
Figure 5