Exercise 15 - Calculating the Free Valence Index

Theoretical Organic Chemistry, 2013

Anastazija Ristovska

O (4)
C3
C2
C1

O (4)
0.000
0.685
0.000
0.000

C3
0.685
0.000
0.543
0.000

C2
0.000
0.543
0.000
0.832

C1
0.000
0.000
0.832
0.000

Table 1: Acrolein Bond Orders

Bond order between C1 and C2: 0.832

Bond order between C2 and C3: 0.543
Bond order between C3 and O: 0.685
The general carbon atom -bond maximum degree of bonding is 1.73. Therefore the free valence indices
of the three carbon atoms of acrolein are:

1
= 1.73-0.832 = 0.898

2
= 1.73-(0.832+0.543) = 0.355

3
= 1.73-(0.543+0.685) = 0.502

Atom 1
Atom 2
Atom 3
Atom 4
Atom 5
Atom 6
Atom 7

Atom 1
0
0.440 |
0
0
0.397 |
0
0

Atom 2
0.440 |
0
0.772 ||
0
0
0
0

Atom 3
0
0.772 ||
0
0.577 ||
0
0
0

Atom 4
0
0
0.577 ||
0
0.708 ||
0
0

Atom 5
0.397 |
0
0
0.708 ||
0
0.445 |
0

Atom 6
0
0
0
0
0.445 |
0
0.890 ||

Atom 7
0
0
0
0
0
0.890 ||*
0

Table 2: 2-EthenylPyrrole Bond Orders

The free valence index of each of the 6 carbon atoms of 2-ethenylpyrrole is:

2
= 1.73-(0.440+0.397) = 0.893

3
= 1.73-(0.772+0.577) = 0.381

4
=

1.73-(0.577+0.708) = 0.445

5
=

1.73-(0.394+0.708+0.445) = 0.183

6
= 1.73-(0.445+0.890) = 0.395

7
= 1.73-0.890 = 0.840

Free Valence Indices of

2-Ethenylpyrrole

0.893
2

0.381

0.445

0.183

0.395

0.840

Hydrocarbon molecule 4-ethenyl -3-methylene-hept-1,4,6-triene calculations:

1
2
3
4
5
6
7
8
9

Atom
Pair
C2-C6
C9-C10
C1-C5
C7-C8
C3-C4
C3-C5
C4-C9
C6-C7
C4-C7

Bond Order
0.908
0.888
0.857
0.813
0.717
0.505
0.441
0.410
0.397

Double
Type of
Double
Bond
Double
Double
Double
Single
Single
Single
Single

1
= 1.73-0.857 = 0.873

2
= 1.73-0.908 = 0.822

Free Valence Indices of

4-ethenyl -3-methylenehept-1,4,6-triene

3
= 1.73-(0.717+0.505) = 0.508

0.873

4
= 1.73-(0.717+0.397+0.441) = 0.175

0.822

0.508

0.175

0.368

0.412

8
= 1.73-0.813 = 0.917

0.110

9
= 1.73-(0.441+0.888) = 0.401

0.917

0.401

10

0.842

5
= 1.73-(0.857+0.505) = 0.368

6
=

1.73-(0.908+0.410) = 0.412

7
=

1.73-(0.397+0.813+0.410) = 0.110

10
= 1.73-0.888 = 0.842

All software calculations were conducted using the Huckel Molecular Orbitals (HMO) Calculations
computer program, Copyright 1993 by David R. Anderson, Department of Chemistry, University of
Colorado, Colorado Springs, CO 80933.