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Chemical Kinetics and

Equilibrium
Joanne Katherine T. Manlusoc, MSc.
CHEMISTRY THROWBACK
Chemistry - study of the property of matter and the changes
it undergoes.

Topics in Chemistry which involved studying the property of


matter are:
• Classification
• Energetics and Thermodynamics
• Electrochemistry
• Chemical and physical bonds
• Molecular geometry
• Solutions and solubility

Changes in matter are reactions. otherwise termed as


chemical reactions.
CHEMISTRY THROWBACK
Qualitative Chemistry – branch of chemistry that
deals with the identification of what matter is by
examination of its properties and changes undergone
Quantitative Chemistry – branch of chemistry that
deals with the identification of how much matter
there is by examination of its properties and changes
undergone
Pharmaceutical Chemistry – branch of pharmacy
and chemistry that deals with the use of properties
and changes of significant compound to bring out
certain uses in the pharmacy practice.
CHEMISTRY THROWBACK
Concentration Expressions
Recall that the concentration (amount of solute present)
in a solution can be expressed in the following ways:
Molarity = g solute/ L solvent
Molality = g solute/ kg solvent
Normality = Equivalents solute/ L solvent

Also, dilution is important in case the concentration is


meant to be altered.
M1V1 = M2V2
CHEMICAL KINETICS
Kinetics – related to motion or movement.

Chemical Kinetics is the branch of chemistry


concerned with the 1) rate or speed of reactions, 2)
factors affecting them, and the 3) number of
mechanisms or steps by which they occur.
A. RATE: DEFINITION AND
DETERMINATION
Rate – any quantity divided by time.
(Q/t)

Rate of Reaction - amount of compound (product or


reactant) produced over time.
• Reactants – reduced over time = negative sign.
• Products are formed – produced over time = positive sign.

(via law of conservation of mass)

Q = Amount of reactant (usually expressed in


concentrations as molar [M])
A. RATE: DEFINITION AND
DETERMINATION
In the reaction
A + B -> AB,

Rate of reaction of product


= Q/t; for example
= AB(in M) / t (in seconds)

Rate of reaction of reactant


= (-) Q/t; for example
= (-) A or B (in M) / t (in seconds)
EXAMPLE
NO2 is produced at a rate of 0.0072 M/s.

N2O5 ---> NO2 + O2

1. Find rate of oxygen production.


2. Find rate of N2O5 usage.
B. CONCEPTS AND CORRESPONDING
FACTORS AFFECTING RATE
I. Rate Law: Factor of Concentration
The Rate Law is the core of Chemical Kinetics
simply because it is the single most essential
concept that explains the speed of the feasible
reaction.
a. Concentration – the quantity of matter in a given
mixture.

Rate Law – an equation that relates the rate of reaction


to concentration of reactants.
Concentration – since the rate law depends on the
concentration of reactants, a change on reactant changes
the rate law and the rate law constant.
B. CONCEPTS AND CORRESPONDING
FACTORS AFFECTING RATE
The rate law can be described by its order.
The reaction has an order, based on the units of
reactants involved in the rate law. Individual reactants
have their own order (first order, second order) and the
overall rate law has also an order (the combination of all
individual orders)

Rate = k[A]2[B]

Individual orders: 2nd order for A; 1st order for B


Overall order: 3rd order
EXCERCISE
Trial NO [M] H2[M] Rate [m/s]
Given the following: 1 5 x 10-3 2 x 10-3 1.2 x 10-5
2 10 x 10-3 2 x 10-3 5 x 10-5

NO + H2 -> products 3 10 x 10-3 4 x 10-3 10 x 10-5

1. Give the rate law, orders of reactants, overall


order, constant k.
2. Solve for the rate if NO = 0.031M and H2 = 1.2 M
B. CONCEPTS AND CORRESPONDING
FACTORS AFFECTING RATE
II/III. Collision Theory: Factors of Temperature and
Orientation
The Collision Theory is as important as Rate Law
because it tells about the possibility of the feasible
reaction.
b. Temperature – amount of thermal energy
possessed by a body of matter.
c. Orientation – position of two or more
interacting bodies of matter.
B. CONCEPTS AND CORRESPONDING
FACTORS AFFECTING RATE
Collision Theory – states that two bodies of matter
must make contact to each other in order to have a
chance of making a chemical reaction happen.

• Not all collisions are effective; thus, ineffective


collisions do not induce chemical reactions
(although a physical reaction may take place).
B. CONCEPTS AND CORRESPONDING
FACTORS AFFECTING RATE
The factors that decide
whether the collision is
effective are:

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).

• Special catalysts called enzymes are the most


efficient ever known, existing within biological
systems such as that of the human body. The
reactants on which these catalysts act upon are
called substrates.
C. REACTION MECHANISMS: LOGICAL
LEVEL OF REACTION STUDIES
The conversion of ferric chloride to its ferric and chloride ions
takes only a step and can be expressed just by writing the
formula.

However, formation of a drug from simpler substituents takes


far more than just a single reaction. Reaction mechanisms
explain specifically what happens to reactants in a multi-step
reaction until they become products.

Chemical kinetics covers reaction mechanisms because the


study of reaction rates is not the same in multi-step reactions
compared to that of a simpler single-step reaction.
C. REACTION MECHANISMS: LOGICAL
LEVEL OF REACTION STUDIES
Intermediate – a product in one step of the reaction, but not a
product in the overall reaction.
“A product not seen in the final product side.”
ex. ATP and NADPH in photosynthesis

Catalyst – in reaction mechanisms, is seen as a reactant in one step


that does not become used, and thus is seen at the final product
side.
“A reactant not seen in the final reactant side.“
ex. Concentrated sulfuric acid, palladium

NOTE: Catalysts and intermediates cannot participate in the rate


law as they did not get transformed per se in the reaction.
C. REACTION MECHANISMS: LOGICAL
LEVEL OF REACTION STUDIES
Anatomy of a simple multi-step (2-step) reaction:
A + B ---> C + D
D + E ----> F + B
A + E ---> C + F

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)

Because the second reaction is the slower reaction


and thus the RDS, the rate law will be:

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.

the disturbance has


been neutralized.
LAW OF MASS ACTION AND THE
EQUILIBRIUM-CONSTANT
Law of Mass Action – states that at a given
temperature, a chemical reaction will have a stable
ratio of products and reactants by determining the
concentrations (for liquids) or partial pressures (for
gases) of the reactant-product mixture.

The numerical representation of the ratio between


products formed and reactants retained is shown by
the equilibrium constant Keq.
LAW OF MASS ACTION AND THE
EQUILIBRIUM-CONSTANT
𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
𝐾eq =
𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

Keq can give us ideas regarding the direction of the


reaction in equilibrium.
If the Keq is high, the reaction will favor formation of
products.
If the Keq is low, the reaction will not favor formation
of reactants.
LAW OF MASS ACTION AND THE
EQUILIBRIUM-CONSTANT
1. The coefficient of the species will serve as its
exponent in the Keq constant equation.
Ex. If 2A + B <-> 2C, then keq = [C]2 /[A]2[B]
2. The equilibrium constant is stoichiometric in nature; it
does not aim to discuss reaction mechanisms. It aims to
determine how much, not how.
3. Pure substances (pure solids and liquids) have a
concentration of 1, and are not included in the constant
expression. Reactions with such species are called as
heterogeneous.
Ex. If 2A(g) + B(s) <-> 2C(g), then Keq = [C]2/[A]2
MANIPULATION OF Keq
The Keq can be mathematically manipulated depending
on the changes in the given reaction. For example, we
use the given original equation:
2SO2 + O2 <--> 2SO3 Keq = 0.15
1. Backward reaction = reciprocal of Keq
2SO3 <--> 2SO2 + O2 Keq = 1/0.15 = 6.67
2. Division of equation into two = square root of Keq
SO2 + 1/2 O2 <--> SO3 Keq = √0.15 = 0.39
3. Multiplication of two = square of Keq
4SO2 + 2O2 <--> 4SO3 Keq = (0.15)2 = 0.023
EXCERCISE
1. If the equilibrium constant for the formation of
ethanol from acetaldehyde is 0.000006, what will
the constant be when acetaldehyde becomes the
product?

2. If twice the amount of 2mL formic acid turning


into formate has the constant of 0.000177, what
is the constant of 2mL formic acid turning into
formate?
LE-CHATELIER’S PRINCIPLE
This principle states that a disturbance in equilibrium
(producing a significant net amount of product or
reactant away from equilibrium) will produce a
progress in reaction that will return the reaction back
to equilibrium.
LE-CHATELIER’S PRINCIPLE
1. Concentration – addition of something on one side
will cause a shift to the opposite side and vice-versa
(removal on one side will cause a shift to that side).

3A + 2C <-> 2B

Increase in A will shift the reaction towards the right.


Increase in B will shift the reaction towards the left.
Decrease in C will shift the reaction towards the left.
LE-CHATELIER’S PRINCIPLE
2. Temperature – the nature of the reaction should
be first known. If it is exothermic, the heat will be on
the product side. If it is endothermic, the heat will
be on the reactant side.

Thus, increase in temperature will shift the reaction


toward its opposite side of the reaction, and decrease
in temperature will shift the reaction toward its side
of the reaction.
LE-CHATELIER’S PRINCIPLE

3AC <-> 3A + C + heat


Increase in temperature will shift the reaction
towards the left, and vice-versa.

3AC + heat <-> 3A + C


Increase in temperature will shift the reaction
towards the right, and vice-versa.
LE-CHATELIER’S PRINCIPLE
3. Volume and Pressure – factor applicable only to
gases. Adding pressure will decrease the volume on
the side with lesser volume and causes a shift to that
side; and vice-versa.
2A + 5C <-> 6F
Reactants = 7 moles; Products = 6 moles
In this case, if pressure is applied, the reaction will
shift towards the right. If pressure is relieved, the
reaction will shift towards the left.
(In cases where both reactants and products have same number of moles
of gas, increased/decreased pressure will not disturb the equilibrium)
LE-CHATELIER’S PRINCIPLE
4. Catalysts and Inert Gases – catalysts do not affect
equilibrium. Recall that catalysts lower EA in a
progressing reaction, but a reaction in equilibrium is
already done with progression. Inert gases and
anything that is not used up or produced in the
reaction will not affect the equilibrium as well.
EXERCISE
1. In the human lungs, carbon dioxide is quickly
turned into carbonic acid. If a person inhales twice
the amount of carbon dioxide, what will happen to
the carbonic acid content of the body?
2. The exothermic conversion of magnesium
carbonate to magnesium oxide takes place extremely
slowly in room temperature. If the temperature
from 200 deg. C is increased to 300 degrees, will
there be more or less production of magnesium
oxide?
EXERCISE
3. In the Haber-Bosch process, nitrogen and
hydrogen gases react to form ammonia. If two moles
of ammonia are produced from every three moles of
hydrogen and one mole of nitrogen in a closed
system, what will happen if pressure is applied to the
mixture? Vice-versa?
REACTIONS NEARING
EQUILIBRIUM
• Reactions that will proceed to equilibrium but are
not yet at equilibrium can be represented by
finding the product of the concentration/partial
pressures of the products formed so far. That
product is called the reaction quotient (Qc)
REACTIONS NEARING
EQUILIBRIUM
Several inferences can be made, using the basis of Le
Chatelier’s principle on concentration:

• 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

• Arrhenius – acids produce hydrogen ions in solution,


while bases produce hydroxide ions in solution.
• Bronsted-Lowry – acids donate protons, and bases
receive protons.
• Lewis – acids receive electrons, and bases donate
electrons.
A. WATER, ACIDS, AND BASES:
STRENGTH
Strength of acids and bases: pH/pOH

Acids and bases have a certain strength, chemically on


their ability to donate and accept electrons, respectively.

By visual observation, we can determine the strength of


an acid by its ability to leave out a proton/hydrogen ion
and of a base by its ability to attract a proton/hydrogen.
A. WATER, ACIDS, AND BASES:
STRENGTH
Mathematically, we can calculate acid or base strength by a
numerical value of hydrogen or hydroxide ions released per
amount of substance by pH and pOH In a solution
respectively.
pH = -log [H+]
pOH = -log [OH-]
*Note that a bracket denotes concentration in Molarity

Conversely, if we are given the pH or pOH of the certain acid


or base, we can derive the [H+] or [OH-] by using the antilog
function.
[H+] = antilog(pH)
[OH-] = antilog(pOH)
A. WATER, ACIDS, AND BASES:
STRENGTH
Diversity of the acids and bases allows them to be
separated based on their strength. There are the strong
acids and bases, and there are the weak.

Very important note: Strong acids and bases completely


dissociate in water, where all acid or base molecules (the
reactant) turn into their ions (the products) with no
leftover acid/base – and recall that a reaction without
leftover reactants cannot be reversible i.e. in equilibrium.
Weak acids/bases do not completely dissociate, thus have
leftover reactant molecules, thus have reversible reactions, thus
have equilibrium.
EXERCISE
1. If the pH of an acid is 4.7, what is its [H+]?
2. If the [OH-] of a base is 3.2 x 10-2, what is its pOH?
3. What is the hydrogen ion concentration of an
impure water sample with a pH of 10.48?
4. If the negative logarithm of the hydroxide ion
concentration of an acid is 11.23, find [OH-]
A. WATER, ACIDS, AND BASES:
STRENGTH
Conjugate acids and bases

• Conjugate – joined together; coupled.


• A conjugate base is the acid minus a proton. (ex. H2CO3
is an acid; HCO3- is its conjugate base).
• A conjugate acid is a base plus a proton. (NH3 is a base;
NH4+ is its conjugate acid). Conjugates result from
acid/base equilibrium reactions.
EXERCISE
1. What is the conjugate base of ammonia?
2. In the reaction KHSO4 + K2CO3 <--> K2SO4 + KHCO3,
which is the acid reactant? Its conjugate base. The
base reactant? Its conjugate acid?
A. WATER, ACIDS, AND BASES:
STRENGTH
A. Kw: THE ION-PRODUCT CONSTANT

Pure water is almost stable and non-reactive, especially


strongly bonded together by hydrogen bonds. However,
their occasional disturbances in charge due to induced
dipoles allow them to produce ions within themselves
(Thus, auto- or self-ionization).
A. WATER, ACIDS, AND BASES:
STRENGTH
The reaction is as follows:
H2O + H2O <-> H3O+ + OH-

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

Thus, pH and pOH of water is both 7. pH 7 is called the neutral pH.


A. WATER, ACIDS, AND BASES:
STRENGTH
B. Ka and Kb: ACID/BASE DISSOCIATION CONSTANT

• Acid Dissociation and Base Dissociation constants


The acid dissociation constant (Ka), like any equilibrium
constant, is solved by dividing products by reactants.
Specifically, the product of acid dissociation is the
conjugate base and hydrogen proton, while the reactant is
obviously the original acid.
Ka = [A-][H+]
[HA]
A. WATER, ACIDS, AND BASES:
STRENGTH
The base dissociation constant (Kb) can similarly be
calculated as follows:
Kb = [HB][OH-]
[B-]
Because weak acids and bases release only a small
amount of hydrogen or hydroxide ions respectively, the
term percent ionization (%I) is used to compare how
much ions are released from the original acid/base.

%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

= 3 x 10-3M H+, pH is 2.5 for acetic acid alone


1.8 x 10-5 = x(0.1)/0.5
= 9 x 10-5, pH is 4.04
There is 1.54 units in pH difference.
EXERCISE
1. A 0.25M acetic acid mixed with 0.1M of its
conjugate base has how much difference in terms of
%I to 0.25M acetic acid alone? Ka = 1.8 x 10-5

2. If a 0.12M acid solution contains 0.032M of its


conjugate base, what is the difference in terms of
pOH to 0.12M acid solution alone? pKa = 9.22
A. WATER, ACIDS, AND BASES:
STRENGTH
D. BUFFERS AND THE HENDERSON-HASSELBACH
FORMULA
• Buffers - systems that limit drastic changes in pH by
absorbing produced free hydrogen or hydroxide ions
within themselves.
• Buffers are created by mixing an acid and its conjugate
base. The solution containing these two will have a
specific pH different to the pH of any one of them
(somewhere in between).
• Difference in pH of the buffer to its components is key to
finding the concentration of buffer when acid
concentration is given and vice-versa.
A. WATER, ACIDS, AND BASES:
STRENGTH
The Henderson-Hasselbalch equation can be used to
determine buffer component ratios, utilizing the
differences in pH of buffer and its component
acid/base.

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.

• Solubility is highly dependent on polarity and energy.


Polarity is the chemical basis of solubility that uses the
dipoles of the solute and solvent to predict whether
solvation will take place or not. Energy is important
since even in physical interactions, enough energy must
be used to overcome the intermolecular forces
between like particles.
B. IONS AND PRECIPITATES:
SOLUBILITY
A. Ksp: SOLUBILITY CONSTANT
Much like equilibrium constants, the same
formula goes to calculating the constant
for solutions. Specifically, the product
is/are the ions, while the reactant is the solute.

Ksp = Product of ions


B. IONS AND PRECIPITATES:
SOLUBILITY
Recall that in heterogenous equilibrium, solid
products have a concentration equivalent of 1. Thus,
if we add the solute, the denominator would simply
be 1.

NOTE: If an ion has a coefficient, such will be used as


both coefficient and exponent for the particular ion.
Ex. AB <-> A + 2B, then Ksp = [A][2B]2
EXERCISE
1. CaF2 dissolves into equal portions of calcium and
fluoride ions. Find the Ksp if each ion has a
concentration of 6.24 x 10-6 M.

2. If cuprous hydroxide dissociates into one cuprous


ion and two hydroxide ions. If its Ksp is 2.2 x 10-20,
then what is the concentration of cuprous and
hydroxide ions?
B. IONS AND PRECIPITATES:
SOLUBILITY
B. MOLAR SOLUBILITY

• Molar solubility is defined as the number of moles of


salt that a liter of solution can handle before it becomes
saturated. (n/L or M)

• Solubility is considered as the amount of grams of ions


produced that can saturate a liter of solution.
EXAMPLE
Find molar solubility, Ksp and solubility of AgBr if this
salt saturates a liter of solution with 1.65 x 10-4
grams. MM = 187.8 g/n

Molar solubility = 8.8 x 10-7 M AgBr


Ksp = 7.7 x 10-13
Solubility = 1.65 x 10-4 g/L Ag+ and Br-
EXERCISE
1. If barium sulfate dissociates into barium and
sulfate ions, find molar solubility and solubility if the
given mass to saturate the solution is 2.5 x 10-3 g per
liter. MM barium sulfate = 233 g/n

2. Use the exercise problem #2 for Ksp to find molar


solubility and solubility. MM cuprous hydroxide =
97.5 g/n
B. IONS AND PRECIPITATES:
SOLUBILITY
C. COMMON-ION EFFECT
In a salt solution that is saturated, the Ksp is equal to the
product of the ions produced. If one of the two ions
(usually the anion) is added, the equilibrium will have to
shift to the direction of the salt, because of Le Chatelier’s
principle. The other ion would have to change quantity
to retain the Ksp.
EXERCISE
1. Given that the solution will form a precipitate, the
ksp values for AgCl, AgBr and AgI are 1.6 x 10-10, 7.7 x
10-12, and 8.3 x 10-17, respectively. If silver ions are
slowly added to the solution containing 0.05n of all
these three, which will precipitate first? Which has
the greatest molar solubility?
B. IONS AND PRECIPITATES:
SOLUBILITY
D. PRECIPITATE PREDICTION AND RELATIVE
SOLUBILITIES
In a salt solution that is saturated, the ksp will be equal to
the product of the ions produced. If two other salts with
the cation and anion components are mixed together,
their resultant ions may be measured and a new constant
may be derived. This is usually denoted as Q.
B. IONS AND PRECIPITATES:
SOLUBILITY
Because the target salt would have its own ksp, Q and
ksp can be compared:

• If Q > Ksp, precipitation, supersaturation occurs and will


proceed the reduction of products.
• If Q = Ksp, no precipitation, saturation occurs,
equilibrium is achieved and reaction progress stops.
• If Q < Ksp, no precipitation, unsaturation occurs and will
proceed the addition of products.
EXAMPLE
If 0.01M NaOH is added to a liter of 0.1M CuCl2, will
Cu(OH)2 precipitate? Ksp = 1.6 x 10-19

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

2. What if 0.2M of 250mL PbBr2 was used in problem


#1?
REFERENCES
1. Brown, T.L., LeMay, H.E., Bursten, B.E. (2004). Chemistry: The Central Science Ninth Edition. San
Francisco: Pearson Education, Inc.
2. McMurry, J. (2007). Organic Chemistry: A Biological Approach. Belmont, CA: Thomson Brooks/Cole.
3. Boyer, R. (2005). Concepts in Biochemistry Fifth Edition. New York: John Wiley and Sons, Inc.
4. Burdge, J. (2009). Chemistry. New York: McGraw Hill, Inc.
5. Silberberg, M.S. (2009). Chemistry: The Molecular Level of Matter and Change Fifth Edition. New York:
McGraw Hill, Inc.
6. Manansala, M.E.J. (2010). Lecture notes in Pharmaceutical Chemistry 1. University of Santo Tomas.