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Chemistry Review Group

University of Santo Tomas


Faculty of Pharmacy
Scholia Tutorial Club

REVIEWER: FIRST AND SECOND SHIFTING PERIODS


ANALYTICAL CHEMISTRY (CHEM 301)/ PHARMACEUTICAL CHEMISTRY 1 LECTURE
Prepared by:
Ser Loisse R. Mortel
Chemistry Review Group
REVIEW PROPER #1: COLLIGATIVE
PREREQUISITE: CHEMISTRY 100 PROPERTIES OF SOLUTIONS
(ANALYTICAL CHEMISTRY TOPIC ONLY)
Chemistry - study of the property of matter and the Colligative adj. dependent on quantity instead of
changes it undergoes. nature
Topics in Chemistry which involved studying the - Colligative properties are specific for solutions, which
property of matter are: depend on the number of solute particles instead of
- Classification their nature.
- Energetics and Thermodynamics
- Electrochemistry 1. Vapor Pressure Lowering the pressure exerted by
- Chemical and physical bonds the vapor being given off by the liquid at a given
- Molecular geometry temperature
- Solutions and solubility Rule: The lowering of vapor pressure of a solvent is
Changes in matter are otherwise termed as chemical equal to the product of mole fraction solute and vapor
reactions. pressure of pure solvent.

Qualitative Chemistry branch of chemistry that P = P x MF solute


deals with the identification of what matter is by Where P = lowering of vapor pressure
examination of its properties and changes undergone P = vapor pressure of solvent
Quantitative Chemistry branch of chemistry that P = Vp solution Vp solvent
deals with the identification of how much matter
there is by examination of its properties and changes P (pressure of solution) = P - P
undergone
Qualitative and quantitative chemistries are Ex. A solution contains 1.75 moles of sucrose in a liter
combined into what is known as analytical chemistry. of water. What is the vapor pressure lowering of the
Pharmaceutical Chemistry branch of pharmacy and solvent? What is the vapor pressure of the solution?
chemistry that deals with the use of properties and P = 23.72 C
changes of significant compound to bring out certain P = P x MF solute
uses in the pharmacy practice. MF solute = moles solute/ moles solution
* moles solution = moles solute + solvent
Concentration Expressions Moles solvent = 100g/ 18 = 55.56 moles water
Recall that the concentration (amount of solute Moles solution = 57.31
present) in a solution can be expressed in the MF solute = 1.75/57.31 = 0.031
following ways:
Molarity = g solute/ mm solute (L solvent) P = 23.72(0.031)
Molality = g solute/ mm solute (kg solvent) = 0.727 mmHg
Normality = Equivalents solute/ L solvent
P = P - P
Also, dilution is important in case the concentration is = 23.72 0.727 = 23.0 mmHg
meant to be altered.
M1V1 = M2V2 2. Boiling Point Elevation the boiling point is the
temperature at which the liquid state turns into the
gaseous state.
Rule: The boiling point elevation of the solvent is
directly proportional to the molecular concentration of
the solution.

Tb = ikb(m)
Where kb = molal bpt constant/ ebullioscopic constant
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i = vant Hoff factor (#ions formed in solution) REVIEW PROPER #2: CHEMICAL
m = molality
Tb = boiling point elevation KINETICS
Tb (boiling point of solution) = Tb + Tb Kinetics adj. related to motion or movement.
- Chemical Kinetics is the branch of chemistry
Ex. What is the boiling point elevation of 60.0g of concerned with the 1) rate or speed of reactions, 2)
water that contains 2.00g of glycerol, C3H5(OH)3? factors affecting them, and the 3) number of
Molality = 0.362, Bpt constant of water = 0.51C mechanisms or steps by which they occur.
Tb = kb(m)
Tb = 1(0.51C)(0.362) = 0.185C A. RATE: DEFINITION AND DETERMINATION
Thus, if bpt solvent is 100C, the bpt of the entire Rate any quantity divided by time. (Q/t)
solution becomes 100.185C. - Rate of Reaction - amount of compound (product or
reactant) produced over time.
- Reactants reduced over time = negative sign.
3. Freezing Point Depression the freezing point is - Products are formed produced over time = positive
the temperature where the liquid state turns into the sign.
solid state. (Via law of conservation of mass)
Rule: The freezing point depression is directly
proportional to the molal concentration of the Q = Amount of reactant (usually expressed in
solution. concentrations as molar [M])

Tf = ikf(m) In the reaction


Where Tf = freezing point depression A + B -> AB,
i = vant Hoff factor
m = molality Rate of reaction of product
kf = molal fpt constant/ cryoscopic constant
= Q/t; for example
= AB(in M) / t(in seconds)
Tf (freezing point of solution) = Tf - Tf
Rate of reaction of reactant
Ex. Calculate the freezing point depression of 0.46
= (-) Q/t; for example
molal diphenyl-naphthalene solution in 200g of
= (-) A or B (in M) / t(in seconds)
benzene. Freezing point of naphthalene = 5.5C; molal
freezing point constant= 5.12C
Exercise:
NO2 is produced at a rate of 0.0072 M/s.
T = 1(5.12C)(0.46m) = 2.3C
Tf = Tf - T
2N2O5 ---> 4NO2 + O2
Tf = 5.5C - 2.3C
= 3.2C
1. Find rate of oxygen production.
2. Find rate of N2O5 usage.
4. Increase in Osmotic Pressure () pressure that is
required to stop osmosis.
B. CONCEPTS AND CORRESPONDING
= MRT FACTORS AFFECTING RATE
Where M = molarity
R = gas constant I. Rate Law: Factor of Concentration
T = temperature (K) The Rate Law is a core of Chemical Kinetics simply
because it is the single most essential concept that
Ex: What is the osmotic pressure of a selection at explains the speed of the feasible reaction.
29.0C that contains 15.0g of glucose in 80.0mL a. Concentration the quantity of matter in a given
solution? mixture.
= MRT
= [150g / (180g/n x 0.08L)] x 0.0821L-atm/mol-K x Rate Law an equation that relates the rate of
302K reaction to concentration of reactants.
= 25.8 atm
Concentration since the rate law depends on the
concentration of reactants, a change on reactant
changes the rate law and the rate law constant.

The rate law can be described by its order.


The reaction has a order, based on the units of
reactants involved in the rate law. Individual reactants

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have their own order (first order, second order) and
the overall rate law has also an order (the IV. Catalysis: Factor of Catalysts
combination of all individual orders) A catalyst is a substance that helps in increasing the
rate of reaction. The following are characteristic of
Ex. Rate = k[A]2[B] most catalysts:
Individual orders: 2nd order for A; 1st order for B 1. A catalyst speeds rate of reactions thru
Overall order: 3rd order lowering of the activation energy;
2. It is not used up in the reaction;
Exercise: Given the following: 3. It does not affect chemical equilibrium (refer
NO + H2 -> products to section on chemical equilibrium); and
Trial NO [M] H2[M] Rate [m/s] 4. It usually acts by physical forces, forming a
1 5 x 10-3
2 x 10-3
1.2 x 10-5 temporary complex with the target reactant
2 10 x 10 -3
2 x 10-3
5 x 10-5 to stabilize transition state.
3 10 x 10-3 4 x 10-3 10 x 10-5

Give the rate law, orders of reactants, overall order,


constant k.
Solve for the rate if NO = 0.031M and H2 = 1.2 M

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 Catalysts can be generally categorized into two:
possessed by a body of matter. Heterogenous catalysts - exist in a phase
c. Orientation position of two or more different from that of the reactant (ex. metal
interacting bodies of matter. catalyst in gas production)
Homogenous catalysts - exist in a phase same
Collision Theory states that two bodies of matter with that of the reactant (ex. liquid catalyst in
must make contact to each other in order to have a aqueous/liquid reactant).
chance of making a chemical reaction happen.
Not all collisions are effective; thus, ineffective Special catalysts called enzymes are the most efficient
collisions do not induce chemical reactions ever known, existing within biological systems such as
(although a physical reaction may take place). that of the human body. The reactants on which these
The factors that decide whether the collision is catalysts act upon are called substrates.
effective are:
C. REACTION MECHANISMS: LOGICAL LEVEL
1. Temperature enough (thermal) energy is
OF REACTION STUDIES
needed upon collision to favor the formation of
The conversion of ferric chloride to its ferric and
new products. This required energy to make the
chloride ions takes only a step and can be expressed
chemical reaction possible is called the energy of
just by writing the formula.
activation/ activation energy. (EA)
However, formation of a drug from simpler
substituents takes far more than just a single reaction
(some have 5, 10, even 20 or more reactions in
between!) 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.

Anatomy of a simple multi-step (2-step) reaction:


A + B ---> C + D
D + E ----> F + B
2. Orientation colliding particles must be properly
A + E ---> C + F
oriented in order to amplify the attraction
A, E = reactants D = intermediate
between each other, making more possible the F, C = products B = catalyst
achievement of EA.

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Intermediate a product in one step of the reaction, REVIEW PROPER #3: INTRODUCTION
but not a product in the overall reaction.
A product not seen in the final product side. TO EQUILIBRIUM
ex. ATP and NADPH in photosynthesis
A. DEFINITION
Catalyst in reaction mechanisms, is seen as a Equilibrium - state wherein the amount of products
reactant in one step that does not become used, and and reactants stay the same in an equal reaction
thus is seen at the final product side. process.
A reactant not seen in the final reactant side. Unless the products exist with leftover reactant,
ex. Concentrated sulfuric acid, palladium equilibrium cannot happen because it only
happens on reversible reactions. (Double arrow
NOTE: Catalysts and intermediates cannot participate <-----> is used to denote a reversible reaction).
in the rate law as they did not get transformed per se Equilibrium on reversible reactions is achieved
in the reaction. only when NET production of either products or
reactants is zero.
II. Reaction Mechanisms and the Rate Law Therefore, there will be a flat graph of
The integration of chemical kinetics and reaction concentration vs. time on an energy diagram
mechanisms relies on three general rules: for reactions in equilibrium to denote that
1. The individual steps must add up to the overall zero net production.
balanced equation; If the reaction is returned to progress (aka
2. The individual steps are bound to all rules set up disturbed with a corresponding rise or fall in
by chemical kinetic principles; and the flat graph), there will be changes to maintain
3. The reaction mechanism is derived from the rate equilibrium and the graph will return to flatness
law, not the other way around. after the disturbance has been neutralized.

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 Mathematical/quantitative study of equilibrium
in the entire reactions rate law. depends highly on equilibrium constants.

ex. B. LAW OF MASS ACTION AND THE


NO + O2 <----> NO3 (fast) EQUILIBRIUM-CONSTANT
NO3 + NO -----> 2NO2 (slow)
Law of Mass Action states that at a given
Because the second reaction is the slower reaction temperature, a chemical reaction will have a stable
and thus the RDS, the rate law will be: ratio of products and reactants by determining the
Rate = k[NO3][NO] concentrations (for liquids) or partial pressures (for
gases) of the reactant-product mixture.
Exercises: The numerical representation of the ratio
1. Give the rate law for the following reaction between products formed and reactants retained
mechanism: is shown by the equilibrium constant Keq.
N2O -----> N2 + O (slow)
N2O + O ----->N2 + O2
2. Give the rate law for the following reaction eq =

mechanism:
A + B <--> AB (slow) Keq can give us ideas regarding the direction of the
AB --->A + C 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.

Notes:
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]
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2. The equilibrium constant is stoichiometric in 3AC + heat <-> 3A + C
nature; it does not aim to discuss reaction Increase in temperature will shift the reaction
mechanisms. It aims to determine how much, not towards the right, and vice-versa.
how.
3. Pure substances (pure solids and liquids) have a 3. Volume and Pressure factor applicable only to
concentration of 1, and are not included in the gases. Adding pressure will decrease the volume on
constant expression. Reactions with such species the side with lesser volume and causes a shift to that
are called as heterogeneous. side; and vice-versa.
Ex. If 2A(g) + B(s) <-> 2C(g), then Keq = [C]2/[A]2 Ex. 2A + 5C <-> 6F
Reactants = 7 moles; Products = 6 moles
C. MANIPULATION OF Keq In this case, if pressure is applied, the reaction will
The Keq can be mathematically manipulated shift towards the right. If pressure is relieved, the
depending on the changes in the given reaction. For reaction will shift towards the left.
(In cases where both reactants and products have same number of moles
example, we use the given original equation: of gas, increased/decreased pressure will not disturb the equilibrium)
2SO2 + O2 <--> 2SO3 Keq = 0.15
4. Catalysts and Inert Gases catalysts do not affect
1. Backward reaction = reciprocal of Keq equilibrium. Recall that catalysts lower EA in a
2SO3 <--> 2SO2 + O2 Keq = 1/0.15 = 6.67 progressing reaction, but a reaction in equilibrium is
already done with progression. Inert gases and
2. Division of equation into two = square root of Keq anything that is not used up or produced in the
SO2 + 1/2 O2 <--> SO3 Keq = 0.15 = 0.39 reaction will not affect the equilibrium as well.
3. Multiplication of two = square of Keq Exercises:
4SO2 + 2O2 <--> 4SO3 Keq = (0.15)2 = 0.023 1. In the human lungs, carbon dioxide is quickly
turned into carbonic acid. If a person inhales
Exercises: twice the amount of carbon dioxide, what will
1. If the equilibrium constant for the formation happen to the carbonic acid content of the
of ethenol (<correct spelling) from acetaldehyde body?
is 0.000006, what will the constant be when 2. The exothermic conversion of magnesium
acetaldehyde becomes the product? carbonate to magnesium oxide takes place
2. If twice the amount of 2mL formic acid extremely slowly in room temperature. If the
turning into formate has the constant of temperature from 200 deg. C is increased to
0.000177, what is the constant of 2mL 300 degrees, will there be more or less
formic acid turning into formate? production of magnesium oxide?
3. In the Haber-Bosch process, nitrogen and
D. LE-CHATELIERS PRINCIPLE hydrogen gases react to form ammonia. If two
This principle states that a disturbance in moles of ammonia are produced from every
equilibrium (producing a significant net amount three moles of hydrogen and one mole of
of product or reactant away from equilibrium) nitrogen in a closed system, what will happen if
will produce a progress in reaction that will pressure is applied to the mixture? Vice-versa?
return the reaction back to equilibrium.
E. REACTIONS NEARING EQUILIBRIUM
1. Concentration addition of something on one side Reactions that will proceed to equilibrium but are not
will cause a shift to the opposite side and vice-versa yet at equilibrium can be represented by finding the
(removal on one side will cause a shift to that side). product of the concentration/partial pressures of the
ex. 3A + 2C <-> 2B products formed so far. That product is called the
Increase in A will shift the reaction towards the right. reaction quotient (Qc)
Increase in B will shift the reaction towards the left. Several inferences can be made, using the basis of Le
Decrease in C will shift the reaction towards the left. Chateliers principle on concentration:

2. Temperature the nature of the reaction should be If Qc > Keq, the reaction has too many products,
first known. If it is exothermic, the heat will be on the and will shift the equilibrium to the left (towards
product side. If it is endothermic, the heat will be on reactants)
the reactant side. If Qc < Keq, the reaction has too many reactants,
Thus, increase in temperature will shift the and will shift the equilibrium to the right (towards
reaction toward its opposite side of the reaction, products)
and decrease in temperature will shift the reaction Qc = Keq when the reaction is in equilibrium
toward its side of the reaction.
Ex. 3AC <-> 3A + C + heat Exercise: Given that the Keq for a reaction is 21, give
Increase in temperature will shift the reaction the inference when the products A and B are both
towards the left, and vice-versa. 5.3M while the only reactant is 1.85M.

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REVIEW PROPER #4: SPECIFIC c. Conjugate acids and bases
Conjugate adj. joined together; coupled.
EQUILIBRIUM A conjugate acid is the acid minus a proton. (ex.
H2CO3 is an acid; HCO3- is its conjugate acid).
SUB-PROPER #1: WATER, ACIDS, AND A conjugate base is a base plus a proton. (NH3 is a
BASES: STRENGTH base; NH4+ is its conjugate base). Conjugates
result from acid/base equilibrium reactions.
A. REVIEW AND INTRODUCTION
a. Definitions Exercises:
Arrhenius acids produce hydrogen ions in solution, 1. What is the conjugate base of ammonia?
while bases produce hydroxide ions in solution. 2. In the reaction KHSO4 + K2CO3 <--> K2SO4 +
Bronsted-Lowry acids donate protons, and bases KHCO3, which is the acid reactant? Its conjugate
receive protons. base. The base reactant? Its conjugate acid?
Lewis acids receive electrons, and bases donate
electrons. B. Kw: THE ION-PRODUCT CONSTANT
Pure water is almost stable and non-reactive,
b. Strength of acids and bases: pH/pOH especially strongly bonded together by hydrogen
Acids and bases have a certain strength, chemically on bonds. However, their occasional disturbances in
their ability to donate and accept electrons, charge due to induced dipoles allow them to produce
respectively. ions within themselves (Thus, auto- or self-
ionization). The reaction is as follows:
By visual observation, we can determine the strength
of an acid by its ability to leave out a H2O + H2O <-> H3O+ + OH-
proton/hydrogen ion and of a base by its ability to
attract a proton/hydrogen. The Keq of water by 25 deg. C is 1.0x10-14. This is also
called the ion-product constant for water (Kw),
Mathematically, we can calculate acid or base
strength by a numerical value of hydrogen or Kw = [H+][OH-]
hydroxide ions released per amount of substance by
pH and pOH In a solution respectively. Thus, we can get the concentration of ions produced.
pH = -log [H+]
pOH = -log [OH-] H+ = 1.00 x 10-7; pH = 7
*Note that a bracket denotes concentration in Molarity OH- = 1.00 x 10-7; pOH = 7
Conversely, if we are given the pH or pOH of the
certain acid or base, we can derive the [H+] or [OH-] Thus, pH and pOH of water is both 7. pH 7 is called
by using the antilog function. the neutral pH.
[H+] = antilog(pH)
[OH-] = antilog(pOH) C. Ka and Kb: ACID/BASE DISSOCIATION
CONSTANT
Diversity of the acids and bases allows them to be
separated based on their strength. There are the a. Acid Dissociation and Base Dissociation constants
strong acids and bases, and there are the weak. The acid dissociation constant (Ka), like any
equilibrium constant, is solved by dividing products by
Very important note: Strong acids and bases reactants. Specifically, the product of acid dissociation
completely dissociate in water, where all acid or base is the conjugate acid, while the reactant is obviously
molecules (the reactant) turn into their ions (the the original acid.
products) with no leftover acid/base and recall that Ka = [A-][H+]
a reaction without leftover reactants cannot be [HA]
reversible i.e. in equilibrium.
Weak acids/bases do not completely dissociate, The base dissociation constant (Kb) can similarly be
thus have leftover reactant molecules, thus have calculated as follows:
reversible reactions, thus have equilibrium. Kb = [HB][OH-]
[B-]
Exercises: Because weak acids and bases release only a small
1. If the pH of an acid is 4.7, what is its [H+]? amount of hydrogen or hydroxide ions respectively,
2. If the [OH-] of a base is 3.2 x 10-2, what is its the term percent ionization (%I) is used to compare
pOH? how much ions are released from the original
3. What is the hydrogen ion concentration of an acid/base.
impure water sample with a pH of 10.48?
4. If the negative logarithm of the hydroxide ion %I = [H+] or [OH-]
concentration of an acid is 11.23, find [OH-] [HA] or [B-]

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terms of pOH to 0.12M acid solution alone?
Exercises: pKa = 9.22
1. The Ka of phosphoric acid at is 7.2 x 10-3. Find
its pKa. E. BUFFERS AND THE HENDERSON-HASSELBACH
2. The Kb of methylamine is 4.4 x 10-4. Find its FORMULA
pKb. Buffers - systems that limit drastic changes in pH by
3. If a 0.19M base has a pH of 10.88, find its Kb. absorbing produced free hydrogen or hydroxide ions
Find %I. within themselves.
4. If the hydrogen ion concentration of a 0.77M Buffers are created by mixing an acid and its
weak acid is 1.32 x 10-4, what is its pKa? conjugate base. The solution containing these two
will have a specific pH different to the pH of any
b. Dissociation constants and Ion concentrations: Ka, one of them (somewhere in between).
Kb, Kw, [H+], [OH-] and their negative logarithms Difference in pH of the buffer to its components is
Because the conjugate acid or base in the ionization key to finding the concentration of buffer when
of an acid or base is accompanied with either a acid concentration is given and vice-versa.
hydrogen ion or a hydroxide ion, by getting the Ka or The Henderson-Hasselbalch equation can be used to
Kb, we can get the molarity of either H+ or OH- determine buffer component ratios, utilizing the
produced, and ultimately the pH and pOH. differences in pH of buffer and its component
acid/base.
Exercises:
1. If the Kb of Diethylamine is 8.6 x 10-4, what is pH = pKa + log[A-]
its pKb? [HA]
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 Exercises:
10-10, should have a Kb of what? 1. What is the pH of a 0.2M NH3/NH4Cl buffer?
4. If a 1M formic acid has a pKa of 3.77, find its 2. Find the ratio of an acetic acid/sodium
Kb and %I [H+]. acetate if the pH is 4.63. (pH acetic acid = 4.74).
5. A 0.75M monoprotic acid has a [H+] of 2.3 x If 0.25M acetic acid was used, how many moles
10-12. Find its Ka. of sodium acetate was used?
6. Given that urea has a Kb of 1.5 x 10-14, find its 3. If the the pH of a secondary phosphate buffer
pKa. is 12.34, what is the ratio of acid to conjugate
7. Ethylamine has a Kb of 5.6 x 10-4. Find its pOH. base? (pH secondary phosphate = 12.38)
8. Benzoic acid has a Ka of 6.5 x 10-5. Find its 4. A lactic acid buffer contains equal amounts of
hydroxide ion concentration and pOH. acid and conjugate base. If its Ka is 1.4 x 10-4,
9. A 0.35M base has a pOH of 4.24. Find its OH- what is its pH?
concentration, Kb, pKb, pKa, Ka, H+ concentration,
pH and %I [OH-].
SUB-PROPER #2 IONS AND PRECIPITATES:
D. COMMON-ION EFFECT SOLUBILITY
In pure weak acid solution (consider an acid first), the
Ka will be equal to the product of the hydrogen and A. DEFINITION AND CONCEPTS
conjugate base. If more conjugate base is added, the A solution is a homogenous mixture that consists of a
equilibrium will have to shift to the direction of the solute and solvent. The process by which the solute
acid, because of Le Chateliers principle. successfully dissolves in solvent is solvation/
Ex. A 0.5M acetic acid mixed with 0.1M sodium dissolution.
acetate should have what difference in pH compared
to that of the acid alone? Ka = 1.8 x 10-5 Solubility is highly dependent on polarity and energy.
Ka = [H+][A]/[HA] Polarity is the chemical basis of solubility that uses
1.8 x 10-5 = x2/0.5 x the dipoles of the solute and solvent to predict
*remove x if the constant is less than 10-4 whether solvation will take place or not. Energy is
= 3 x 10-3M H+, pH is 2.5 for acetic acid alone important since even in physical interactions, enough
1.8 x 10-5 = x(0.1)/0.5 energy must be used to overcome the intermolecular
= 9 x 10-5, pH is 4.04 forces between like particles.
There is 1.54 units in pH difference.
B. Ksp: SOLUBILITY CONSTANT
Exercises: Much like equilibrium constants, the same formula
1. A 0.25M acetic acid mixed with 0.1M of its goes to calculating the constant for solutions.
conjugate base has how much difference in Specifically, the product is/are the ions, while the
terms of %I to 0.25M acetic acid alone? Ka = 1.8 reactant is the solute.
x 10-5
2. If a 0.12M acid solution contains 0.032M of Ksp = Product of ions
its conjugate base, what is the difference in
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Recall that in heterogenous equilibrium, solid as Q. Because the target salt would have its own ksp, Q
products have a concentration equivalent of 1. Thus, and ksp can be compared:
if we add the solute, the denominator would simply
be 1. If Q > Ksp, precipitation, supersaturation occurs
NOTE: If an ion has a coefficient, such will be used as and will proceed the reduction of products.
both coefficient and exponent for the particular ion. If Q = Ksp, no precipitation, saturation occurs,
Ex. AB <-> A + 2B, then Ksp = [A][2B]2 equilibrium is achieved and reaction progress
stops.
Exercises: If Q < Ksp, no precipitation, unsaturation occurs
1. CaF2 dissolves into equal portions of calcium and will proceed the addition of products.
and fluoride ions. Find the Ksp if each ion has a
concentration of 6.24 x 10-6 M. Ex. If 0.01M NaOH is added to a liter of 0.1M CuCl2,
2. If cuprous hydroxide dissociates into one will Cu(OH)2 precipitate? Ksp = 1.6 x 10-19
cuprous ion and two hydroxide ions. If its Ksp is Resultant molarities:
2.2 x 10-20, then what is the concentration of MNaOH = (10)(0.01)/1010 = 9.9 x 10-5 M
MCuCl2 = (1000)(0.01)/1010 = 9.9 x 10-3 M
cuprous and hydroxide ions?
Q = [Cu][OH]2 = 9.7 x 10-11; Q>Ksp, thus precipitate will form

C. MOLAR SOLUBILITY Exercises:


Molar solubility is defined as the number of moles of 1. If PbCl2 has a ksp of 1.7 x 10-5, will a precipitate
salt that a liter of solution can handle before it form if 3g of PbBr2 is added to a liter of 0.77g of
becomes saturated. (n/L or M) NaCl? MM PbBr2 = 367.2; MM NaCl = 58
Solubility is considered as the amount of grams of 2. What if 0.2M of 250mL PbBr2 was used in
ions produced that can saturate a liter of solution. problem #1?

Ex. Find molar solubility, Ksp and solubility of AgBr if


this salt saturates a liter of solution with 1.65 x 10-4 References:
grams. MM = 187.8 g/n 1. Brown, T.L., LeMay, H.E., Bursten, B.E. (2004).
Molar solubility = 8.8 x 10-7 M AgBr Chemistry: The Central Science Ninth Edition. San
Ksp = 7.7 x 10-13 Francisco: Pearson Education, Inc.
Solubility = 1.65 x 10-4 g/L Ag+ and Br- 2. McMurry, J. (2007). Organic Chemistry: A Biological
Exercises: Approach. Belmont, CA: Thomson Brooks/Cole.
1. If barium sulfate dissociates into barium and 3. UST Faculty of Pharmacy Department of
sulfate ions, find molar solubility and solubility Biochemsitry. Laboratory Manual in General
if the given mass to saturate the solution is 2.5 x Chemistry. University of Santo Tomas.
10-3 g per liter. MM barium sulfate = 233 g/n 4. Boyer, R. (2005). Concepts in Biochemistry Fifth
2. Use the exercise problem #2 for Ksp to find Edition. New York: John Wiley and Sons, Inc.
molar solubility and solubility. MM cuprous 5. Burdge, J. (2009). Chemistry. New York: McGraw
hydroxide = 97.5 g/n Hill, Inc.
6. Silberberg, M.S. (2009). Chemistry: The Molecular
D. COMMON-ION EFFECT Level of Matter and Change Fifth Edition. New York:
McGraw Hill, Inc.
In a salt solution that is saturated, the Ksp is equal to
7. Gregorio, E.B. (2009). Lecture notes in Chemistry.
the product of the ions produced. If one of the two
HS Chemistry. University of Santo Tomas High
ions (usually the anion) is added, the equilibrium will
School. Espana, Manila
have to shift to the direction of the salt, because of Le
8. Manansala, M.E.J. (2010). Lecture notes in
Chateliers principle. The other ion would have to
Pharmaceutical Chemistry 1. University of Santo
change quantity to retain the Ksp.
Tomas.
Exercise: 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?

E. 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
SLRM2015 | 8
Chemistry Review Group
ANSWER KEY Common-ion effect
1. 0.83% difference in %I [H+]
Rate of reactions 2. 3.58 difference in pOH
1. 0.0018 M/s
2. 0.0036 M/s Buffers
1. 9.25 (where pKa = pH)
Rate law: 2. 0.78:1 ; 0.195 moles
R = k[A]2[B] 3. 0.91: 1
K = 240 4. 3.85
R = 0.277 M/s
Ksp
Reaction mechanisms 1. 3.43 x 10-13
1. R = k[N2O] 2. 8.15 x 10-8 M Cupric ions, 2.17 x 10-21 M
2. R = (k1/k2)k3[A][B] or k[A][B] hydroxide ions

Keq Manipulation Molar solubilities


1. 1.67 x 105 1. 1.07 x 10-5 n/L; 2.49 x 10-3 g/L
2. 0.0133 2. 1.48 x 10-10 n/L; 1.45 x 10-8 g/L

Le Chateliers Principle Common-ion effect


1. Carbonic acid products will increase Chloride precipitates first; iodide has greatest molar
2. The reaction will shift to the left solubility.
3. The reaction will shift to the reactants side
at pressure increase; pressure decrease Precipitate prediction
causes shift towards the products 1. Q = 1.08 x 10-4; Yes
2. Q = 4.25 x 10-4; Yes.
Qc
Qc = 15.18
Qc < Keq
Formation of more products will happen

pH/pOH
1. 2.00 x 10-5 M
2. 1.49
3. 3.1 x 10-11 M
4. 5.89 x 10-12 M

Conjugates
1. Ammonium (NH4+)
2. Acid - KHSO4
Conjugate base = K2SO4
Base = K2CO3
Conjugate acid = KHCO3

Ka/Kb
1. 2.14
2. 3.36
3. 3.02 x 10-6; 0.399%
4. 7.64

1. 3.07
2. 7.94 x 10-5
3. 7.69 x 10-5
4. 5.89 x 10-11; 1.30%
5. 7.05 x 10-24
6. 0.175
7. 1.63
8. 1.24 x 10-12; 11.91
9. 5. 75 x 10-5 M; 9.45 x 10-9, 8.02, 5.98, 1.05 x
10-6 M; 1.02 x 10-3M; 2.99; 1.64 x 10-2 %

SLRM2015 | 9