CHAPTER 5

Principles of Chemical Reactions

• Stoichometry: How many mole will react with how many moles
theoretically.
• First balance elements other than C,H,O.
• Than balance other elements in both sides of the equation
Types of Reactions
• Acid-base
• Precipitation-dissolution
• Complexation ( ligand with metals, CN-, Cl- functional groups)
• Redox reactions
Acid-base reactions
• Ionization of acids

Strong acids Weak acids

• Weak acids ionize partially, on the other hand;
strong acids completely ionize in water.
• The degree of ionization is dependent on pH of
solution and pKa (ionization constant) of the acid.
• As you know: pH = -log(H+), pKa=-log(Ka)
pKa=-log Ka= -log (5*10-7)=6.3
• Amphoteric substances can act as an acid or a base.example: H2O,
HCO3-
• Rain water is slightly acidic because of CO2.
• Ex: NH3 is toxic to fish. The dissociation of
ammonium in water ( most natural waters have a pH
between 6-9). Find the ratio of NH3/ NH4+ at pH=10
(pKa: 9.25)

• 6 times more ammonia than ammonium

(1/7 NH4+ and 6/7 NH3)
• Degree of ionization= 6/7
Complexation
• Complex metals form bonds with functional groups in water.
• The functional groups are called «ligands»: Anions that bind with a
central metal ion to form soluble complexes. Common ligands include
CN−, OH−,Cl−, F−, CO32− , NO3− , SO42−, PO43−
• Chelation: a special case of complexation.
• When the functional group bonds to the metal ion in more than one
site, it is called chelation. And the functional group is termed as
chelating agent.
Ionic strength
• When solution is not dilute (i.e. Dissolved ion concentrations are
high), ions affect interactions of other ions’ (i.e. rxns). To account for
this, we use activity {} instead of molarity [ ]
• Activity of ions as ions (Dancing in a room full of couples is more
difficult than dancing in an empty room)

I: Ionic strength (mol/L)

Ci: Concentration
Zi: Charge
Ionic strength (I)
• We need to know Ci for all species in water to calculate I.
• If not known, we can approximately estimate I by:

• ϒi>1 for nonelectrolytes

• ϒi<1 for electrolytes
• Electrolytes create an electrically conducting medium when added to
water (e.g. NaCl)
• As the solution becomes dilute ϒ≈1 hence {}=[] (valid for most of our
cases)
• For pure solids or liquids in equlibrium with a solution {i}=1
• For gases, activity is proportional to its partial pressure, {i}= ϒi*xi (xi=
mole fraction of species i)
How to calculate ϒ
• Use Debye-Hückel limiting law for electrolytes in solutions with I<
0.005 M.

A is constant, 0.51 at 25°C.

• For more concentrated solutions (up to I ≤ 0.1 M) use Davies eq.
Example
• I=0.001 M at 25°C, ϒ =?
.
REACTION THERMODYNAMICS
• For a reaction to proceed the free energy change must be LESS THAN
ZERO.

• Free energy is energy associated with a chemical reaction that can be

used to do work.

G: developed by Gibbs, hence G

H: entalphy
S: entropy
• The driving force for the
reaction is the difference
between initial&equilibrium
energy states.
• At equilibrium ΔGrxn=0
means that there is no
driving force any more
• At standard conditions we have tables of free energy change
• For our specific case, use:

= ( free energy change of formation of species i)

• For a reaction, first find

F F
• For this case,

• free energy change of rxn per mole of A, (KJ/mole)

At equilibrium, 0
Example (Problem 5.20)
Dependence on Temperature
• For a T other than 25°C:

• We use this equation assuming does not change significantly

with temperature change (which is the case for water T range 0-
30°C).
• K at different temperatures can be found with this equation, it is
called Von’t Hoff relationship.
• (Read study example 5-5 for the application of these two equations)
Reaction Kinetics
• Reaction Rate= Change in concentration /Change in time
Order of reaction

Order of the reaction is m+n

Reaction rate

• k is the reaction rate

constant
• The unit of k changes
with the order of the
reaction
How to determine the order of a reaction?
• Create a table including Time, C, ln (C) and (1/C)
• If;
• C vs t graph is linear zero order
• ln(C) vs t graph is linear  first order
• 1/C vs t graph is linear  second order
Effect of Temperature on Reaction Rate
• Temperature, pH and the presence of catalysis are important in the rate of the
reaction.
• For the effect of temperature: Arrhenius eq is used:

Ea: activation energy (kJ/mol)

A: frequency factor same unit as k

• Plot ln K vs (1/T) via a lab experiment to determine the Arrhenius relationship.