1. AP Review: Unit 6A By Harrison Alch and Karen Sittig May 1, 2008

2. Quantum Mechanics: Constants c = the speed of light = 2.998*10 8 m/s c = the speed of light = 2.998*10 8 m/s λ = wavelength (generally in nm) λ = wavelength (generally in nm) h = Planck’s constant = 6.63*10 -34 J*s h = Planck’s constant = 6.63*10 -34 J*s E = energy (generally in J) E = energy (generally in J) m = mass m = mass mass of an electron = 9.11*10-31 kg mass of an electron = 9.11*10-31 kg

3. Quantum Mechanics: Equations c=λv c=λv Wavelength of a photon (massless) Wavelength of a photon (massless) E = hv E = hv Energy of a photon Energy of a photon λ = h / mv λ = h / mv deBroglie wavelength – takes mass of a particle into account deBroglie wavelength – takes mass of a particle into account

4. Example problem It requires a photon with a minimum energy of It requires a photon with a minimum energy of 4.41 x 10 -19 J to emit electrons from sodium metal. 4.41 x 10 -19 J to emit electrons from sodium metal. What is the minimum frequency needed to emit electrons from sodium via the photoelectric effect? What is the minimum frequency needed to emit electrons from sodium via the photoelectric effect? E = hv E = hv 4.41 x 10 -19 J = (6.626 x 10 -34 J*s) * v 4.41 x 10 -19 J = (6.626 x 10 -34 J*s) * v v = 6.66 x 10 14 Hz v = 6.66 x 10 14 Hz Calculate the wavelength of one photon of this light. What color would it be? Calculate the wavelength of one photon of this light. What color would it be? λ = c/v λ = c/v Λ = (2.998 x 10 8 m/s)/(6.66 x 10 14 Hz) Λ = (2.998 x 10 8 m/s)/(6.66 x 10 14 Hz) λ = 450 nm λ = 450 nm This light would be blue This light would be blue

5. Example problem cont. If sodium is irradiated with light of 439 nm, what is the maximum possible kinetic energy of the emitted electrons? If sodium is irradiated with light of 439 nm, what is the maximum possible kinetic energy of the emitted electrons? E 439 = hc/ λ E 439 = hc/ λ E 439 = (6.626 x 10 -34 J*s)(2.998 x 10 8 m/s)/(439 x 10 -9 m) E 439 = (6.626 x 10 -34 J*s)(2.998 x 10 8 m/s)/(439 x 10 -9 m) E 439 = 4.52 x 10 -19 J E 439 = 4.52 x 10 -19 J E k = E 439 – E min E k = E 439 – E min E k = (4.52 x 10 -19 J) – (4.41 x 10 -19 J) E k = (4.52 x 10 -19 J) – (4.41 x 10 -19 J) E k = 1.1 x 10 -20 J/e - E k = 1.1 x 10 -20 J/e -

6. IMFAs “Intermolecular forces of attraction” “Intermolecular forces of attraction” General types: General types: London Dispersion Forces London Dispersion Forces Dipole-Dipole Forces Dipole-Dipole Forces Ion-Dipole Forces Ion-Dipole Forces Hydrogen Bonds Hydrogen Bonds

7. London Dispersion Forces Exist between all atoms and molecules Exist between all atoms and molecules Are the only forces between nonpolar atoms and molecules Are the only forces between nonpolar atoms and molecules The weakest type of intermolecular forces, caused by instantaneous dipoles The weakest type of intermolecular forces, caused by instantaneous dipoles Dispersion forces tend to increase in strength with increasing molecular weight. Dispersion forces tend to increase in strength with increasing molecular weight.

8. Dipole-Dipole and Ion-Dipole Dipole-Dipole Forces Dipole-Dipole Forces Exist between polar molecules when the net positive end of one attracts the net negative end of another Exist between polar molecules when the net positive end of one attracts the net negative end of another Only exist when molecules are close together. Only exist when molecules are close together. Ion-Dipole Forces Ion-Dipole Forces exist between ions and polar molecules exist between ions and polar molecules A cation attracts the negative ends of polar molecules, an anion attracts the positive ends. A cation attracts the negative ends of polar molecules, an anion attracts the positive ends.

9. Hydrogen Bonds Exist only between an H bonded to an O, F, or N in a very polar bond and usually another O, F, or N, or other very electronegative atom. Exist only between an H bonded to an O, F, or N in a very polar bond and usually another O, F, or N, or other very electronegative atom. The strongest type of intermolecular forces. The strongest type of intermolecular forces. from http://kentsimmons.uwinnipeg.ca/

10. Comparative Strength of IMFAs When molecules of 2 substances are relatively the same mass, the different strengths of attractive forces are due to differences in the length of the dipole moment. When molecules of 2 substances are relatively the same mass, the different strengths of attractive forces are due to differences in the length of the dipole moment. When molecules of 2 substances are different masses, the different strengths of attractive forces are due to the strength of dispersion forces (the more massive one generally has stronger attractive forces). When molecules of 2 substances are different masses, the different strengths of attractive forces are due to the strength of dispersion forces (the more massive one generally has stronger attractive forces).

11. Some Properties of Liquids Viscosity Viscosity The resistance of liquid to flow The resistance of liquid to flow Liquids that have stronger IMFAs are more viscous Liquids that have stronger IMFAs are more viscous Viscosity also increases with the increasing ability of molecules to become tangled (some isomers are more viscous than others) Viscosity also increases with the increasing ability of molecules to become tangled (some isomers are more viscous than others) Surface Tension Surface Tension The amount of energy required to increase the surface area of a liquid by a given amount The amount of energy required to increase the surface area of a liquid by a given amount Liquids that have stronger IMFAs tend to have more surface tension Liquids that have stronger IMFAs tend to have more surface tension The surface tension of water at 293 K is 0.0729 J/m 2 The surface tension of water at 293 K is 0.0729 J/m 2 The surface tension of mercury at 239 K is 0.46 J/m 2 The surface tension of mercury at 239 K is 0.46 J/m 2

12. Example Problems Why is the surface tension of CHBr3 g greater than CHCL3? CHBr3 has a higher molar mass, is more polarizable, and has stronger dispersion forces, so the surface tension is greater. Why does as temperature increases, oil flow faster through a narrow tube? The viscosity of the oil decreases because the average kinetic energy of the molecules increase.

13. Periodic Trends Size Size Generally, size decreases across a period and increases down a family Generally, size decreases across a period and increases down a family As the nuclear charge increases but no new electron orbitals are added, the valence electrons are held more strongly by the nucleus, decreasing the size As the nuclear charge increases but no new electron orbitals are added, the valence electrons are held more strongly by the nucleus, decreasing the size In transition metals, the electrons in filled d orbitals tend to repel one another strongly enough to result in a deviation from this trend In transition metals, the electrons in filled d orbitals tend to repel one another strongly enough to result in a deviation from this trend Electron Affinity Electron Affinity Generally, electron affinity increases across a period and decreases down a family Generally, electron affinity increases across a period and decreases down a family Across a period, the effective nuclear charge increases, more readily attracting electrons Across a period, the effective nuclear charge increases, more readily attracting electrons Down a family, the distance from the nucleus decreases, making it more difficult to attract electrons Down a family, the distance from the nucleus decreases, making it more difficult to attract electrons

14. Period Trends cont. Ionization Energy Ionization Energy Ionization energy tends to increase across a period and up a family Ionization energy tends to increase across a period and up a family As more protons are added to the nucleus, they increase the effective nuclear charge and hold the valence electrons more tightly, so removing an electron requires more energy As more protons are added to the nucleus, they increase the effective nuclear charge and hold the valence electrons more tightly, so removing an electron requires more energy As more orbitals are added, the valence electrons are farther away from the nucleus, reducing the pull of the protons on the electrons and allowing them to be removed more easily. As more orbitals are added, the valence electrons are farther away from the nucleus, reducing the pull of the protons on the electrons and allowing them to be removed more easily. Ionic Radii Ionic Radii Cations are smaller than their parent atoms due to the remaining electrons being held more tightly than before Cations are smaller than their parent atoms due to the remaining electrons being held more tightly than before Anions are larger than their parent atoms due to increased electron- electron repulsions Anions are larger than their parent atoms due to increased electron- electron repulsions For a series of isoelectronic ions and atoms, atomic radius decreases with increasing atomic number (and increasing nuclear charge) For a series of isoelectronic ions and atoms, atomic radius decreases with increasing atomic number (and increasing nuclear charge)

15. Example Problems Put these atoms in order of increasing size: Na, Ca, K, Be, & S Be, S, Na, Ca, K Which gas has a lower boiling point, Cl2 or Kr? Kr would have a lower boiling point, despite its higher molar mass. Which has stronger IMFAs, CH4 or CH3OH? CH3OH would have stronger IMFAs due to its polar –OH group.

16. Drawing Lewis Structures 1. Pick a central atom. This should be of the element with the lowest electronegativity (generally from families 3, 4, or 5, or a noble gas) 2. Determine how many bonds are needed by subtracting the valence electrons (number of family) from the total electrons needed to complete octets (or duets etc) and dividing by two. 3. Connect each atom with a single bond. 4. Add more bonds if needed. Otherwise, complete the octets on the outer atoms. 5. If there are extra electrons, add them to the central atom.

17. Example Problems XeF 4 XeF 4 CH 4 CH 4 NH 3 NH 3 H 3 O + H 3 O +

18. Molecular Shapes Can be classified by electron geometry or molecular geometry Can be classified by electron geometry or molecular geometry Electron geometry doesn’t take lone pairs into account when assigning names, molecular geometry does Electron geometry doesn’t take lone pairs into account when assigning names, molecular geometry does The hybridization of the central atom is determined by the electron geometry The hybridization of the central atom is determined by the electron geometry

19. Electron Geometry Linear 2 bonding domains No hybrid orbitals Trigonal Planar 3 bonding domains sp hybridized Tetrahedral 4 bonding domains sp 2 hybridized Pictures from www.wikipedia.org

20. Electron Geometry cont. Trigonal Bipyramidal 5 bonding domains sp 2 d hybridized Octahedral 6 bonding domains sp 2 d 2 hybridized Pictures from www.wikipedia.org

21. Molecular Geometry Pictures from www.wikipedia.org Bent 1 or 2 lone pairs sp or sp 2 hybridized Trigonal Pyramidal 1 lone pair sp 2 hybridized See-Saw 6 bonding domains sp 2 d hybridized

22. Molecular Geometry cont. Pictures from www.wikipedia.org Square Planar 2 lone pairs sp 2 d 2 hybridized Square Pyramidal 1 lone pair sp 2 d 2 hybridized Linear 3 lone pairs sp 2 d hybridized T-Shaped 2 lone pairs sp 2 d hybridized

23. Sample Problems Name the electron geometry: Name the electron geometry: XeF 4 XeF 4 CH 4 CH 4 SF 6 SF 6 Name the molecular geometry: Name the molecular geometry: NH 3 NH 3 H 2 O H 2 O PCl 5 PCl 5 State the hybridization of the central atom: State the hybridization of the central atom: XeF 2 XeF 2 BrF 5 BrF 5 SO 2 SO 2

24. Solutions to Sample Problems Name the electron geometry: Name the electron geometry: XeF 4 - Octahedral XeF 4 - Octahedral CH 4 - Tetrahedral CH 4 - Tetrahedral ClF 3 – Trigonal Bipyramidal ClF 3 – Trigonal Bipyramidal Name the molecular geometry: Name the molecular geometry: NH 3 – Trigonal Pyramidal NH 3 – Trigonal Pyramidal H 2 O - Bent H 2 O - Bent PCl 5 - Octahedral PCl 5 - Octahedral State the hybridization of the central atom: State the hybridization of the central atom: XeF 2 - XeF 2 - sp 2 d 2 BeCl 2 - unhybridized BeCl 2 - unhybridized SO 2 – sp 2 SO 2 – sp 2