ANACHEM WEEK 3 1.

Nature of Reactants
KINETICS AND CHEMICAL EQUILIBRIUM
• CHEMICAL EQUILIBRIUM
- nearly all the chemical reactions which are pertinent
to qualitative analysis are ionic, occurring in aqueous
solution
- reactions of this type proceed rapidly, but the
extent to which they approach completion depends
upon the nature of the reacting substances and the
external conditions to which they are subjected.
• REVERSIBLE REACTIONS
- refers to chemical reactions which occurs in either
directions
- all ionic reactions may be considered to be
reversible to some degree
- any chemical reaction once initiated maybe
regarded as being the result of two opposing
reactions:
• one proceeding toward the products and
the other,
• the products recombining to produce the
initial reactants
• REACTION VELOCITY
- when two reacting substances are brought together,
they are in their maximum concentrations only at the
moment of contact
- after the reaction commences, the concentrations
of the original materials decrease in proportion to the
concentrations of the products formed
o REACTION VELOCITY
▪ the change in concentration in unit
time
o REACTION KINETICS
▪ also called “chemical kinetics” ▪ the
study of rates of chemical reactions
and the factors which influence
reaction velocities
FACTORS AFFECTING RATE OF REACTION
1. Nature of Reactants
2. Presence of Catalysts
3. Temperature
4. Concentration
A) Ionic Bonds/Ionic Compounds:
• Since chemical bonds are broken and reformed in a
chemical reaction, the nature of the bonds changes
the rate of reaction. That is, how readily the bonds
are broken and formed.
• Ions have opposite charges. Opposite charges
attract which will form new ionic bonds. Reactions
that involve ions in solution tend to be fast.
B) Covalent Compounds
• Reactants that involve covalent bonds tend to be
very slow, unless they are highly exothermic
(combustions).For example, the decomposition of
hydrogen peroxide into hydrogen gas and oxygen gas
happens very slowly
C) Phase of Reactants
• The phase of the reactants is also important. That
is, reactants in liquid, solution, or gas form react
much more rapidly than solids.
D) Surface Area
• The exposed surface area also affects the rate of
reaction. The greater the surface area, the faster the
reaction. This is usually done by grinding into a
powder or breaking into smaller pieces. For example,
kindling vs. logs when starting a fire
E) Mechanical Mixing
• Stirring also increases the reaction rate because it
increases the frequency of collisions.
2. PRESENCE OF CATALYSTS
• Catalysts are substance that increases or decreases
the rate of chemical reaction without being
consumed or transformed
• has two (2) types:
▪ POSITIVE
➢accelerates or increases the reaction rate
through lowering of activation energy (Ea)
▪ NEGATIVE
➢retards or slows down the reaction rate

• NATURE OF REACTANTS
o determines the amount of activation
energy that should be present for a
reaction to occur
o E.g., charged ions does not require
high energy
o also refers to the physical state of the
reacting substances
▪ when substances are in
different phases, contact
only occurs in the interface;
therefore, vigorous stirring
or grinding may be needed
3. TEMPERATURE
• a measure of the average kinetic energy of the
molecule
• the more energetic are the molecules, the greater is
the impact when they collide - the faster the reaction
takes place
• Particles of substances reacting in solution
▪ the rate of reaction is dependent upon the
rate of diffusion of the particles in the
solvent
• ⬆ mobility, ⬆ collision, ⬆ rate of reaction
• ⬆ temperature, ⬆ rate of reaction
4. CONCENTRATION
• the amount of substance per unit volume • velocity
of the reaction is dependent upon the effective
contacts between reacting particles
• ⬆ concentration, the number of colliding molecules
⬆, and the probability of having more effective
collisions in a given time ⬆
LAW OF MASS ACTION
- The law of mass action states that: “The rate of
chemical reaction is proportional to the active masses
of the reacting substances present at the time.”
• ACTIVE MASS
▪ formula weight concentration
• usually describes the effect of
concentration of a reactant upon the rate
of reaction
• IMPORTANCE
▪ there is a definite relationship between
the concentration of reactants and products
before and after a state of equilibrium is
reached
LAW OF MASS ACTION
• If two substances A & B of known formula weight
concentration react, then A + B ➜ products
• The reaction velocity is proportional to the product
of the formula weight (where k = proportionality
constant)
𝑽 = 𝒌 × 𝑨 × [𝑩]
• If the concentration of A is doubled, the probability
of molecules of A coming into contact with molecules
of B is also doubled
• If A and B are doubled, the rate is fourfold
LAW OF CHEMICAL EQUILIBRIUM
• CHEMICAL EQUILIBRIUM
▪ state reached by a reaction mixture when
the rates of forward and reverse have become equal
• given the general equilibrium equation:
• A, B, D, E - chemical species involved
• a, b, d, e - coefficients in the balanced equation
• with respect to the law of mass action, the
equilibrium condition is described by the expression:
• the relationship above can be described as the
equilibrium-constant expression where Kc is the
equilibrium constant
• Kc is the numerical value obtained upon
substituting the molar equilibrium concentrations
into the equilibrium-constant expression
• NUMERATOR
▪ product of the concentrations of all
substances on the product side of the
equilibrium equation
• DENOMINATOR
▪ similarly derived from the reactant side of
the equilibrium equation
LAW OF CHEMICAL EQUILIBRIUM SAMPLE EXERCISE
1. What is Kc for the following equilibrium when
the equilibrium concentration of each substance
is: [SO2]= 0.60M,∣O2∣=0.82M and [SO3]=1.90M ?
• 2SO2(g)+O2(g)⇌2SO3(g)
• The value of Kc for the reaction 3O2(g)⇌2O3(g) is
2.0×10−50 at 25oC. If the equilibrium concentration
of O2 in air at 25oC is 1.6×10−2 M, what is the
concentration of O3?
•Write the equilibrium expression Kc and Kp for the
following reaction:
• 1N2(g) + 3 H2 (g) -→ 2 NH3 (g)
• Nitrogen reacts with Chlorine to produce Nitrogen
Trichloride. At equilibrium, the concentrations of
each gas were found to be (N2)= 0.15 M, (Cl2)= 0.25
M, and (NCl3)= 0.50 M. Calculate the value of
equilibrium constant ((Kc)?
• 1 N2 (g) + 3 Cl2 (g) -→ 2 NCl3 (g)
• Sulfur dioxide reacts with Oxygen gas to produce
Sulfur trioxide. At equilibrium, the partial pressure of
each were found to be 0.10 atm, 0.30 atm, and 0.45
atm for SO2, 02 and S03 respectively. Calculate the
equilibrium constant (Kp).
• 2 SO2 (g) + 1 02 (g) → 2 SO3 (g)
• LE CHÂTELIER’S PRINCIPLE
• by French chemist Henri-Louis Le Châtelier
• the principle states that:
“if a chemical system in equilibrium is
disturbed by some form of a stress, the system
goes to a new point of equilibrium to remove
that stress”
• “stress” refers to the following factors
affecting equilibrium
▪ CONCENTRATION, TEMPERATURE, PRESSURE
and VOLUME, CATALYST
“STRESSES” ON CHEMICAL EQUILIBRIUM
1. Concentration
2. Temperature
3. Pressure & Volume
4. Catalyst
“STRESSES” ON CHEMICAL EQUILIBRIUM
CONCENTRATION
• when increase of concentration is applied to either
the reactants or products, there is a shift of the point
of equilibrium in the direction which relieves the
stress
• e.g., N2O4 (g) ⇄ 2NO2 (g)
➔WHERE WILL THE SHIFT BE DIRECTED IF:
▪ there will be addition of N2O4
▪ there will be removal of N2O4
▪ there will be addition of NO2
▪ there will be removal of NO2
STRESSES” ON CHEMICAL EQUILIBRIUM
TEMPERATURE
• if the temperature is changed, the value of
equilibrium constant is altered
• when the temperature of a system is increased, the
system reacts as if we add a reactant to an
endothermic reaction or a product to an exothermic
reaction; equilibrium shifts in the direction that
CONSUMES the EXCESS REACTANT (or product),
namely HEAT
• ENDOTHERMIC & EXOTHERMIC REACTIONS
▪ Endothermic Reaction - heat is regarded
as a REACTANT
▪ Exothermic Reaction - heat is regarded as
a PRODUCT
consider the equilibrium:
N2O4 (g) ⇄ 2 NO2 (g)
Task: Predict the shift in equilibrium under the
following circumstances.
A. increase in temperature
B. decrease in temperature
“STRESSES” ON CHEMICAL EQUILIBRIUM PRESSURE
& VOLUME
• for a gaseous equilibrium, an ⬆ in pressure results in
a shift to lesser the total number of molecules
• ⬆ of pressure unless extremely large has little effect
upon equilibria reactions involving solid and liquid
• the effect of a pressure is dependent on the
volume:
▪ ⬆ P ⬇ V shift – lesser number of gaseous
molecules
▪ ⬇ P ⬆ V shift – greater number of gaseous
molecules
• total pressure in the reaction vessel might also be
increased with the addition of a gas that is not
involved in the equilibrium
▪ WILL CAUSE NO SHIFT IN THE EQUILIBRIUM
consider the equilibrium:
N2O4 (g) ⇄ 2 NO2 (g)
Task: Predict the shift in equilibrium under the
following circumstances.
A. addition of N2
B. increase in volume

“STRESSES” ON CHEMICAL EQUILIBRIUM CATALYSTS

• the following are the contributions of catalysts
being stressors on chemical equilibrium:
▪ ⬆ rate of FORWARD and REVERSE
reactions
▪ ⬇ Eact of FORWARD and REVERSE reactions
▪ ⬇ time to reach EQUILIBRIUM
▪ × effect/influence in the Kc
▪ × promote shift in position of a system

POST-SESSION EXERCISE
given the equilibrium below:
H2O2 l ⇋ H2 (g) + O2 (g)
with ∆H = 187 kJ/mol
Predict which way will the equilibrium shift if:
1. more H2 will be added
2. O2 is removed
3. the volume is reduced
4. the temperature increases