CHEM 1251

Problem Set #15

Textbook Reading
Sections 8.7-8.9

Textbook Problems
8.53, 57, 69, 73, 79, 81, 95
RESONANCE STRUCTURES

What do you do if you have multiple structures with the same formal charges? In these cases, one
single Lewis structure cannot accurately represent the true nature of the bonding, so you must draw all of
the resonance structures that, taken together, give a picture of the bonding. The actual structure of a
molecule exhibiting resonance is an average of its resonance structures.
Note that resonance structures can be drawn for any molecule that has more than one possible
bonding scheme, regardless of the formal charges. The most contributing structures, however, are those
with the lowest overall formal charges.
1. In the top box, name the compound. In the middle box, draw appropriate bond dipoles between each
pair of elements. In the bottom box, draw Lewis structures of the compounds, obeying the octet rule
whenever possible. Dont forget to label non-zero formal charges. If multiple structures are possible, show
all of the resonance structures, and circle the most contributing structure.
(a) CS2

(b) ICl3

NAME: carbon disulfide

(c) KrF3+

NAME: iodine trichloride

bad example sorry! same EN!

(c) BH3

(d) NO2

borane

NAME: nitrite

(e) H2SO4 (Hint: H connects to O)

NAME: sulfuric acid

2. One of the 20 standard amino acids is methionine, which has the formula C 5H11NO2S at physiological
pH.
(a) Fill in the Lewis structure below by adding
any missing lone pairs, multiple bonds, and/or
formal charges to complete all octets. (Hint:
There should be two formal charges.)

(b) In the box below, draw a resonance structure

for methionine. Make sure that all formal charges
are labeled.

(c) If this molecule has formal charges, why is there no overall charge on the molecule?

All of the formal charges add up to equal the overall charge on the entire molecule. Because
methionine is neutral overall, the +1 and 1 charges cancel one another out.

3. One component of smog is nitrogen dioxide, NO2, which affords the brown coloration to smog layers.
(a) Draw the two resonance structures of nitrogen dioxide. (Hint: How many total electrons are there?)

Note that
and
are also possible structures, although these do not
follow the rules for drawing Lewis structures.
(b) At low temperatures, a nitrogen-nitrogen single bond can form from reaction of two nitrogen dioxide
molecules, yielding colorless, gaseous dinitrogen tetroxide. Draw the four resonance structures.

4. Write the name of the compound in the top box. Then, draw Lewis structures that obey the octet rule for
the compounds below. Include any non-zero formal charges.
(a) PCl5

(b) P2O5 (hint: bridging O between two P atoms)

phosphorus pentachloride

diphosphorus pentoxide

(c) PO33

(d) PO43

phosphite

phosphate

5. Draw Lewis structures of PO33- (phosphite) and of PO43- (phosphate) with minimized formal charges.
(a) phosphite

(b) phosphate

(c) phosphoric acid

6. (a) Draw three valid Lewis structures of thiocyanate, CNS (hint: the connectivity is N-C-S). Be sure to
label any formal charges.

(b) Which is/are the most contributing resonance structure(s)? Justify your answer.

The most contributing resonance structures are those with (a) the lowest overall formal
charges, and with (b) the negative formal charge on the more electronegative element. In
this case, N is more electronegative than S, so the middle structure is the most contributing
structure. (Remember, though, the actual structure is a weighted average of the three!)
BOND STRENGTH AND BOND LENGTH
Now that you can draw Lewis structures, you can use them to compare properties of bonds, such as
bond strength and bond length. The number of bonds is called the bond order. We can easily describe a
single, double, or triple bond, but we can also have fractional bond orders, such as cases with resonance
structures where average bond orders must be calculated. Higher bond orders correlate to greater bond
strengths and shorter bond lengths.
The strength of bond can also be measured through average bond enthalpies, which tell us the
enthalpy change ( H) required to break a particular bond in one mole of a gaseous substance. Many of
these values are tabulated, and we can now use average bond enthalpies to calculate the enthalpy change
for a reaction through the equation:
Hrxn = (bond enthalpies of bonds broken) (bond enthalpies of bonds formed)
7. Rank the N-O bond lengths, from shortest to longest, in NO+, NO2, and NO3. Justify your answer.

NO+ < NO2 < NO3. The Lewis structure of NO+ has an N-O triple bond; stronger bonds are
shorter. NO2 has two equivalent resonance structures with a single and double bond, so it
has a 1.5 bond, on average. NO3 has three equivalent resonance structures with one double
and two single bonds, so the average structure has a 1.33 bond, and will be the longest.
8. Acetylene torches are used for cutting and welding metals and quartz glass. Acetylene torches burn very
hot at about 2500 C in air compared to methane flames, which burn at about 1950 C in air.
(a)Write and balance the reaction for the combustion of acetylene (HCCH) gas. Assume that the water
formed is gaseous, and include all of the physical states.

C2H2(g) + 5/2 O2(g) H2O(g) + 2 CO2(g) If you double the coefficients, you should double all
of the answers in the following parts.

(b) Draw Lewis structures for each of the molecules in your reaction from part (a).

reactants

products

(c) Calculate the change in enthalpy for the combustion of acetylene using the bond enthalpies provided in
the table to the right. Show all your work.
bond
H (kJ/mol)
Hrxn = [2D(C-H) + 1D(C C) +5/2D(O=O)] [2D(O-H) +4D(C=O)]
= [2 mol(413 kJ/mol) + 1 mol(839 kJ/mol) + 2.5 mol(495 kJ/mol)]
[2 mol(463 kJ/mol) + 4 mol(799 kJ/mol)]
= 1220. kJ (for the combustion of one mole of C2H2)

(d) Justify why your value of Hrxn makes sense for this reaction.

This is a combustion reaction, so it should be pretty highly

exothermic, especially for a torch used to weld metals and
quartz glasses.

H-H

436

C-H

413

O-O

146

O=O

495

C-C

348

C=C

614

C C

839

C-O

358

C=O

799

C O

1072

O-H

463

9. Calculate the enthalpy change for the decomposition of gaseous hydrogen peroxide to gaseous water
and gaseous oxygen.

2 H2O2(g) 2 H2O(g) + O2(g) Be sure to include a balanced reaction!

Hrxn = [4D(O-H) + 2D(O-O)] [4D(O-H) +1D(O=O)]

= [4 mol(463 kJ/mol) + 2 mol(146 kJ/mol)] [4 mol(463 kJ/mol) + 1 mol(495 kJ/mol)]
= 2144 kJ 2347 kJ = 203 kJ (per 2 mol H2O2 that reacts)