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1 Intermolecular Forces and Liquids and Solids Chapter 11 Copyright The McGraw Hill Companies, Inc. Permission required for 1
2 A phase is a homogeneous part of the system in contact with other parts of the system but separated from them by a well defined boundary. 2 Phases Solid phase ice Liquid phase water
3 Intermolecular Forces Intermolecular forces are attractive forces between molecules. Intramolecular forces hold atoms together in a molecule. Intermolecular vs Intramolecular 41 kj to vaporize 1 mole of water (inter) 930 kj to break all O H bonds in 1 mole of water (intra) Generally, intermolecular forces are much weaker than intramolecular forces. Measure of intermolecular force boiling point melting point H vap H fus H sub
4 Intermolecular Forces Dipole Dipole Forces Attractive forces between polar molecules Orientation of Polar Molecules in a Solid Nonpolar molecules do not have dipole dipole forces
5 Intermolecular Forces Ion Dipole Forces Attractive forces between an ion and a polar molecule Pretty strong attractive force. This is the attractive between water and ionic solute. Ion Dipole Interaction
6 Dispersion Forces Intermolecular Forces Attractive forces that arise as a result of temporary dipoles induced in atoms or molecules Present in all molecules, but the only intermolecular force in NONPOLAR MOLECULES, or in Gaseous atoms. ion induced dipole interaction dipole induced dipole interaction 11.2 He He the temporary dipole induces a temporary dipole in a neighboring He atom both electrons on the same side atom set up a TEMPORARY DIPOLE. 6
7 Dispersion Forces Continued Intermolecular Forces Polarizability is the ease with which the electron distribution in the atom or molecule can be distorted. Polarizability increases with: greater number of electrons more diffuse electron cloud Dispersion forces usually increase with molar mass
8 What type(s) of intermolecular forces exist between each of the following molecules? HBr HBr is a polar molecule: dipole dipole forces. There are also dispersion forces between HBr molecules. CH 4 CH 4 is nonpolar: dispersion forces. S O O SO 2 SO 2 is a polar molecule: dipole dipole forces. There are also dispersion forces between SO 2 molecules
9 Hydrogen Bond Intermolecular Forces The hydrogen bond is a special dipole dipole interaction between they hydrogen atom in a polar N H, O H, or F H bond and an electronegative O, N, or F atom. A H B or A H A A & B are N, O, or F
10 Why is the hydrogen bond considered a special dipole dipole interaction? Decreasing molar mass Decreasing boiling point
11 11
12 Rank the following in order of increasing boiling point: HBr CH 3 OH CH 2 O CH 4 NaCl He CH 3 CH 3 12
13 Properties of Liquids Surface tension is the amount of energy required to stretch or increase the surface of a liquid by a unit area. Strong intermolecular forces High surface tension
14 Properties of Liquids Cohesion is the intermolecular attraction between like molecules Adhesion is an attraction between unlike molecules Adhesion Cohesion
15 Properties of Liquids Viscosity is a measure of a fluid s resistance to flow. Strong intermolecular forces High viscosity
16 Water is a Unique Substance Maximum Density 4 0 C Density of Water Ice is less dense than water
17 A crystalline solid possesses rigid and long range order. In a crystalline solid, atoms, molecules or ions occupy specific (predictable) positions. An amorphous solid does not possess a well defined arrangement and long range molecular order. A unit cell is the basic repeating structural unit of a crystalline solid. lattice point At lattice points: Atoms Molecules Ions Unit Cell Unit cells in 3 dimensions
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19
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22 Shared by 8 unit cells Shared by 2 unit cells
23 1 atom/unit cell (8 x 1/8 = 1) 2 atoms/unit cell (8 x 1/8 + 1 = 2) 4 atoms/unit cell (8 x 1/8 + 6 x 1/2 = 4)
24
25 When silver crystallizes, it forms face centered cubic cells. The unit cell edge length is 409 pm. Calculate the density of silver. d = m V V = a 3 = (409 pm) 3 = 6.83 x cm 3 4 atoms/unit cell in a face centered cubic cell m = 4 Ag atomsx g x mole Ag 1 mole Ag x = 7.17 x g atoms d = m V 7.17 x g = 6.83 x cm 3 = 10.5 g/cm
26
27 Extra distance =BC + CD =2d sinθ = nλ (Bragg Equation)
28 X rays of wavelength nm are diffracted from a crystal at an angle of Assuming that n = 1, what is the distance (in pm) between layers in the crystal? nλ = 2d sin θ n = 1 θ = λ = nm = 154 pm d = nλ 2sinθ = 1 x 154 pm 2 x sin14.17 = 77.0 pm
29 Types of Crystals Ionic Crystals Lattice points occupied by cations and anions Held together by electrostatic attraction Hard, brittle, high melting point Poor conductor of heat and electricity CsCl ZnS CaF
30 Types of Crystals Covalent Crystals Lattice points occupied by atoms Held together by covalent bonds Hard, high melting point Poor conductor of heat and electricity carbon atoms diamond graphite
31 Types of Crystals Molecular Crystals Lattice points occupied by molecules Held together by intermolecular forces Soft, low melting point Poor conductor of heat and electricity
32 Types of Crystals Metallic Crystals Lattice points occupied by metal atoms Held together by metallic bonds Soft to hard, low to high melting point Good conductors of heat and electricity nucleus & inner shell e mobile sea of e Cross Section of a Metallic Crystal 11.6 A metallic bond is the attractive force between the nucleus of the metal atoms and the "sea" of mobile electrons. 32
33 Types of Crystals
34 An amorphous solid does not possess a well defined arrangement and long range molecular order. A glass is an optically transparent fusion product of inorganic materials that has cooled to a rigid state without crystallizing Crystalline quartz (SiO 2 ) Non crystalline quartz glass
35 Least Order Evaporation Condensation T 2 > T 1 Greatest Order
36 The equilibrium vapor pressure is the vapor pressure measured when a dynamic equilibrium exists between condensation and evaporation H 2 O (l) H 2 O (g) Dynamic Equilibrium Rate of condensation = Rate of evaporation
37 Before Evaporation At Equilibrium
38 Molar heat of vaporization ( H vap ) is the energy required to vaporize 1 mole of a liquid. Clausius Clapeyron Equation ln P = H vap RT + C P = (equilibrium) vapor pressure T = temperature (K) R = gas constant (8.314 J/K mol)
39 The boiling point is the temperature at which the (equilibrium) vapor pressure of a liquid is equal to the external pressure. The normal boiling point is the temperature at which a liquid boils when the external pressure is 1 atm
40 The critical temperature (T c ) is the temperature above which the gas cannot be made to liquefy, no matter how great the applied pressure. The critical pressure (P c ) is the minimum pressure that must be applied to bring about liquefaction at the critical temperature
41 H 2 O (s) H 2 O (l) The melting point of a solid or the freezing point of a liquid is the temperature at which the solid and liquid phases coexist in equilibrium Melting Freezing
42 Molar heat of fusion ( H fus ) is the energy required to melt 1 mole of a solid substance
43
44 H 2 O (s) H 2 O (g) Molar heat of sublimation ( H sub ) is the energy required Sublimation to sublime 1 mole of a solid. Deposition H sub = H fus + H vap ( Hess s Law)
45 A phase diagram summarizes the conditions at which a substance exists as a solid, liquid, or gas. Phase Diagram of Water
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47 47
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