1. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro Solution Draw Lewis symbols for calcium and chlorine based on their number of valence electrons, obtained from their group number in the periodic table. Calcium must lose its two valence electrons (to be left with an octet in its previous principal shell), while chlorine only needs to gain one electron to get an octet. Draw two chlorine anions, each with an octet and a 1– charge, and one calcium cation with a 2+ charge. Place brackets around the chlorine anions and indicate the charges on each ion. Finally, write the formula with subscripts to indicate the number of atoms. CaCl 2 For Practice 9.1 Use Lewis symbols to predict the formula for the compound that forms between magnesium and nitrogen. Use Lewis symbols to predict the formula for the compound that forms between calcium and chlorine. Example 9.1Using Lewis Symbols to Predict the Chemical Formula of an Ionic Compound

2. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro Solution KBr and KCl should have lattice energies of smaller magnitude than CaO and SrO because of their lower ionic charges (1+, 1– compared to 2+, 2–.) When you compare KBr and KCl, you expect KBr to have a lattice energy of lower magnitude due to the larger ionic radius of the bromide ion relative to the chloride ion. Between CaO and SrO, you expect SrO to have a lattice energy of lower magnitude due to the larger ionic radius of the strontium ion relative to the calcium ion. Order of increasing magnitude of lattice energy: KBr < KCl < SrO < CaO Actual lattice energy values: For Practice 9.2 Arrange the following in order of increasing magnitude of lattice energy: LiBr, KI, and CaO. For More Practice 9.2 Which compound has a lattice energy of higher magnitude, NaCl or MgCl 2 ? Arrange these ionic compounds in order of increasing magnitude of lattice energy: CaO, KBr, KCl, SrO. Example 9.2Predicting Relative Lattice Energies

3. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro Solution a.In Figure 9.8, find the electronegativity of Sr (1.0) and of F (4.0). The electronegativity difference (ΔEN) is ΔEN = 4.0 – 1.0 = 3.0. Using Table 9.1, classify this bond as ionic. b.In Figure 9.8, find the electronegativity of N (3.0) and of Cl (3.0). The electronegativity difference (ΔEN) is ΔEN = 3.0 – 3.0 = 0. Using Table 9.1, classify this bond as covalent. c.In Figure 9.8, find the electronegativity of N (3.0) and of O (3.5). The electronegativity difference (ΔEN) is ΔEN = 3.5 – 3.0 = 0.5. Using Table 9.1, classify this bond as polar covalent. Determine whether the bond formed between each pair of atoms is covalent, polar covalent, or ionic. a.Sr and Fb. N and Clc. N and O Example 9.3Classifying Bonds as Pure Covalent, Polar Covalent, or Ionic FIGURE 9.8 Electronegativities of the Elements Electronegativity generally increases as we move across a row in the periodic table and decreases as we move down a column.

4. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro For Practice 9.3 Determine whether the bond formed between each pair of atoms is pure covalent, polar covalent, or ionic. a.I and Ib. Cs and Brc. P and O Continued Example 9.3Classifying Bonds as Pure Covalent, Polar Covalent, or Ionic

5. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro Example 9.4Writing Lewis Structures Write the Lewis Structure for CO 2. Procedure For… Writing Lewis Structures for Covalent Compounds Solution Step 1Write the correct skeletal structure for the molecule. Because carbon is the less electronegative atom, put it in the central position. O C O Step 2Calculate the total number of electrons for the Lewis structure by summing the valence electrons of each atom in the molecule. Step 3Distribute the electrons among the atoms, giving octets (or duets for hydrogen) to as many atoms as possible. Begin with the bonding electrons, and then proceed to lone pairs on terminal atoms, and finally to lone pairs on the central atom. Bonding electrons are first. O:C:O (4 of 16 electrons used)

6. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro Example 9.4Writing Lewis Structures Continued Lone pairs on terminal atoms are next. (16 of 16 electrons used) Step 4If any atom lacks an octet, form double or triple bonds as necessary to give them octets. Since carbon lacks an octet, move lone pairs from the oxygen atoms to bonding regions to form double bonds. For Practice 9.4 Write the Lewis structure for CO.

7. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro Example 9.5Writing Lewis Structures Write the Lewis Structure for NH 3. Procedure For… Writing Lewis Structures for Covalent Compounds Solution Step 1Write the correct skeletal structure for the molecule. Since hydrogen is always terminal, put nitrogen in the central position. Step 2Calculate the total number of electrons for the Lewis structure by summing the valence electrons of each atom in the molecule.

8. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro Step 3Distribute the electrons among the atoms, giving octets (or duets for hydrogen) to as many atoms as possible. Begin with the bonding electrons, and then proceed to lone pairs on terminal atoms, and finally to lone pairs on the central atom. Bonding electrons are first. (6 of 8 electrons used) Lone pairs on terminal atoms are next, but none is needed on hydrogen. Lone pairs on central atom are last. (8 of 8 electrons used) Step 4Since all of the atoms have octets (or duets for hydrogen), the Lewis structure for NH 3 is complete as shown in the previous step. For Practice 9.5 Write the Lewis structure for H 2 CO. Example 9.5Writing Lewis Structures Continued

9. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro Solution Begin by writing the skeletal structure. Since hydrogen is always terminal, put the nitrogen atom in the central position. Calculate the total number of electrons for the Lewis structure by summing the number of valence electrons for each atom and subtracting 1 for the 1+ charge. Place two bonding electrons between every two atoms. Since all of the atoms have complete octets, no double bonds are necessary. (8 of 8 electrons used) Write the Lewis structure for the NH 4 + ion. Example 9.6Writing Lewis Structures for Polyatomic Ions

10. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro Lastly, write the Lewis structure in brackets with the charge of the ion in the upper right-hand corner. For Practice 9.6 Write the Lewis structure for the hypochlorite ion, ClO –. Example 9.6Writing Lewis Structures for Polyatomic Ions Continued

11. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro Solution Begin by writing the skeletal structure. Since nitrogen is the least electronegative atom, put it in the central position. Calculate the total number of electrons for the Lewis structure by summing the number of valence electrons for each atom and adding 1 for the 1– charge. Place two bonding electrons between each pair of atoms. (6 of 24 electrons used) Write a Lewis structure for the NO 3 – ion. Include resonance structures. Example 9.7Writing Resonance Structures

12. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro Distribute the remaining electrons, first to terminal atoms. There are not enough electrons to complete the octet on the central atom. (24 of 24 electrons used) Form a double bond by moving a lone pair from one of the oxygen atoms into the bonding region with nitrogen. Enclose the structure in brackets and include the charge. Continued Example 9.7Writing Resonance Structures

13. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro Since the double bond can form equally well with any of the three oxygen atoms, write all three structures as resonance structures. (The actual space filling model of NO 3 – is shown here for comparison. Note that all three bonds are equal in length.) For Practice 9.7 Write a Lewis structure for the NO 2 – ion. Include resonance structures. Continued Example 9.7Writing Resonance Structures

14. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro Solution Calculate the formal charge on each atom by finding the number of valence electrons and subtracting the number of nonbonding electrons and one-half the number of bonding electrons. The sum of all formal charges for each structure is –1, as it should be for a 1– ion. Structures A and B have the least amount of formal charge and are therefore to be preferred over structure C. Structure A is preferable to B because it has the negative formal charge on the more electronegative atom. You therefore expect structure A to make the biggest contribution to the resonance forms of the cyanate ion. Assign formal charges to each atom in the resonance forms of the cyanate ion (OCN – ). Which resonance form is likely to contribute most to the correct structure of OCN – ? Example 9.8Assigning Formal Charges

15. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro For Practice 9.8 Assign formal charges to each atom in the resonance forms of N 2 O. Which resonance form is likely to contribute most to the correct structure of N 2 O? For More Practice 9.8 Assign formal charges to each of the atoms in the nitrate ion (NO 3 – ). The Lewis structure for the nitrate ion is shown in Example 9.7. Continued Example 9.8Assigning Formal Charges

16. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro Solution Begin by writing the skeletal structure. For organic compounds, the condensed structural formula (in this case CH 3 NO 2 ) indicates how the atoms are connected. Calculate the total number of electrons for the Lewis structure by summing the number of valence electrons for each atom. Draw the Lewis structure (including resonance structures) for nitromethane (CH 3 NO 2 ). For each resonance structure, assign formal charges to all atoms that have formal charge. Example 9.9Drawing Resonance Structures and Assigning Formal Charge for Organic Compounds

17. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro Place a dash between each pair of atoms to indicate a bond. Each dash counts for two electrons. (12 of 24 electrons used) Distribute the remaining electrons, first to terminal atoms then to interior atoms. (24 of 24 electrons used) If there are not enough electrons to complete the octets on the interior atoms, form double bonds by moving lone pair electrons from terminal atoms into the bonding region with interior atoms. Continued Example 9.9Drawing Resonance Structures and Assigning Formal Charge for Organic Compounds

18. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro Draw any necessary resonance structures by moving only electron dots. (In this case, you can form a double bond between the nitrogen atom and the other oxygen atom.) Assign formal charges (FC) to each atom. FC = # valence e – – (# nonbonding e – + ½ # bonding e – ) Carbon, hydrogen, and the doubly-bonded oxygen atoms have no formal charge. Nitrogen has a +1 formal charge [5 – ½ (8)] and the singly bonded oxygen atom in each resonance structure has a –1 formal charge [6 – (6 + ½ (2))]. Continued Example 9.9Drawing Resonance Structures and Assigning Formal Charge for Organic Compounds

19. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro For Practice 9.8 Draw the Lewis structure (including resonance structures) for diazomethane (CH 2 N 2 ). For each resonance structure, assign formal charges to all atoms that have formal charge. Continued Example 9.9Drawing Resonance Structures and Assigning Formal Charge for Organic Compounds

20. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro Solution Begin by writing the skeletal structure. Since xenon is the less electronegative atom, put it in the central position. F Xe F Calculate the total number of electrons for the Lewis structure by summing the number of valence electrons for each atom. Place two bonding electrons between the atoms of each pair of atoms. F:Xe:F (4 of 22 electrons used) Write the Lewis structure for XeF 2. Example 9.10Writing Lewis Structures for Compounds Having Expanded Octets

21. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro Distribute the remaining electrons to give octets to as many atoms as possible, beginning with terminal atoms and finishing with the central atom. Arrange additional electrons around the central atom, giving it an expanded octet of up to 12 electrons. (16 of 22 electrons used) (22 of 22 electrons used) For Practice 9.10 Write the Lewis structure for XeF 4. For More Practice 9.10 Write the Lewis structure for H 3 PO 4. If necessary, expand the octet on any appropriate atoms to lower formal charge. Continued Example 9.10Writing Lewis Structures for Compounds Having Expanded Octets

22. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro Solution Begin by rewriting the reaction using the Lewis structures of the molecules involved. Determine which bonds are broken in the reaction and sum the bond energies of these. Hydrogen gas, a potential fuel, can be made by the reaction of methane gas and steam. Use bond energies to calculate ΔH rxn for this reaction. Example 9.11Calculating Δ H rxn from Bond Energies

23. © 2014 Pearson Education, Inc. Chemistry: A Molecular Approach, 3rd Edition Nivaldo J. Tro Determine which bonds are formed in the reaction and sum the negatives of their bond energies. Find ΔH rxn by summing the results of the previous two steps. For Practice 9.11 Another potential future fuel is methanol (CH 3 OH). Write a balanced equation for the combustion of gaseous methanol and use bond energies to calculate the enthalpy of combustion of methanol in kJ/mol. For More Practice 9.11 Use bond energies to calculate ΔH rxn for this reaction:. Continued Example 9.11Calculating Δ H rxn from Bond Energies