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Equilibrium
Joanne Katherine T. Manlusoc, MSc.
CHEMISTRY THROWBACK
Chemistry - study of the property of matter and the changes
it undergoes.
Rate = k[A]2[B]
1. Temperature – enough
(thermal) energy is needed
upon collision to favor the
formation of new products.
This required energy to make
the chemical reaction
possible is called the energy
of activation/ activation
energy. (EA)
B. CONCEPTS AND CORRESPONDING
FACTORS AFFECTING RATE
2. Orientation – colliding particles must be properly
oriented in order to amplify the attraction between
each other, making more possible the achievement of
EA.
B. CONCEPTS AND CORRESPONDING
FACTORS AFFECTING RATE
IV. Catalysis: Factor of Catalysts
A catalyst is a substance that helps in
increasing the rate of reaction. The
following are characteristic of most
catalysts:
1. A catalyst speeds rate of reactions
thru lowering of the activation
energy;
2. It is not used up in the reaction;
3. It does not affect chemical
equilibrium; and
4. It usually acts by physical forces,
forming a temporary complex with
the target reactant to stabilize
transition state.
B. CONCEPTS AND CORRESPONDING
FACTORS AFFECTING RATE
Catalysts can be generally categorized into two:
• Heterogenous catalysts - exist in a phase different from
that of the reactant (ex. metal catalyst in gas production)
• Homogenous catalysts - exist in a phase same with that
of the reactant (ex. liquid catalyst in aqueous/liquid
reactant).
A, E = reactants D = intermediate
F, C = products B = catalyst
II. Reaction Mechanisms and the
Rate Law
The integration of chemical kinetics and reaction
mechanisms relies on three general rules:
1. The individual steps must add up to the overall
balanced equation;
2. The individual steps are bound to all rules set up
by chemical kinetic principles; and
3. The reaction mechanism is derived from the rate
law, not the other way around.
II. Reaction Mechanisms and the
Rate Law
Individual steps have individual rates
Not all steps of a multi-step reaction have significant
duration. A two-step reaction might have a 0.001
second step, followed by a 5 second step. Definitely,
the second step in the example is far more useful in
determining the kinetics of the reaction.
Rate-determining step (RDS) –slower/slowest
step of a reaction mechanism. The
concentration of reactants in the RDS are the
only ones considered in the entire reaction’s
rate law.
EXAMPLE
NO + O2 <----> NO3 (fast)
NO3 + NO -----> 2NO2 (slow)
Rate = k[NO3][NO]
EXERCISE
1. Give the rate law for the following reaction
mechanism:
N2O -----> N2 + O (slow)
N2O + O ----->N2 + O2 (fast)
CHEMICAL EQUILIBRIUM
Equilibrium - state wherein the amount of products
and reactants stay the same in an equal reaction
process.
• Unless the products exist with leftover reactant,
equilibrium cannot happen because it only happens on
reversible reactions. (Double arrow <-----> is used to
denote a reversible reaction).
• Equilibrium on reversible reactions is achieved only
when NET production of either products or reactants is
zero.
• Therefore, there will be a flat graph of concentration vs. time
on an energy diagram for reactions in equilibrium to denote
that zero net production.
CHEMICAL EQUILIBRIUM
• If the reaction is
returned to progress
(aka disturbed – with a
corresponding rise or
fall in the flat graph),
there will be changes
to maintain equilibrium
and the graph will Mathematical/quantitative study of equilibrium
return to flatness after depends highly on equilibrium constants.
3A + 2C <-> 2B
• If Qc > Keq, the reaction has too many products, and will
shift the equilibrium to the left (towards reactants)
• If Qc < Keq, the reaction has too many reactants, and will
shift the equilibrium to the right (towards products)
• Qc = Keq when the reaction is in equilibrium
EXERCISE
1. Given that the Keq for a reaction is 21, give the
inference when the products A and B are both 5.3M
while the only reactant is 1.85M.
SPECIFIC EQUILIBRIUM
A. WATER, ACIDS, AND BASES: STRENGTH
The Keq of water by 25 deg. C is 1.0x10-14. This is also called the ion-
product constant for water (Kw),
Kw = [H+][OH-]
Thus, we can get the concentration of ions produced.
H+ = 1.00 x 10-7; pH = 7
OH- = 1.00 x 10-7; pOH = 7
%I = [H+] or [OH-]
[HA] or [B-]
EXERCISE
1. The Ka of phosphoric acid at is 7.2 x 10-3. Find its
pKa.
2. The Kb of methylamine is 4.4 x 10-4. Find its pKb.
3. If a 0.19M base has a pH of 10.88, find its Kb. Find
%I.
4. If the hydrogen ion concentration of a 0.77M weak
acid is 1.32 x 10-4, what is its pKa?
A. WATER, ACIDS, AND BASES:
STRENGTH
• Dissociation constants and Ion concentrations: Ka, Kb,
Kw, [H+], [OH-] and their negative logarithms
Because the conjugate acid or base in the ionization of
an acid or base is accompanied with either a hydrogen
ion or a hydroxide ion, by getting the Ka or Kb, we can
get the molarity of either H+ or OH- produced, and
ultimately the pH and pOH.
EXERCISE
1. If the Kb of Diethylamine is 8.6 x 10-4, what is its
pKb?
2. Ascorbic acid has a pKa of 4.10. What is its Ka?
3.Phenol, an acidic compound with a Ka of 1.3 x 10-10,
should have a Kb of what?
4. If a 1M formic acid has a pKa of 3.77, find its Kb
and %I [H+].
5. A 0.75M monoprotic acid has a [H+] of 2.3 x 10-12.
Find its Ka.
EXERCISE
6. Given that urea has a Kb of 1.5 x 10-14, find its pKa.
7. Ethylamine has a Kb of 5.6 x 10-4. Find its pOH.
8. Benzoic acid has a Ka of 6.5 x 10-5. Find its
hydroxide ion concentration and pOH.
9. A 0.35M base has a pOH of 4.24. Find its OH-
concentration, Kb, pKb, pKa, Ka, H+ concentration, pH
and %I [OH-].
A. WATER, ACIDS, AND BASES:
STRENGTH
C. COMMON-ION EFFECT
In pure weak acid solution (consider an acid
first), the Ka will be equal to the product of the
hydrogen and conjugate base. If more
conjugate base is added, the equilibrium will
have to shift to the direction of the acid,
because of Le Chatelier’s principle.
EXAMPLE
A 0.5 M acetic acid mixed with 0.1M sodium acetate should
have what difference in pH compared to that of the acid
alone? Ka = 1.8 x 10-5
Ka = [H+][A]/[HA]
1.8 x 10-5 = x2/0.5 – x
*remove x if the constant is less than 10-4
pH = pKa + log[A-]
[HA]
EXERCISE
1. What is the pH of a 0.2M NH3/NH4Cl buffer?
2. Find the ratio of an acetic acid/sodium acetate if
the pH is 4.63. (pka acetic acid = 4.74). If 0.25M
acetic acid was used, how many moles of sodium
acetate was used?
3. If the the pH of a secondary phosphate buffer is
12.34, what is the ratio of acid to conjugate base?
(pka secondary phosphate = 12.38)
4. A lactic acid buffer contains equal amounts of acid
and conjugate base. If its Ka is 1.4 x 10-4, what is its
pH?
B. IONS AND PRECIPITATES:
SOLUBILITY
• A solution is a homogenous mixture that consists of a
solute and solvent. The process by which the solute
successfully dissolves in solvent is
solvation/dissolution.
Resultant molarities:
MNaOH = (10)(0.01)/1010 = 9.9 x 10-5 M
MCuCl2 = (1000)(0.01)/1010 = 9.9 x 10-3 M
Q = [Cu][OH]2 = 9.7 x 10-11; Q>Ksp, thus precipitate
will form
EXERCISE
1. If PbCl2 has a ksp of 1.7 x 10-5, will a precipitate
form if 3g of PbBr2 is added to a liter of 0.77g of
NaCl? MM PbBr2 = 367.2; MM NaCl = 58