Assignment 8 SOLUTIONS

Chem1000A

1. (a) Draw the molecular orbital (MO) diagram for the nitrosyl ion, NO+. (b) Is NO+
diamagnetic or paramagnetic? If it is paramagnetic how many unpaired electrons does it have?
(c) Determine the bond order of the NO bond in NO+ from the MO diagram. (d) When NO is
ionized to from NO+, is the nitrogen-oxygen bond becoming stronger or weaker than in NO?
a)

N+

NO+

E
2p*

2p*

2p

2p

2p
2p

2s*

2s

2s

2s
Alternatively, N can be combined with O+. The core orbitals are omitted in the diagram.
Electron configuration of NO+: (1s)2 (1s*)2 (2s)2 (2s*)2 (2p)4 (2p)2
b) The NO+ cation is diamagnetic, since all electrons are paired.
1

c) bond order
= (number of electrons in bonding MOs number of electrons in antibonding MOs
= (8-2) = (6) = 3
The bond order of the nitrogen-oxygen bond in NO+ is three (triple bond).
d) The additional electron in NO is located in an antibonding MO. Therefore, the bond order in
NO is 2.5 (as discussed in class). Upon ionization of NO, the nitrong-oxygen bond becomes
stronger, i.e., the bond order increases from 2.5 (in NO) to 3 (in NO+).
2. Draw the Lewis structure of NO+, include the most important resonance structures. Discuss
which resonance structure describes the cation the best considering the information that you
obtained from the MO diagram. Discuss whether this finding is in agreement with your
expectation without the knowledge of the MO theoretical results.
+ ..
:N O
:N O +
:
..
These two resonance structure are the only structures that contain one formal charge. The first
resonance structure provides the best description of the NO+ structure since it contains a triple
bond, which is also found in the MO diagram. The second resonance structure has no significant
contribution to the real structure.
The unfavorable aspect of the first resonance structure is the localization of the positive formal
charge on oxygen, the more electronegative element in the molecule. In the second resonance
structure the positive formal charge is located on nitrogen, which is less electronegative than
oxygen, however, nitrogen has an electron sextet, which is not favorable. Therefore, the first
resonance structure with electron octets around nitrogen and oxygen is far more stable. In
conclusion, the resonance structure description of the NO+ cation is in agreement with the MO
diagram.
3. Describe the bonding situation in the NO+ cation using VB theory: (a) What is the
hybridization of nitrogen and oxygen in this molecule, (b) describe the orbitals involved in the
formation of the multiple bonds in this ion. (c) How many and how many bonds do you have
in the NO+ cation. (d) Draw an energy level diagram (like the one in Figure 10.7 in your text
book) indicating the hybridization of the nitrogen, starting from the atomic orbitals yielding the
hybrid orbitals.
(a) Nitrogen and oxygen in NO+ are sp hybridized.
(b) A bond is formed by overlap of an sp hydrid orbital on nitrogen with one sp hybrid orbital
on oxygen. One bond is formed by overlap of the px orbital on nitrogen and the px orbital on
oxygen (the molecular axis is taken as the z-axis). The second bond is formed by overlap of the
py orbital on nitrogen and the py orbital on oxygen.
(c) One bond and two bonds are present between N and O in the NO+ cation.
(d)
E


2p
px py

sp

2s
2

4. Aspirin (C9H8O4) is produced by the reaction of salicylic acid (C7H6O3) and acetic anhydride
(C4H6O3).
C7H6O3(s) + C4H6O3(l) C9H8O4(s) + CH3COOH(aq)
(a) If you mix 100.g salicylic acid with 125 g of acetic anhydride, what is the maximum mass of
aspirin that can be obtained.
M(C7H6O3) = 138.1226 g mol-1
M(C4H6O3) = 102.0900 g mol-1
M(C9H8O4) = 180.1604 g mol-1
n(C7H6O3) = 100. g /138.1226 g mol-1 = 0.724 mol
n(C4H6O3) = 125 g /102.0900 g mol-1 = 1.22 mol
The mole ratio between the two reactants is:
n(C7H6O3) : n(C4H6O3) = 0.724 mol : 1.22 mol = 1.00 mol : 1.69 mol
The stoichiometric relationship between the two reactants in the reaction equation is 1 mol : 1
mol. Therefore, salicylic acid is the limiting reagent and has to be considered when calculating
the theoretical yield of aspirin.
n(C9H8O4) = (1 mol C9H8O4 produced)/(1mol C7H6O3) 0.724 mol C7H6O3
= 0.724 mol C9H8O4 produced
m(C9H8O4) = 180.1604 g mol-1 0.724 mol = 130 g
(b) In this experiment you isolate 121 g of salicylic acid. What is your theoretical, actual, and
percent yield?
130 g is the theoretical yield. 121 g is the actual yield that was obtained in this experiment.
(121 g/ 130 g) 100 % = 93.1 %
93.1 % is the percent yield.
(c) On page 163 in your textbook, molecular models of the two reactants and the two products
are depicted (black: C, red: O, grey: H). Draw the Lewis structures of the four molecules and
indicate the hybridization of every carbon and oxygen atom in these compounds.
Salicylic acid:
acetic anhydride:
aspirine:
sp3
..

H O:

sp2 C

sp3

..
H O:

sp2
..

O:

sp2

H
O
.. :

sp2

sp2

sp2

sp2

sp3

CH3

sp3

sp2

sp3

CH3

sp2
C .. C
O
:O
:
..
O
..
.. sp2

sp2

sp2

..sp2
:
O
sp2
H3C C
sp3
:OH
..

acetic acid:

sp3

sp2

sp2C
sp2

sp2
sp2

..sp2
O:
H

sp3
..

H
O
.. sp2 C sp3
sp2 C
H
sp2 :O :
sp2

5. A combustion analysis of aspirin is performed. Write the balanced reaction equation for the
combustion of aspirin. How many grams of CO2 and H2O will be produced during the
combustion of 2.1203 g of aspirin?
C9H8O4 + 9O2 9CO2 + 4H2O
M(C9H8O4) = 180.1604 g mol-1
M(CO2) = 44.0098 g mol-1
M(H2O) = 18.01534 g mol-1
n(C9H8O4) = 2.1203g/180.1604 g mol-1= 0.011769 mol = 11.769 mmol
n(CO2)= (9 mol CO2 produced)/(1 mol aspirin consumed) 0.011769 mol aspirin
= 0.10592 mol CO2
m(CO2) = 0.10592 mol 44.0098 g mol-1 = 4.6615 g
n(H2O) = (4 mol H2O produced)/(1 mol aspirin consumed) 0.011769 mol aspirin
= 0.047076 mol H2O
m(H2O) =0.047076 mol 18.01534 g mol-1 = 0.84809 g
4.6615 g and 0.84809 g of CO2 and H2O, respectively, will be produced during the combustion
of 2.1203 g of aspirin.