Chapter 10 Chemical Bonding II

1. Chemistry: A Molecular Approach, 2nd Ed.Nivaldo Tro Chapter 10Chemical Bonding II Roy Kennedy Massachusetts Bay Community College Wellesley Hills, MA

2. Taste • The taste of a food depends on the interaction between the food molecules and taste cells on your tongue • The main factors that affect this interaction are the shape of the molecule and charge distribution within the molecule • The food molecule must fit snugly into the active site of specialized proteins on the surface of taste cells • When this happens, changes in the protein structure cause a nerve signal to transmit Tro: Chemistry: A Molecular Approach, 2/e

3. Sugar & Artificial Sweeteners • Sugar molecules fit into the active site of taste cell receptors called Tlr3 receptor proteins • When the sugar molecule (the key) enters the active site (the lock), the different subunits of the T1r3 protein split apart • This split causes ion channels in the cell membrane to open, resulting in nerve signal transmission • Artificial sweeteners also fit into the Tlr3 receptor, sometimes binding to it even stronger than sugar • making them “sweeter” than sugar Tro: Chemistry: A Molecular Approach, 2/e

4. Structure Determines Properties! • Properties of molecular substances depend on the structure of the molecule • The structure includes many factors, such as: • the skeletal arrangement of the atoms • the kind of bonding between the atoms • ionic, polar covalent, or covalent • the shape of the molecule • Bonding theory should allow you to predict the shapes of molecules Tro: Chemistry: A Molecular Approach, 2/e

5. Molecular Geometry • Molecules are 3-dimensional objects • We often describe the shape of a molecule with terms that relate to geometric figures • These geometric figures have characteristic “corners” that indicate the positions of the surrounding atoms around a central atom in the center of the geometric figure • The geometric figures also have characteristic angles that we call bond angles Tro: Chemistry: A Molecular Approach, 2/e

6. Lewis Theory PredictsElectron Groups • Lewis theory predicts there are regions of electrons in an atom • Some regions result from placing shared pairs of valence electrons between bonding nuclei • Other regions result from placing unshared valence electrons on a single nuclei Tro: Chemistry: A Molecular Approach, 2/e

7. Using Lewis Theory to PredictMolecular Shapes • Lewis theory says that these regions of electron groups should repel each other • because they are regions of negative charge • This idea can then be extended to predict the shapes of molecules • the position of atoms surrounding a central atom will be determined by where the bonding electron groups are • the positions of the electron groups will be determined by trying to minimize repulsions between them Tro: Chemistry: A Molecular Approach, 2/e

8. VSEPR Theory • Electron groups around the central atom will be most stable when they are as far apart as possible – we call this valence shell electron pair repulsion theory • because electrons are negatively charged, they should be most stable when they are separated as much as possible • The resulting geometric arrangement will allow us to predict the shapes and bond angles in the molecule Tro: Chemistry: A Molecular Approach, 2/e

9. Tro: Chemistry: A Molecular Approach, 2/e

10. there are three electron groups on N three lone pair one single bond one double bond • • • • • • • • O N O • • • • Electron Groups • The Lewis structure predicts the number of valence electron pairs around the central atom(s) • Each lone pair of electrons constitutes one electron group on a central atom • Each bond constitutes one electron group on a central atom • regardless of whether it is single, double, or triple Tro: Chemistry: A Molecular Approach, 2/e

11. Electron Group Geometry • There are five basic arrangements of electron groups around a central atom • based on a maximum of six bonding electron groups • though there may be more than six on very large atoms, it is very rare • Each of these five basic arrangements results in five different basic electron geometries • in order for the molecular shape and bond angles to be a “perfect” geometric figure, all the electron groups must be bonds and all the bonds must be equivalent • For molecules that exhibit resonance, it doesn’t matter which resonance form you use – the electron geometry will be the same Tro: Chemistry: A Molecular Approach, 2/e

12. Linear Electron Geometry • When there are two electron groups around the central atom, they will occupy positions on opposite sides of the central atom • This results in the electron groups taking a linear geometry • The bond angle is 180° Tro: Chemistry: A Molecular Approach, 2/e

13. Linear Geometry Tro: Chemistry: A Molecular Approach, 2/e

14. Trigonal Planar Electron Geometry • When there are three electron groups around the central atom, they will occupy positions in the shape of a triangle around the central atom • This results in the electron groups taking a trigonal planar geometry • The bond angle is 120° Tro: Chemistry: A Molecular Approach, 2/e

15. Trigonal Geometry Tro: Chemistry: A Molecular Approach, 2/e

16. Tetrahedral Electron Geometry • When there are four electron groups around the central atom, they will occupy positions in the shape of a tetrahedron around the central atom • This results in the electron groups taking a tetrahedral geometry • The bond angle is 109.5° Tro: Chemistry: A Molecular Approach, 2/e

17. Tetrahedral Geometry Tro: Chemistry: A Molecular Approach, 2/e

18. Trigonal Bipyramidal Electron Geometry • When there are five electron groups around the central atom, they will occupy positions in the shape of two tetrahedra that are base-to-base with the central atom in the center of the shared bases • This results in the electron groups taking a trigonal bipyramidal geometry • The positions above and below the central atom are called the axial positions • The positions in the same base plane as the central atom are called the equatorial positions • The bond angle between equatorial positions is 120° • The bond angle between axial and equatorial positions is 90° Tro: Chemistry: A Molecular Approach, 2/e

19. Trigonal Bipyramid Tro: Chemistry: A Molecular Approach, 2/e

20. Trigonal Bipyramidal Geometry Tro: Chemistry: A Molecular Approach, 2/e

21. Tro: Chemistry: A Molecular Approach, 2/e

22. Octahedral Electron Geometry • When there are six electron groups around the central atom, they will occupy positions in the shape of two square-base pyramids that are base-to-base with the central atom in the center of the shared bases • This results in the electron groups taking an octahedral geometry • it is called octahedral because the geometric figure has eight sides • All positions are equivalent • The bond angle is 90° Tro: Chemistry: A Molecular Approach, 2/e

23. Octahedral Geometry Tro: Chemistry: A Molecular Approach, 2/e

24. Octahedral Geometry Tro: Chemistry: A Molecular Approach, 2/e

25. Tro: Chemistry: A Molecular Approach, 2/e

26. Molecular Geometry • The actual geometry of the molecule may be different from the electron geometry • When the electron groups are attached to atoms of different size, or when the bonding to one atom is different than the bonding to another, this will affect the molecular geometry around the central atom • Lone pairs also affect the molecular geometry • they occupy space on the central atom, but are not “seen” as points on the molecular geometry Tro: Chemistry: A Molecular Approach, 2/e

27. Not Quite Perfect Geometry Because the bonds and atom sizes are not identical in formaldehyde, the observed angles are slightly different from ideal Tro: Chemistry: A Molecular Approach, 2/e

28. The Effect of Lone Pairs • Lone pair groups “occupy more space” on the central atom • because their electron density is exclusively on the central atom rather than shared like bonding electron groups • Relative sizes of repulsive force interactions is Lone Pair – Lone Pair > Lone Pair – Bonding Pair > Bonding Pair – Bonding Pair • This affects the bond angles, making the bonding pair – bonding pair angles smaller than expected Tro: Chemistry: A Molecular Approach, 2/e

29. Effect of Lone Pairs The bonding electrons are shared by two atoms, so some of the negative charge is removed from the central atom The nonbonding electrons are localized on the central atom, so area of negative charge takes more space Tro: Chemistry: A Molecular Approach, 2/e

30. Bond Angle Distortion from Lone Pairs Tro: Chemistry: A Molecular Approach, 2/e

31. Bond Angle Distortion from Lone Pairs Tro: Chemistry: A Molecular Approach, 2/e

32. Bent Molecular Geometry:Derivative of Trigonal Planar Electron Geometry • When there are three electron groups around the central atom, and one of them is a lone pair, the resulting shape of the molecule is called a trigonal planar — bent shape • The bond angle is less than 120° • because the lone pair takes up more space Tro: Chemistry: A Molecular Approach, 2/e

33. Pyramidal & Bent Molecular Geometries:Derivatives of Tetrahedral Electron Geometry • When there are four electron groups around the central atom, and one is a lone pair, the result is called a pyramidal shape • because it is a triangular-base pyramid with the central atom at the apex • When there are four electron groups around the central atom, and two are lone pairs, the result is called a tetrahedral—bent shape • it is planar • it looks similar to the trigonal planar—bent shape, except the angles are smaller • For both shapes, the bond angle is less than 109.5° Tro: Chemistry: A Molecular Approach, 2/e

34. Methane Tro: Chemistry: A Molecular Approach, 2/e

35. Pyramidal Shape Tro: Chemistry: A Molecular Approach, 2/e

36. Pyramidal Shape Tro: Chemistry: A Molecular Approach, 2/e

37. Tetrahedral–Bent Shape Tro: Chemistry: A Molecular Approach, 2/e

38. Tetrahedral–Bent Shape Tro: Chemistry: A Molecular Approach, 2/e

39. Derivatives of theTrigonal Bipyramidal Electron Geometry • When there are five electron groups around the central atom, and some are lone pairs, they will occupy the equatorial positions because there is more room • When there are five electron groups around the central atom, and one is a lone pair, the result is called the seesaw shape • aka distorted tetrahedron • When there are five electron groups around the central atom, and two are lone pairs, the result is called the T-shaped • When there are five electron groups around the central atom, and three are lone pairs, the result is a linear shape • The bond angles between equatorial positions are less than 120° • The bond angles between axial and equatorial positions are less than 90° • linear = 180° axial–to–axial Tro: Chemistry: A Molecular Approach, 2/e

40. Replacing Atoms with Lone Pairsin the Trigonal Bipyramid System Tro: Chemistry: A Molecular Approach, 2/e

41. Seesaw Shape Tro: Chemistry: A Molecular Approach, 2/e

42. T–Shape Tro: Chemistry: A Molecular Approach, 2/e

43. T–Shape Tro: Chemistry: A Molecular Approach, 2/e

44. Linear Shape Tro: Chemistry: A Molecular Approach, 2/e

45. Derivatives of theOctahedral Geometry • When there are six electron groups around the central atom, and some are lone pairs, each even number lone pair will take a position opposite the previous lone pair • When there are six electron groups around the central atom, and one is a lone pair, the result is called a square pyramid shape • the bond angles between axial and equatorial positions is less than 90° • When there are six electron groups around the central atom, and two are lone pairs, the result is called a square planar shape • the bond angles between equatorial positions is 90° Tro: Chemistry: A Molecular Approach, 2/e

46. Square Pyramidal Shape Tro: Chemistry: A Molecular Approach, 2/e

47. Square Planar Shape Tro: Chemistry: A Molecular Approach, 2/e

48. Tro: Chemistry: A Molecular Approach, 2/e

49. Predicting the Shapes Around Central Atoms 1. Draw the Lewis structure 2. Determine the number of electron groups around the central atom 3. Classify each electron group as bonding or lone pair, and count each type • remember, multiple bonds count as one group 4. Use Table 10.1 to determine the shape and bond angles Tro: Chemistry: A Molecular Approach, 2/e

50. Example 10.2: Predict the geometry and bond angles of PCl3 Tro: Chemistry: A Molecular Approach, 2/e 1. Draw the Lewis structure a) 26 valence electrons 2. Determine the Number of electron groups around central atom a) four electron groups around P