Acidity, basicity, and pKa

TAIBAH UNIVERSITY
COLLEGE OF SCIENCE
CHEMISTRY DEPARTMENT
Presented by:
Zubaydah Abdullah
* Acids and bases are obviously important
because many organic and biological reactions
are catalysed by acids or bases.

* pKa tells us how acidic (or not) a given
hydrogen atom in a compound is
Types of Acids and Bases
In the 1800s chemical concepts were based on the
reactions of aqueous solutions.
Svante Arrhenius developed a concept of acids and
bases relevant to reactions in H
2
O.
Arrhenius acid produces hydrogen ions in water.
Arrhenius base produce hydroxide ions in water.
Strong acids and bases are 100% dissociated.
A broader ,more modern concept of acids and bases was
developed later.
The idea that acids are solutions containing a lot of H
+ and bases are solutions containing a lot of OH- is
not very useful in organic chemistry.

Bronsted-Lowry acid- can donate a proton.
Bronsted Lowry base can accept a proton.
Conjugate acid-base pairs.
A Brnsted-Lowry acid-base reaction results in the transfer
of aproton from an acid to a base.
In an acid-base reaction, one bond is broken, and another one
is formed
There is an inverse relationship between the strength of an acid and
the strength of its conjugate base: the stronger the acid, the weaker
its conjugate base
Conjugate acid- compound formed when an base
gains a hydrogen ion.
Conjugate base compound formed when an acid
loses a hydrogen ion.
Summary of
AcidBase Definitions

What is The pH Scale?
The pH scale is only a measure of how acidic or
basic a solution is.
The pH scale is the concentration of hydrogen
ions in a given substance.
[ ]
+
! = H pH log
The pH scale depends on the concentration of acid
acidic solutions all have a pH of less than 7the lower the
pH the more acidic the solution.
alkaline solutions all have pHs greater than 7the higher
the pH, the more basic the solution.
The pH 7 is neither acidic nor alkaline but neutral.
Aqueous any strong acid has a lower pH than an equal
concentration of aqueous any weak acid; because it is more
fully dissociated and thereby produces more hydronium
ions.
The pH scale also depends on the acid in question
For hydrochloric acid, the equilibrium lies well over to the right:
in effect, HCl is completely dissociated.
Acetic acid is not fully dissociatedthe solution contains both
acetic acid and acetate ions.
If a strong acid is added to water, the water acts as a base
and is protonated by the acid to become



If we added a strong base to water, the base would deprotonate
the water to give hydroxide ion, , and here the water would
be acting as an acid.



Such compounds that can act as either an acid or a base
are called amphoteric.
can behave as an acid or as a base Water
The amino are amphoteric. Unlike water, these
compounds have separate acidic and basic groups built
into the same molecule.

When amino acids are dissolved in water, the acidic end protonates
the basic end to give a species with both a positive and a negative
charge on it.
A neutral species that contains both a positive and a negative charge
is called a zwitterion.


Pure water at 25 C has a pH of 7.00. This means that the
concentration of hydronium ions in water must be

Hydronium ions in pure water can arise only from the self-
dissociation or autoprotolysis of water.


In this reaction, one molecule of water is acting as a base,
receiving a proton from the other, which in turn is acting as an
acid by donating a proton
The ionization of water
Weak acid: a substance that dissociates only partially in water to
produce H3O+ ions .
acetic acid, for example, is a weak acid; in water, acetic acid is
incompletely ionized in aqueous solution.




Weak base: a substance that dissociates only partially in water to
produce OH- ions.
ammonia, for example, is a weak base.
Acid and Base Strength
Acid strength is the tendency of an acid to donate a proton.
The more readily a compound donates a proton, the stronger an
acid it is.
When a Brnsted-Lowry acid HA is dissolved in water, an
acid-base reaction occurs, the position of equilibrium is measured
by the equilibrium constant for this reaction Keq.
Stronger acids have larger Keq.
Acid and Base Strength
The concentration of water as a solvent does not change
significantly when it is protonated.
with dilute solutions of acids wherever the equilibrium may be
and a new equilibrium constant, Ka, is defined and called the
acidity constant .
It is generally more convenient when describing acid
strength to use pKa values than K values. Like pH,
this is also expressed in a logarithmic form, pKa.
Because of the minus sign in this definition, the lower the pKa,
the larger the equilibrium constant, Ka, is and hence the stronger
the acid.
The pKa of the acid is the pH where it is exactly half
dissociated. At pHs above the pKa, the acid HA exists as
in water; at pHs below the pKa, it exists as undissociated HA.
we can increase the solubility of a neutral acid in water by
increasing the proportion of its conjugate base present. All we
need to do is raise the pH.
organic bases such as amines can be dissolved by lowering the
pH
In a mixture of two acids or two bases :
The ratio of Ka values gives us an indication of the equilibrium
constant for the reaction between a base and an acid
The difference in pKas gives us the log of the equilibrium
constant
The stronger the acid HA, the weaker its conjugate base, A
The stronger the base A, the weaker its conjugate acid AH
Acid and conjugate base strength
An acids pKa depends on the stability of its conjugate base.
The LOWER the pka the
more acidic it is

The HIGHER the pka the
more basic it is.
Remember
The deference between Ka and pKa
- The strongest base in aqueous solution is OH and
the strongest acid in aqueous solution is H3O+.
Addition of stronger bases than OH just gives more OH by the
deprotonation of water.
Addition of stronger acids than H3O+ just gives more H3O+ by
protonation of water
The pH of pure water at 25C is 7.00 (not the pKa)
The pKa of H2O is 15.74
The pKa of H3O+ is 1.74
Remember
the more
electronegative
the element
the more stable
the conjugate
base
the stronger
the acid
Acid Strength
Bond strength AH. Clearly, the
easier it is to break this bond, the
stronger the acid.

The solvent. The better the solvent
is at stabilizing the ions formed, the
easier it is for the reaction to occur.
Factors affect the strength of an acid
1) Electronegativity
Electronegativity of the atom bearing the negative charge; within a
period.
The greater the electronegativity of the atom bearing the negative
charge, the more polarized the bond to H, H becomes more positive
and the bond is easier to break; the greater the acidity of the acid HA,
the less willing it is to share those electrons with a proton, so the
weaker the base.
Electronegativity C < N < O < F
Stability

Acidity
Electronegativity Increase
Acidity Increase
Basicity Increase
2) Size of the atom
Down a column of the periodic table, the acidity of HA
increases as the size of A increases.
Acidity & Size Increase
Acidity H-F < H-Cl < H-Br < H-I


Stability
I-
Br-
Cl-
F-
As size increases, Weak AH bonds is easier to break; is
make stronger acids.
A larger size also stabilizes the anion
Factors affect the strength of an acid
Increasing Basicity
3) Resonance; delocalization of the negative charge
the charge can be more delocalized, and this makes the anion more
stable.
the greater the resonance stabilization of the anion, the more acidic
the compound.
If the negative charge can be delocalized on to more electronegative
atoms such as oxygen or nitrogen, the conjugate base will be
stabilized and hence the acid will be stronger, and it is going to be
less basic than one with a more concentrated, localized charge
Factors affect the strength of an acid
4) The Inductive Effect
Any group that withdraws electrons will help to stabilize the
conjugate base and therefore increase the strength of the acid.
An inductive effect is the pull of electron density through
bonds Caused by electronegativity differences in atoms,
Which cause polarization of the bond.
The reason for the increased acidity is that the electronegative chlorine atoms
stabilize the negatively charged conjugate base.
Factors affect the strength of an acid
1. More electronegative atoms stabilize regions of high electron density by
an electron withdrawing inductive effect.
2. The more electronegative the atom and the closer it is to the site of the
negative charge, the greater the effect.




3. The acidity of HA increases with the presence of electron withdrawing
groups in A
Factors affect the strength of an acid
4) The Inductive Effect
Electron-donating groups decrease acidity
The most common electron-donating groups encountered in
organic chemistry are the alkyl groups. These are weakly
electron-releasing.
Factors affect the strength of an acid
4) The Inductive Effect
Strong
Moderate
Weak
Electron-withdrawing
Electron-donating
Remember
5) Hybridization
The higher the percent of s-character of the hybrid orbital,
the closer the lone pair is held to the nucleus, and the more
stable the conjugate base.
Increasing Acidity & Stability
Factors affect the strength of an acid
Increasing Basicity
This makes an sp hybridized carbon less electron-donating
than an sp2 one, which in turn is less electron-donating than an
sp3 carbon.
The more
s-character an
orbital
The more it
holds on to
the electrons
in it
Factors affect the strength of an acid
5) Hybridization
If we can delocalize the negative charge of a conjugate anion, the
anion is more stable and consequently the acid is stronger.
Aromaticity increase acidity; because the conjugate
base of the most acidic compound has more resonance
structure over which spread its electron density.
Factors affect the strength of an acid
5) Hybridization
The more stabilized the conjugate base, A, the stronger is
the acid, HA. Ways to stabilize A include:

Having the charge on an electronegative element
Delocalizing the negative charge over other carbon atoms, or even
better, over more electronegative atoms .
Spreading out the charge over electron-withdrawing groups by
the polarization of " bonds (inductive)
Having the negative charge in an orbital with more s-character
Becoming aromatic.
Summary
Summary
Nitrogen acids
Amines are not acidic, amides are weakly acidic (about the
same as alcohols), and imides are definitely acidic (about the
same as phenols).
Basicity

A base is a substance that can accept a proton by donating a pair
of electrons.
Some organic bases and their relative strengths in proton-transfer
reactions
Any substituent that increases the electron density on the nitrogen
therefore raises the energy of the lone pair thus making it more
available for protonation and increasing the basicity of the amine.
Neutral nitrogen bases
Amidines are stronger bases than amides or amines
Oxygen bases in general are so much weaker than their nitrogen
because oxygen is more electronegative and wants to keep hold of its
electrons.
Neutral oxygen bases
Note: that acidity and basicity are just the reverse of each other.
AND Therefore, both are affected by the same factors, just in opposite ways.
The End