Israel Rodriguez

S00361070
Qumica Inorgnica CHEM 311
Chapter Acid and Base Summary
4/20/2014
Prof Cesar Lozano Ph.D.
In this summary several areas of acid-base chemistry and their
application to reactions of inorganic substances will be described.
The Arrhenius Theory of acids and bases
Acids are substances that produce hydrogen ions in solution.
Bases are substances that produce hydroxide ions in solution.
Neutralization happens because hydrogen ions and hydroxide ions
react to produce water.
Hydrochloric acid is neutralized by both sodium hydroxide solution and
ammonia solution. In both sodium hydroxide solution and ammonia
solution a colorless solution is produced that can crystallize to either
sodium chloride or ammonium chloride.
NaO H aq + HC l aq NaC l aq + H 2 Ol
Brnsted-Lowry concept
In the Brnsted-Lowry concept we refer to a hydrogen ion as a
proton. That is because a proton is all that is left when a hydrogen
atom loses an electron to become an ion. Brnsted and Lowry
independently came up with the idea that an acid is an acid because it
provides or donates a proton to something else. When an acid reacts,
the proton is transferred from one chemical to another and the
chemical that accepts the proton is a base. When an acid dissolves and
dissociates in water it gives a proton to the water. In the BrnstedLowry concept is the acid gives a proton to water to make two ions,
one being H3O+. H3O+ is called hydronium ion. In the following equation
HCl is giving a proton to a hydroxide ion rather than water:
HCl + OHH2O + ClIn order for an acid to act like an acid there needs to be a base. A base
is a proton acceptor. Bases are the opposite of acids. Bases are basic
because they take or accept protons. Hydroxide ion can accept a
proton to form water. Brnsted and Lowry realized that not all bases
had to have a hydroxide ion. As long as something can accept a proton
it is a base. The water molecules that accept protons when HCl
dissolves in water are acting as bases. Ammonia can accept or react

with hydrogen ion to give ammonium ion NH4+. Carbonate ion can
accept a hydrogen ion, or accept a proton, to become bicarbonate ion.
Water molecules can act as a base by accepting protons. Hydroxide,
ammonia, carbonate and water are all Brnsted-Lowry bases. NH3,
ammonia, is a base and NH4+, ammonium, is an acid. They are different
because one has one more proton than the other. The acid dissolves in
water to form hydronium ions and a base dissolves in water to form
hydroxide ions.
The leveling effect states that one cannot use an acid or base in
a solvent that has a stronger conjugate base or acid than the acid one
is trying to use. The solvent limits both the strongest acid you can use,
the conjugate acid of the solvent, and the strongest base, the
conjugate base of the solvent. A superacid is any acid that is stronger
than sulfuric acid. Super acid systems are necessarily nonaqueous,
since the acidity of any aqueous system is limited by the fact that the
strongest acid that can exist in the presence of water is H 3 O . A
strong Brnsted-Lowry acid is able to donate protons to the solvent
with greater ease, than a weaker Brnsted-Lowry acid. Fluorosulfuric
acid, HSO3F, is one of the earliest known superacids and is also one of
the strongest known Brnsted-Lowry acids. Fluorosulfuric acid is about
1,000 times stronger than sulfuric acid. The reaction between water
and fluorosulfuric acid is very violent, releasing much more energy
than the reaction between water and sulfuric acid. A superbase is an
extremely strong base. A superbase is a compound that has a high
affinity for protons. The hydroxide ion is the strongest base possible in
aqueous solutions. The purest measures of acid-base strength are gas
phase acidity and basicity parameters. For the majority of bases the
reaction is essentially bond breaking without the benefit of any
solvation of the products. Increasing proton affinity and gas phase
basicity magnitudes indicate increasing difficulty to remove the
hydrogen. The more positive proton affinity and gas phase basicity
magnitudes are the stronger the base becomes and the weaker the
acid will be in the gas phase. Binary hydrogen compounds range from
strong acids, HCl, to weak basis, NH3 or non-acidic molecules CH4. In
the series of oxyacids of chlorine, the acid strength in aqueous solution
is decreasing in the order HClO4>HClO3> HClO2>HClO. With
increasing number of electronegative substituents on Cl, the OH bond
is weakened due to the increasing positive charge on Cl. At the same
time the negative charge of the conjugate base is further stabilized.
The effects result in an increasing acidity.
The Lewis Theory of acids and bases
In the Lewis theory an acid is an electron pair acceptor and a
base is an electron pair donor. The Brnsted Theory defines acids and

bases as proton donors and acceptors. The Brnsted-Lowry theory is

based on the transfer of protons. The Lewis theory is based on the
transfer of electrons. A Lewis acid is a substance that can accept a pair
of electrons to form a new bond. They are sometimes referred to as
electrophiles. A Lewis base is a substance that can donate a pair of
electrons to form a new bond. They are sometimes referred to as
nucleophiles. Neutralization is the sharing of an electron pair between
an acid and base. The product formed in a neutralization reaction is
called an adduct. Lewis acid base adducts involving metal ions are
called coordination compounds. Coordination compounds are formed
from a central metal ion that has other smaller ions joined around it. A
Lewis base is often the ligand of a coordination compound with the
metal acting as the Lewis Acid. In the reaction the Aluminum ion is the
metal and is a cation with an unfilled valence shell making it a Lewis
acid. Water has lone-pair electrons and is an anion so it is a Lewis
base. The Lewis acid accepts the electrons from the Lewis base:
Al3+ + 6 H2O [Al (H2O)6]3+
Lewis basicity is defined as the thermodynamic tendency of a
substance to act as a Lewis base. A set of Lewis bases can very
depending on the reference acid used. Gas phase measurements are
ideal to measure Lewis basicitys without the complications of solvation
effects. The solubilitys of I2 in different solvents provide an effective
way to interpret the Lewis basicity of the solvents toward I2. The Lewis
acid BF3 is the most common reference to prove Lewis basicity. The
affinity of BF3 towards many bases has been measured in
dichloromethane solution where the affinity is defined as the
magnitude of the enthalpy change of adducts formation. Increasing
BF3 affinities indicate stronger coordinate covalent bonding,
consequently increasing Lewis basicity of the base towards BF3. In the
Lewis theory halogen bonding (XB) is the non-covalent interaction that
occurs between a halogen atom, Lewis acid, and a Lewis base. The
strength and effectiveness of chlorine and fluorine in XB formation
depend on the nature of the XB donor. If the halogen is bonded to an
electronegative moiety, it is more likely to form stronger halogen
bonds. An inductive effect is the pull of electron density through
bonds caused by electronegativity differences between atoms.

Frontier molecular orbital theory

Frontier molecular orbital theory is an application of MO theory
describing HOMO and LUMO interactions. The frontier orbital theory

predicts that a site where the lowest unoccupied orbital is localized is a

good electrophilic site. The HOMO is the orbital of highest energy that
is still occupied. Energetically it is the easiest orbital to remove
electrons. The LUMO is the lowest lying orbital that is empty.
Energetically it is the easiest orbital to add more electrons. In HF, the
HOMO orbital is the double degenerate 2 p x and 2 p y orbitals,

while the LUMO is the 2 pz orbital. The HOMO and LUMO can help us
predict what will happen in a chemical reaction. Consider the reaction
of HF with H2O:
+
+ H 3 O

HF + H 2 O F

In the reaction of HF with H2O in Lewis structures the H of HF is trading

+ .
the shared pair in the H bond for one in the H O The water molecule
3
donates one of its lone pairs to the HF molecule, causing the HF bond
to rupture, thereby allowing liberated proton to attach to the water
molecule. The electron pair donated by the water molecule must go

into the LUMO of HF. Since the LUMO is a 2 pz orbital, the

occupancy of this orbital by two electrons changes the bond order of
HF from 1 to 0. This causes the bond to be destabilized and rupture,
freeing up the proton H to react with H2O. In frontier molecular orbital
theory a Lewis base has an electron pair in a HOMO of suitable
symmetry to interact with the LUMO of the acid. The more similar the
energies of the HOMO and LUMO the stronger the interaction will be.
Hydrogen bonding can be understood in terms of frontier orbital
concepts. For a hydrogen bond FHF - the LUMO of the acid HF has
comparable energy to the HOMO of the base F- resulting in a
compound that has lower overall energy. Reactions of I2 as a Lewis
acid with Lewis basic solvents show effect of adduct formations. The
spectral changes caused by the changes in energy of the electron
energy levels are easy to view. The characteristic purple color of I2 is
due to absorption at ~500 nm, due to promotion of electrons from the

4 g MO, HOMO, to the 9 u MO, LUMO. Donor solvents form

adducts with I2 through interaction of the solvents HOMO and iodines
LUMO causing the adduct LUMO to rise and shifting the absorption to
higher energy. Non-donor or weak donor solvents do not have effective
HOMO- LUMO interactions. Solutions in hexane and benzene have
purple color similar to I2. Strong donors have effective LUMO-HOMO
interactions between I2 acid and base. This causes greater energy
separation between the adduct HOMO and LUMO. In the HOMO LUMO
model of Ammonia there are two pairs of degenerate orbitals, one
bonding and one anti-bonding. This highest occupied orbital has a lobe

pointing away from the three hydrogens. The three lowest energy
MO's lead to the description of the three N-H bonds of the Lewis
structure. The lone pair is relatively high in energy, and is responsible
for the Lewis base properties of ammonia.

Hard and Soft Acids and Bases

The polarizability of an acid or base plays a role in its reactivity.
Hard acids and bases are small, compact, and non-polarizable. Soft
acids and bases are larger, with a more diffuse distribution of
electrons. Hard acids react preferentially with hard bases, and soft
acids react preferentially with soft bases. LiBr> LiCl> LiI> LiF.. LiF
should have a higher concentration than the other salts, yet it is the
least soluble in water. This is due to the strong hard acid (Li+)/hard
base (F-) interaction. In Thiocyanate bonding SCN displays linkage
isomerism as the ligand coordinates to metals via the sulfur or the
nitrogen. Mercury (II) ion bonds to the sulfur, a soft-soft interaction,
whereas zinc ion bonds to the nitrogen atom. There have been many
attempts to categorize various metal ions and anions to predict
reactivity and solubility. R.G. Pearson categorized acids and bases as
either hard or soft using the Kf value. Hard acids bond in the following
order: F->Cl->Br->I-. Soft acids bond in the following order: I- >Br- >Cl- >
F-. Hard acids or bases are compact, with the electrons held fairly
tightly by the nucleus. They are not very polarizable. F- is a hard base,
and a metal ion, Li+, is a hard acid. Large, highly polarizable ions are
categorized as soft. Iodide is a soft base. Transition metals with low
charge density, Ag+, are considered to be soft acids. Hard acids tend to
bind to hard bases. Soft acids tend to bind to soft bases. Hard acids
typically have a high charge density. They are often metal ions with a
positive charge and small ionic size. Their d orbitals are often
unavailable to engage in bonding. Soft acids typically have lower
charge density. Soft acids are often 2nd and 3rd row transition metals
with a +1 or +2 charge, and filled or nearly filled d orbitals. The
nitrogen tends to coordinate with harder acids such as Si, whereas the
sulfur tends to coordinate with softer acids such as Pt2+. It is important
to realize that hard/soft considerations have nothing to do with acid or
base strength. An acid or a base may be hard or soft and also be
either weak or strong. Hard acid/hard base adducts tend to have more
ionic character in their bonding. These are generally more favored
energetically. Soft acid/soft base adducts are more covalent in nature.