1. 1 Chapter 8 “Covalent Bonding” Pre-AP Chemistry Charles Page High School Stephen L. Cotton Ball-and-stick model

2. 2 Section 8.1 Molecular Compounds l OBJECTIVES: –Distinguish between the melting points and boiling points of molecular compounds and ionic compounds.

3. 3 Section 8.1 Molecular Compounds l OBJECTIVES: –Describe the information provided by a molecular formula.

4. 4 Bonds are… Forces that hold groups of atoms together and make them function as a unit. Two types: 1) Ionic bonds – transfer of electrons (gained or lost; makes formula unit) 2) Covalent bonds – sharing of electrons. The resulting particle is called a “molecule”

5. 5 Covalent Bonds l The word covalent is a combination of the prefix co- (from Latin com, meaning “with” or “together”), and the verb valere, meaning “to be strong”. l Two electrons shared together have the strength to hold two atoms together in a bond.

6. 6 Molecules  Many elements found in nature are in the form of molecules:  a neutral group of atoms joined together by covalent bonds.  For example, air contains oxygen molecules, consisting of two oxygen atoms joined covalently  Called a “diatomic molecule” (O 2 )

7. 7 How does H 2 form? l The nuclei repel each other, since they both have a positive charge (like charges repel). ++ (diatomic hydrogen molecule) + +

8. 8 How does H 2 form? ++ l But, the nuclei are attracted to the electrons l They share the electrons, and this is called a “covalent bond”, and involves only NONMETALS!

9. 9 Covalent bonds l Nonmetals hold on to their valence electrons. l They can’t give away electrons to bond. –But still want noble gas configuration. l Get it by sharing valence electrons with each other = covalent bonding l By sharing, both atoms get to count the electrons toward a noble gas configuration.

10. 10 Covalent bonding l Fluorine has seven valence electrons (but would like to have 8) F

11. 11 Covalent bonding l Fluorine has seven valence electrons l A second atom also has seven FF

12. 12 Covalent bonding l Fluorine has seven valence electrons l A second atom also has seven l By sharing electrons… FF

13. 13 Covalent bonding l Fluorine has seven valence electrons l A second atom also has seven l By sharing electrons… FF

14. 14 Covalent bonding l Fluorine has seven valence electrons l A second atom also has seven l By sharing electrons… FF

15. 15 Covalent bonding l Fluorine has seven valence electrons l A second atom also has seven l By sharing electrons… FF

16. 16 Covalent bonding l Fluorine has seven valence electrons l A second atom also has seven l By sharing electrons… FF

17. 17 Covalent bonding l Fluorine has seven valence electrons l A second atom also has seven l By sharing electrons… l …both end with full orbitals FF

18. 18 Covalent bonding l Fluorine has seven valence electrons l A second atom also has seven l By sharing electrons… l …both end with full orbitals FF 8 Valence electrons

19. 19 Covalent bonding l Fluorine has seven valence electrons l A second atom also has seven l By sharing electrons… l …both end with full orbitals FF 8 Valence electrons

20. 20

21. 21 Molecular Compounds l Compounds that are bonded covalently (like in water, or carbon dioxide) are called molecular compounds l Molecular compounds tend to have relatively lower melting and boiling points than ionic compounds – this is not as strong a bond as ionic

22. 22 Molecular Compounds l Thus, molecular compounds tend to be gases or liquids at room temperature –Ionic compounds were solids l A molecular compound has a molecular formula: –Shows how many atoms of each element a molecule contains

23. 23 Molecular Compounds l The formula for water is written as H 2 O –The subscript “2” behind hydrogen means there are 2 atoms of hydrogen; if there is only one atom, the subscript 1 is omitted l Molecular formulas do not tell any information about the structure (the arrangement of the various atoms).

24. 24 - Page 215 These are some of the different ways to represent ammonia: 1. The molecular formula shows how many atoms of each element are present 2. The structural formula ALSO shows the arrangement of these atoms! 3. The ball and stick model is the BEST, because it shows a 3-dimensional arrangement.

25. 25 Section 8.2 The Nature of Covalent Bonding l OBJECTIVES: –Describe how electrons are shared to form covalent bonds, and identify exceptions to the octet rule.

26. 26 Section 8.2 The Nature of Covalent Bonding l OBJECTIVES: –Demonstrate how electron dot structures represent shared electrons.

27. 27 Section 8.2 The Nature of Covalent Bonding l OBJECTIVES: –Describe how atoms form double or triple covalent bonds.

28. 28 Section 8.2 The Nature of Covalent Bonding l OBJECTIVES: –Distinguish between a covalent bond and a coordinate covalent bond, and describe how the strength of a covalent bond is related to its bond dissociation energy.

29. 29 Section 8.2 The Nature of Covalent Bonding l OBJECTIVES: –Describe how oxygen atoms are bonded in ozone.

30. 30 A Single Covalent Bond is... l A sharing of two valence electrons. l Only nonmetals and hydrogen. l Different from an ionic bond because they actually form molecules. l Two specific atoms are joined. l In an ionic solid, you can’t tell which atom the electrons moved from or to

31. 31 Sodium Chloride Crystal Lattice Ionic compounds organize in a characteristic crystal lattice of alternating positive and negative ions, repeated over and over.Ionic compounds organize in a characteristic crystal lattice of alternating positive and negative ions, repeated over and over.

32. 32 How to show the formation… l It’s like a jigsaw puzzle. l You put the pieces together to end up with the right formula. l Carbon is a special example - can it really share 4 electrons: 1s 2 2s 2 2p 2 ? –Yes, due to electron promotion! l Another example: lets show how water is formed with covalent bonds, by using an electron dot diagram

33. 33 Water H O Each hydrogen has 1 valence electron - Each hydrogen wants 1 more The oxygen has 6 valence electrons - The oxygen wants 2 more They share to make each other complete

34. 34 Water l Put the pieces together l The first hydrogen is happy l The oxygen still needs one more H O

35. 35 Water l So, a second hydrogen attaches l Every atom has full energy levels H O H Note the two “unshared” pairs of electrons

36. 36 Examples: 1. Conceptual Problem 8.1 on page 220 2. Do PCl 3

37. 37 Multiple Bonds l Sometimes atoms share more than one pair of valence electrons. l A double bond is when atoms share two pairs of electrons (4 total) l A triple bond is when atoms share three pairs of electrons (6 total) l Table 8.1, p.222 - Know these 7 elements as diatomic: Br 2 I 2 N 2 Cl 2 H 2 O 2 F 2 What’s the deal with the oxygen dot diagram?

38. 38 Dot diagram for Carbon dioxide l CO 2 - Carbon is central atom ( more metallic ) l Carbon has 4 valence electrons l Wants 4 more l Oxygen has 6 valence electrons l Wants 2 more O C

39. 39 Carbon dioxide l Attaching 1 oxygen leaves the oxygen 1 short, and the carbon 3 short O C

40. 40 Carbon dioxide l Attaching the second oxygen leaves both of the oxygen 1 short, and the carbon 2 short O C O

41. 41 Carbon dioxide l The only solution is to share more O C O

42. 42 Carbon dioxide l The only solution is to share more O C O

43. 43 Carbon dioxide l The only solution is to share more O CO

44. 44 Carbon dioxide l The only solution is to share more O CO

45. 45 Carbon dioxide l The only solution is to share more O CO

46. 46 Carbon dioxide l The only solution is to share more O CO

47. 47 Carbon dioxide l The only solution is to share more l Requires two double bonds l Each atom can count all the electrons in the bond O CO

48. 48 Carbon dioxide l The only solution is to share more l Requires two double bonds l Each atom can count all the electrons in the bond O CO 8 valence electrons

49. 49 Carbon dioxide l The only solution is to share more l Requires two double bonds l Each atom can count all the electrons in the bond O CO 8 valence electrons

50. 50 Carbon dioxide l The only solution is to share more l Requires two double bonds l Each atom can count all the electrons in the bond O CO 8 valence electrons

51. 51 How to draw them? Use the handout guidelines: 1)Add up all the valence electrons. 2)Count up the total number of electrons to make all atoms happy. 3)Subtract; then Divide by 2 4)Tells you how many bonds to draw 5)Fill in the rest of the valence electrons to fill atoms up.

52. 52 Example l NH 3, which is ammonia l N – central atom; has 5 valence electrons, wants 8 l H - has 1 (x3) valence electrons, wants 2 (x3) l NH 3 has 5+3 = 8 l NH 3 wants 8+6 = 14 l (14-8)/2= 3 bonds l 4 atoms with 3 bonds N H

53. 53 NHH H Examples l Draw in the bonds; start with singles l All 8 electrons are accounted for l Everything is full – done with this one.

54. 54 Example: HCN l HCN: C is central atom l N - has 5 valence electrons, wants 8 l C - has 4 valence electrons, wants 8 l H - has 1 valence electron, wants 2 l HCN has 5+4+1 = 10 l HCN wants 8+8+2 = 18 l (18-10)/2= 4 bonds l 3 atoms with 4 bonds – this will require multiple bonds - not to H however

55. 55 HCN l Put single bond between each atom l Need to add 2 more bonds l Must go between C and N (Hydrogen is full) NHC

56. 56 HCN l Put in single bonds l Needs 2 more bonds l Must go between C and N, not the H l Uses 8 electrons – need 2 more to equal the 10 it has NHC

57. 57 HCN l Put in single bonds l Need 2 more bonds l Must go between C and N l Uses 8 electrons - 2 more to add l Must go on the N to fill its octet NHC

58. 58 Another way of indicating bonds l Often use a line to indicate a bond l Called a structural formula l Each line is 2 valence electrons HHO = HHO

59. 59 Other Structural Examples H CN C O H H

60. 60 A Coordinate Covalent Bond... l When one atom donates both electrons in a covalent bond. l Carbon monoxide (CO) is a good example: OC Both the carbon and oxygen give another single electron to share

61. 61 Coordinate Covalent Bond l When one atom donates both electrons in a covalent bond. l Carbon monoxide (CO) is a good example: OC Oxygen gives both of these electrons, since it has no more singles to share. This carbon electron moves to make a pair with the other single.

62. 62 Coordinate Covalent Bond l When one atom donates both electrons in a covalent bond. l Carbon monoxide (CO) OC C O The coordinate covalent bond is shown with an arrow as:

63. 63 Coordinate covalent bond l Most polyatomic cations and anions contain covalent and coordinate covalent bonds l Table 8.2, p.224 l Sample Problem 8.2, p.225 l The ammonium ion (NH 4 1+ ) can be shown as another example

64. 64 Bond Dissociation Energies... l The total energy required to break the bond between 2 covalently bonded atoms l High dissociation energy usually means the chemical is relatively unreactive, because it takes a lot of energy to break it down.

65. 65 Resonance is... l When more than one valid dot diagram is possible. l Consider the two ways to draw ozone (O 3 ) l Which one is it? Does it go back and forth? l It is a hybrid of both, like a mule; and shown by a double-headed arrow l found in double-bond structures!

66. 66 Resonance in Ozone Neither structure is correct, it is actually a hybrid of the two. To show it, draw all varieties possible, and join them with a double-headed arrow. Note the different location of the double bond

67. 67 Resonance Occurs when more than one valid Lewis structure can be written for a particular molecule (due to position of double bond) These are resonance structures of benzene. The actual structure is an average (or hybrid) of these structures.

68. 68 Resonance in a carbonate ion (CO 3 2- ): Resonance in an acetate ion (C 2 H 3 O 2 1- ): Polyatomic ions – note the different positions of the double bond.

69. 69 The 3 Exceptions to Octet rule l For some molecules, it is impossible to satisfy the octet rule #1. usually when there is an odd number of valence electrons –NO 2 has 17 valence electrons, because the N has 5, and each O contributes 6. Note “N” page 228 l It is impossible to satisfy octet rule, yet the stable molecule does exist

70. 70 Exceptions to Octet rule Another exception: Boron Page 228 shows boron trifluoride, and note that one of the fluorides might be able to make a coordinate covalent bond to fulfill the boron #2 -But fluorine has a high electronegativity (it is greedy), so this coordinate bond does not form #3 -Top page 229 examples exist because they are in period 3 or beyond

71. 71 Section 8.3 Bonding Theories l OBJECTIVES: –Describe the relationship between atomic and molecular orbitals.

72. 72 Section 8.3 Bonding Theories l OBJECTIVES: –Describe how VSEPR theory helps predict the shapes of molecules.

73. 73 Molecular Orbitals are... l The model for covalent bonding assumes the orbitals are those of the individual atoms = atomic orbital l Orbitals that apply to the overall molecule, due to atomic orbital overlap are the molecular orbitals –A bonding orbital is a molecular orbital that can be occupied by two electrons of a covalent bond

74. 74 Molecular Orbitals - definitions l Sigma bond- when two atomic orbitals combine to form the molecular orbital that is symmetrical along the axis connecting the nuclei l Pi bond- the bonding electrons are likely to be found above and below the bond axis (weaker than sigma) l Note pictures on the next slide

75. 75 - Pages 230 and 231 Sigma bond is symmetrical along the axis between the two nuclei. Pi bond is above and below the bond axis, and is weaker than sigma

76. 76 VSEPR: stands for... l V alence S hell E lectron P air R epulsion l Predicts the three dimensional shape of molecules. l The name tells you the theory: –Valence shell = outside electrons. –Electron Pair repulsion = electron pairs try to get as far away as possible from each other. l Can determine the angles of bonds.

77. 77 VSEPR l Based on the number of pairs of valence electrons, both bonded and unbonded. l Unbonded pair also called lone pair. l CH 4 - draw the structural formula l Has 4 + 4(1) = 8 l wants 8 + 4(2) = 16 l (16-8)/2 = 4 bonds

78. 78 VSEPR for methane (a gas): l Single bonds fill all atoms. l There are 4 pairs of electrons pushing away. l The furthest they can get away is 109.5º CHH H H This 2-dimensional drawing does not show a true representation of the chemical arrangement.

79. 79 4 atoms bonded l Basic shape is tetrahedral. l A pyramid with a triangular base. l Same shape for everything with 4 pairs. C HH H H 109.5º

80. 80 Other angles, pages 232 - 233 l Ammonia (NH 3 ) = 107 o l Water (H 2 O) = 105 o l Carbon dioxide (CO 2 ) = 180 o l Note the shapes of these that are pictured on the next slide

81. 81 - Page 232 Methane has an angle of 109.5 o, called tetrahedral Ammonia has an angle of 107 o, called pyramidal Note the unshared pair that is repulsion for other electrons.

82. 82 Section 8.4 Polar Bonds and Molecules l OBJECTIVES: –Describe how electronegativity values determine the distribution of charge in a polar molecule.

83. 83 Section 8.4 Polar Bonds and Molecules l OBJECTIVES: –Describe what happens to polar molecules when they are placed between oppositely charged metal plates.

84. 84 Section 8.4 Polar Bonds and Molecules l OBJECTIVES: –Evaluate the strength of intermolecular attractions compared with the strength of ionic and covalent bonds.

85. 85 Section 8.4 Polar Bonds and Molecules l OBJECTIVES: –Identify the reason why network solids have high melting points.

86. 86 Bond Polarity l Covalent bonding means shared electrons –but, do they share equally? l Electrons are pulled, as in a tug-of- war, between the atoms nuclei –In equal sharing (such as diatomic molecules), the bond that results is called a nonpolar covalent bond

87. 87 Bond Polarity l When two different atoms bond covalently, there is an unequal sharing –the more electronegative atom will have a stronger attraction, and will acquire a slightly negative charge –called a polar covalent bond, or simply polar bond.

88. 88 Electronegativity? The ability of an atom in a molecule to attract shared electrons to itself. The ability of an atom in a molecule to attract shared electrons to itself. Linus Pauling 1901 - 1994

89. 89 Table of Electronegativities

90. 90 Bond Polarity l Refer to Table 6.2, p. 177 (or handout) l Consider HCl H = electronegativity of 2.1 Cl = electronegativity of 3.0 –the bond is polar –the chlorine acquires a slight negative charge, and the hydrogen a slight positive charge

91. 91 Bond Polarity l Only partial charges, much less than a true 1+ or 1- as in ionic bond l Written as: HCl l the positive and minus signs (with the lower case delta: ) denote partial charges.    and  

92. 92 Bond Polarity l Can also be shown: –the arrow points to the more electronegative atom. Table 8.3, p.238 shows how the electronegativity can also indicate the type of bond that tends to form HCl

93. 93 Polar molecules l Sample Problem 8.3, p.239 l A polar bond tends to make the entire molecule “polar” –areas of “difference” l HCl has polar bonds, thus is a polar molecule. –A molecule that has two poles is called dipole, like HCl

94. 94 Polar molecules l The effect of polar bonds on the polarity of the entire molecule depends on the molecule shape –carbon dioxide has two polar bonds, and is linear = nonpolar molecule!

95. 95 Polar molecules l The effect of polar bonds on the polarity of the entire molecule depends on the molecule shape –water has two polar bonds and a bent shape; the highly electronegative oxygen pulls the e - away from H = very polar!

96. 96 Polar molecules l When polar molecules are placed between oppositely charged plates, they tend to become oriented with respect to the positive and negative plates. l Figure 8.24, page 239

97. 97 Attractions between molecules l They are what make solid and liquid molecular compounds possible. l The weakest are called van der Waal’s forces - there are two kinds: #1. Dispersion forces weakest of all, caused by motion of e - increases as # e - increases halogens start as gases; bromine is liquid; iodine is solid – all in Group 7A

98. 98 #2. Dipole interactions l Occurs when polar molecules are attracted to each other. l 2. Dipole interaction happens in water –Figure 8.25, page 240 –positive region of one molecule attracts the negative region of another molecule.

99. 99 #2. Dipole interactions l Occur when polar molecules are attracted to each other. l Slightly stronger than dispersion forces. l Opposites attract, but not completely hooked like in ionic solids. HFHF  HFHF 

100. 100 #2. Dipole Interactions    

101. 101 #3. Hydrogen bonding l …is the attractive force caused by hydrogen bonded to N, O, F, or Cl l N, O, F, and Cl are very electronegative, so this is a very strong dipole. l And, the hydrogen shares with the lone pair in the molecule next to it. l This is the strongest of the intermolecular forces.

102. 102 Order of Intermolecular attraction strengths 1)Dispersion forces are the weakest 2)A little stronger are the dipole interactions 3)The strongest is the hydrogen bonding 4)All of these are weaker than ionic bonds

103. 103 #3. Hydrogen bonding defined: l When a hydrogen atom is: a) covalently bonded to a highly electronegative atom, AND b) is also weakly bonded to an unshared electron pair of a nearby highly electronegative atom. –The hydrogen is left very electron deficient (it only had 1 to start with!) thus it shares with something nearby –Hydrogen is also the ONLY element with no shielding for its nucleus when involved in a covalent bond!

104. 104 Hydrogen Bonding (Shown in water) H H O ++ -- ++ H H O ++ -- ++ This hydrogen is bonded covalently to: 1) the highly negative oxygen, and 2) a nearby unshared pair.

105. 105 Hydrogen bonding allows H 2 O to be a liquid at room conditions. H H O H H O H H O H H O H H O H H O H H O

106. 106 Attractions and properties l Why are some chemicals gases, some liquids, some solids? –Depends on the type of bonding! –Table 8.4, page 244 l Network solids – solids in which all the atoms are covalently bonded to each other

107. 107 Attractions and properties l Figure 8.28, page 243 l Network solids melt at very high temperatures, or not at all (decomposes) –Diamond does not really melt, but vaporizes to a gas at 3500 o C and beyond –SiC, used in grinding, has a melting point of about 2700 o C

108. 108 Covalent Network Compounds Some covalently bonded substances DO NOT form discrete molecules. Diamond, a network of covalently bonded carbon atoms Graphite, a network of covalently bonded carbon atoms

109. 109