This document discusses inductive effects in organic chemistry. It begins by defining inductive effects as the withdrawal of electrons from a σ bond to the more electronegative atom or group, creating a dipole. This effect can alter the reactivity of other groups on the molecule. More electronegative substituents increase the acidity of carboxylic acids by withdrawing electron density from the acidic proton. The document also examines how inductive effects influence aromatic systems' affinity for carbon dioxide, with methyl groups increasing and halogen groups decreasing this affinity through their respective positive and negative inductive effects.

1. Organic Pedagogical Electronic
Network
Inductive Effects
Colin Swenson
Tewoderos Ayele
University of Utah

2. Inductive Effect
Eric Anslyn and Dennis Dougherty, Modern Physical Organic Chemistry, University Science Books; pp 15-18
Overview: An inductive effect occurs when the
electrons shared between two atoms or groups
of different electronegativities are withdrawn to
the more electronegative atom or group through
the σ bond resulting in a separation of charge,
or dipole. This effect can be felt a few atoms
away affecting the reactivity of other groups on
the molecule.
The yellow arrows show the dipole moment of the molecule,
indicating the direction of electron density.

3. Inductive Effects on Acidity
Reush, W. Carboxylic Acids. https://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/crbacid1.htm
(Accessed October 2015).
The increased acidity of carboxylic acids
can be attributed to electrostatic effects,
such as induction. More electronegative
groups will greatly change the
distribution of electron density in the
molecule by withdrawing electrons. This
effect will make the proton more acidic.
The relative distance of the
electronegative group also affects the
acidity of carboxylic acids. The closer
the electron withdrawing substituent is
to the reactive proton, the more acidic
the molecule becomes.
Acidity increases as more electronegative substituents are
added to the molecule and withdraw electron density from the
acidic proton
Compound pKa
CH3CO2H 4.74
BrCH2CO2H 2.9
ClCH2CO2H 2.85
FCH2CO2H 2.65
CH3CH2ClCO2H 2.89
CH3ClCH2CO2H 4.05
ClCH2CH2CO2H 4.53

4. Case Study
Bell, R., Mellot-Draznieks, C., Torrisi, A. J. Chem. Phys. 130, 194703 (2009)
Inductive Effects on Aromatics for
CO2 Adsorption
Carbon dioxide, a side product in the
production of hydrogen gas for fuel
applications, needs to be separated
from the gaseous mixture at very low
pressures. An economic approach
involves the use of Metal-Organic
Framework materials. The quadrupole
of CO2 interacts with the delocalized pi-
system of aromatics. Substituents
supplying inductive effects have been
studied for enhancement of the affinity
for CO2. Methyl substituents supplying a
positive inductive effect are shown to
stabilize the CO2-aromatic interaction,
whereas halogen substituents supplying
a negative inductive effect are shown to
destabilize the CO2-aromatic interaction.
Delocalized charge on aromatic carbons as a function
of the binding energy (BE) to carbon dioxide of different
substituent groups.

5. Problems
Bell, R., Mellot-Draznieks, C., Torrisi, A. J. Chem. Phys. 130, 194703 (2009)
1. Rank the following in increasing acidity (1 is most acidic)
a. 1
b. 1
c. 1
2. Explain how induction effects differ from resonance effects.
3. Provide an explanation for the trend seen in the delocalization of charge on the
aromatic carbons presented in the case study.
4. Which molecule would you expect to have a greater affinity for CO2 , C6H5NO2
or C6H5NH2 ? Explain.

6. Solutions
Bell, R., Mellot-Draznieks, C., Torrisi, A. J. Chem. Phys. 130, 194703 (2009)
1
a.
b.
c.
2. Resonance effects are directly involved with the movement of electrons, whereas
inductive effects are a result of a change in electron density.
3. There is less delocalized charge on the aromatic carbons as halogens are placed
on the ring because they withdraw electron density from the aromatic system.
4. C6H5NH2 because there will be more delocalized charge on the aromatic system
due to the amine group being less withdrawing than the nitro group.
3 2 1
2 3 1
3 1 2

7. This work is licensed under a
Creative Commons Attribution-
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License.
Contributed by:
Colin Swenson and Tewoderos Ayele (Undergraduates)
University of Utah, 2015