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SLRM2012

Prepared by:
Chemistry Review Group/ Pharmacy Review Group Scholia Tutorial Club UST Faculty of Pharmacy

SLRM2012

PREREQUISITE
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 otherwise termed as chemical reactions. Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

PREREQUISITE
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
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PREREQUISITE
Qualitative and Quantitative Chemistries are combined into what is known as Analytical Chemistry Pharmaceutical Chemistry branch of pharmacy and chemistry that deals with the use of the properties and changes of significant compounds to bring out a certain use in the pharmacy practice.
Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

PREREQUISITE
Concentration Expressions Recall that the concentration (amount of solute present) in a solution can be expressed in the following ways: Molarity = g solute/ mm solute (L solvent) Molality = g solute/ mm solute (kg solvent)

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PREREQUISITE
Normality = Equivalents solute/ L solvent Also, dilution is important in case the concentration is meant to be altered. M1V1 = M2V2

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SLRM2012

REVIEW PROPER #1: COLLIGATIVE PROPERTIES OF SOLUTIONS


Colligative adj. dependent on quantity instead of nature Colligative properties are specific for solutions, which depend on the number of solute particles instead of their nature.

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REVIEW PROPER #1: COLLIGATIVE PROPERTIES OF SOLUTIONS


1. Vapor Pressure the pressure exerted by the vapor being given off by the liquid at a given temperature Rule: The lowering of vapor pressure of a solvent is equal to the product of mole fraction solute and vapor pressure of pure solvent. P = P x MF solute

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REVIEW PROPER #1: COLLIGATIVE PROPERTIES OF SOLUTIONS


Ex. A solution contains 1.75 moles of sucrose in a liter of water. What is the vapor pressure lowering of the solvent? What is the vapor pressure of the solution? P = 23.72 C P = P x MF solute Where : P = vapor pressure lowering; and P = vapor pressure of solvent P = P (Vp solution) P (Vp solvent) MF solute = moles solute/ moles solution * moles solution = moles solute + solvent
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SLRM2012

REVIEW PROPER #1: COLLIGATIVE PROPERTIES OF SOLUTIONS


Moles solvent = 100g/ 18 = 55.56 moles water Moles solution = 57.31 MF solute = 1.75/57.31 = 0.031 P = 23.72(0.031) = 0.727 mmHg

Vapor pressure soln = P - lowering = 23.72 0.727 = 23.0 mmHg


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REVIEW PROPER #1: COLLIGATIVE PROPERTIES OF SOLUTIONS


2. Boiling Point Elevation the pressure exerted by the vapor being given off by the liquid at a given temperature Rule: The boiling point elevation of the solvent is directly proportional to the molecular concentration of the solution. Tb = kb(m) Where kb = molal bpt constant m = molality Tb = bpt elevation Tb = Tb (Bpt. Solution) Tb (Bpt. Solvent)
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SLRM2012

REVIEW PROPER #1: COLLIGATIVE PROPERTIES OF SOLUTIONS


Ex. What is the boiling point elevation of 60.0g of water that contains 2.00g of glycerol, C3H5(OH)3? Molality = 0.362, Bpt constant of water = 0.51C Tb = kb(m) Tb = (0.51C)(0.362) = 0.185C Thus, if bpt solvent is 100C, the bpt of the entire solution becomes 100.185C.
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REVIEW PROPER #1: COLLIGATIVE PROPERTIES OF SOLUTIONS


3. Freezing Point Depression point where liquid turns into solid. Rule: The freezing point depression is directly proportional to the molal concentration of the solution. Tf = kf(m) Where Tf = Fpt. Depression m = molality kf = molal fpt constant Tf = Tf (Fpt. solvent) - Tf (Fpt. Solution)
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REVIEW PROPER #1: COLLIGATIVE PROPERTIES OF SOLUTIONS


Ex. Calculate the freezing point depression of 0.46 molal diphenyl-naphthalene solution in 200g of benzene. Fpt = 5.5C Constant = 5.12C T = (5.12C)(0.46m) = 2.3C T = Fpt - T = 5.5C - 2.3C = 3.2C

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REVIEW PROPER #1: COLLIGATIVE PROPERTIES OF SOLUTIONS


4. Increase in Osmotic Pressure () pressure that is required to stop osmosis = MRT Where M = molarity R = gas constant T = temperature (K)

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REVIEW PROPER #1: COLLIGATIVE PROPERTIES OF SOLUTIONS


Ex: What is the osmotic pressure of a selection at 29.0C that contains 15.0g of glucose in 80.0mL solution? = MRT = [150g / (180g/n x 0.08L)] x 0.0821L-atm/mol-K x 302K = 25.8 atm

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END OF REVIEW PROPER.

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REVIEW PROPER #2: CHEMICAL KINETICS


A. RATE: DEFINITION AND DETERMINATION Rate any quantity divided by time. (Q/t) Rate of Reaction mathematically is defined in a way that the quantity given is the amount of compound (product or reactant) over time. Reactants are used up, and become lesser overtime. Therefore their rate should have a negative sign.
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REVIEW PROPER #2: CHEMICAL KINETICS


Products are formed, and become greater overtime. Therefore their rate should have a positive sign. This sensible argument is justified by the basic law of conservation of mass. Q = Amount of reactant (usually expressed in concentrations as molar [M])

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REVIEW PROPER #2: CHEMICAL KINETICS


(If we use the reaction A + B ---> AB, and use AB as Q): Rate of reaction of product = Q/t = AB(in M) / t(in S) * SINCE AB IS A PRODUCT, ITS RATE SHOULD HAVE A POSITIVE SIGN. Therefore, if we get the rate of any product (either A or B), Rate of reaction of reactant = Q/t = (-) A or B(in M) / t(in S)
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REVIEW PROPER #2: CHEMICAL KINETICS


Exercise: NO2 is produced at a rate of 0.0072 M/s. 2N2O5 ---> 4NO2 + O2 Find rate of oxygen production. Find rate of N2O5 usage.

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REVIEW PROPER #2: CHEMICAL KINETICS


B. CONCEPTS AND CORRESPONDING FACTORS AFFECTING RATE

I. Rate Law: Factor of Concentration The Rate Law is a core of Chemical kinetics simply because it is the single most essential concept that explains the speed of the feasible reaction. Concentration the quantity of matter in a given mixture.
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REVIEW PROPER #2: CHEMICAL KINETICS


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.

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REVIEW PROPER #2: CHEMICAL KINETICS


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 have their own order (first order, second order) and the overall rate law has also an order (the combination of all individual orders) Ex. Rate = k[A]2[B] Individual orders: 2nd order for A; 1st order for B Overall order: 3rd order
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REVIEW PROPER #2: CHEMICAL KINETICS


Exercise: Given the following: NO + H2 -> products
Trial NO [M] H2[M] Rate [m/s]

1 2 3

5 x 10-3 10 x 10-3 10 x 10-3

2 x 10-3 2 x 10-3 4 x 10-3

1.2 x 10-5 5 x 10-5 10 x 10-5

Give the rate law, orders of reactants, overall order, constant k. Solve for the rate if NO = 0.031M, andH2 = 1.2 M
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REVIEW PROPER #2: CHEMICAL KINETICS


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. Temperature amount of thermal energy possessed by a body of matter. Orientation position of two or more interacting bodies of matter.
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SLRM2012

REVIEW PROPER #2: CHEMICAL KINETICS


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 a chemical reactions (Although a physical one may take place). - The factors that decide whether the collision is effective are the two factors under this theory:
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REVIEW PROPER #2: CHEMICAL KINETICS


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. (EA)

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REVIEW PROPER #2: CHEMICAL KINETICS

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SLRM2012

REVIEW PROPER #2: CHEMICAL KINETICS


2. Orientation colliding particles must be properly oriented in order to amplify the attraction between each other, making more possible the achievement of EA.

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REVIEW PROPER #2: CHEMICAL KINETICS


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 (refer to Proper #3) 4. It usually acts by physical forces, forming a temporary complex with the target reactant to stabilize transition state. Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

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REVIEW PROPER #2: CHEMICAL KINETICS

Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

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REVIEW PROPER #2: CHEMICAL KINETICS


Catalysts can be generally categorized into two: Heterogenous and Homogenous. Heterogenous catalysts exist in a phase different from that of the reactant (metal catalyst in gas production), while homogenous catalysts exist in a phase same with that of the reactant (liquid catalyst in aqueous/liquid reactant).

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REVIEW PROPER #2: CHEMICAL KINETICS


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.

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REVIEW PROPER #2: CHEMICAL KINETICS


C. REACTION MECHANISMS: LOGICAL LEVEL OF REACTION STUDIES Reaction mechanisms explain specifically what happens to reactants in a multi-step reaction until they become products.

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REVIEW PROPER #2: CHEMICAL KINETICS


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.

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SLRM2012

REVIEW PROPER #2: CHEMICAL KINETICS


Anatomy of a simple multi-step (2-step) reaction: A + B ---> C + D D + E ----> F + B A + E ---> C + F
A, E = reactants F, C = products D = intermediate B = catalyst

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REVIEW PROPER #2: CHEMICAL KINETICS


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, Palldium NOTE: Catalysts and intermediates cannot participate in the rate law as they did not participate per se in the reaction. Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

REVIEW PROPER #2: CHEMICAL KINETICS


II. Reaction mechanisms and the Rate Law The integration of chemical kinetics and reaction mechanisms relies on three general rules: The individual steps must add up to the overall balanced equation. The individual steps are bound to all rules set up by chemical kinetic principles; and The reaction mechanism is derived from the rate law, not the other way around.
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SLRM2012

REVIEW PROPER #2: CHEMICAL KINETICS


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.

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REVIEW PROPER #2: CHEMICAL KINETICS


Rate-determining step (RDS) the slower/slowest individual step of a reaction mechanism. It can be concretized through the rate law of the multi-step reaction. Thus, the concentration of reactants in the RDS are the only ones considered in the entire reactions rate law. ex. 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 [NO] Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

REVIEW PROPER #2: CHEMICAL KINETICS


Exercises: 1. Give the rate law for the following reaction mechanism: N2O -----> N2 + O (slow) N2O + O ----->N2 + O2 2. Give the rate law for the following reaction mechanism: A + B <--> AB AB --->A + C (slow)
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END OF REVIEW PROPER.

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REVIEW PROPER #3: INTRODUCTION TO EQUILIBRIUM


A. DEFINITION Equilibrium - state wherein the amount of products and reactants stay the same in an equal reaction process. Unless products can return to the reactant compounds, equilibrium cannot happen because it only happens on reversible reactions. (Double arrow <-----> is used to denote a reversible reaction).
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REVIEW PROPER #3: INTRODUCTION TO EQUILIBRIUM


Equilibrium on reversible reactions are 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 (Kinetics, Rate). If the reaction is returned to progress, there will be changes to maintain equilibrium and the graph will deviate temporarily from a flat graph. Mathematical/quantitative study of equilibrium depends highly on equilibrium constants.
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REVIEW PROPER #3: INTRODUCTION TO EQUILIBRIUM

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REVIEW PROPER #3: INTRODUCTION TO EQUILIBRIUM


B. 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 (l) or partial pressures (g) of the reactantproduct mixture. The numerical representation of the ratio between products formed and reactants retained is shown by the equilibrium constant Keq.
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REVIEW PROPER #3: INTRODUCTION TO EQUILIBRIUM

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.
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REVIEW PROPER #3: INTRODUCTION TO EQUILIBRIUM


Notes: 1. The coefficient of the equation will serve as the exponent for the moles of the given species. 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 reactions charted against time or against reaction mechanisms. It aims to measure, not to dissect reaction. 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
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REVIEW PROPER #3: INTRODUCTION TO EQUILIBRIUM


C. 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
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SLRM2012

REVIEW PROPER #3: INTRODUCTION TO EQUILIBRIUM


Exercises: 1. If the equilibrium constant for the formation of ethenol 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?

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SLRM2012

REVIEW PROPER #3: INTRODUCTION TO EQUILIBRIUM


D. LE-CHATELIERS 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.

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REVIEW PROPER #3: INTRODUCTION TO EQUILIBRIUM


Concentration changes in one side of the reaction will cause the inverse change in the other side.

ex. 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.

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REVIEW PROPER #3: INTRODUCTION TO EQUILIBRIUM


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, any increase in temperature will shift the reaction toward the opposite side of the reaction, and any decrease in temperature will shift the reaction toward its side of the reaction.

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REVIEW PROPER #3: INTRODUCTION TO EQUILIBRIUM


Ex. 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.

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REVIEW PROPER #3: INTRODUCTION TO EQUILIBRIUM


Volume and Pressure factor applicable only to gases. The more numerous between reactants in products will have more volume. Thus, increasing pressure will decrease the volume on the greater side and causes a shift to that side; and vice-versa.

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SLRM2012

REVIEW PROPER #3: INTRODUCTION TO EQUILIBRIUM


Ex. 2A + 5C <-> 6F Reactants = 7 moles; Products = 6 moles If pressure is applied, the reaction will shift towards the left. If pressure is relieved, the reaction will shift towards the right.

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SLRM2012

REVIEW PROPER #3: INTRODUCTION TO EQUILIBRIUM


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. (refer to introduction to equilibrium). Inert gases and anything that is not used up or produced in the reaction will not affect the equilibrium as well.
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SLRM2012

REVIEW PROPER #3: INTRODUCTION TO EQUILIBRIUM

Exercises: 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 heat is increased in the equilibrated mixture, what will happen? 3. 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? Viceversa? Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

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REVIEW PROPER #3: INTRODUCTION TO EQUILIBRIUM


E. REACTIONS NEARING EQUILIBRIUM Reactions that will proceed to equilibrium but are not et there can be represented b finding the product of the concentration/partial pressures of the products formed so far. That product is called the Reaction quotient (Qc)

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REVIEW PROPER #3: INTRODUCTION TO EQUILIBRIUM


Several inferences can be made, using the basis of Le Chateliers 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

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SLRM2012

REVIEW PROPER #3: INTRODUCTION TO EQUILIBRIUM


Exercise: 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.

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END OF REVIEW PROPER.

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REVIEW PROPER #4: SPECIFIC EQUILIBRIUM


Can be divided into two sub-propers: 1. Water, Acid, and Base Equilibria (Kw, Ka, Kb, pH, pOH, their antilogs, %I) with common-ion effect and buffers 2. Solubility Equilibria (Ksp) with common-ion effect and the new ion product

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WATER, ACIDS, AND BASES


A. WATER, ACIDS, AND BASES: STRENGTH I. Review and Introduction a. Definitions
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.
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WATER, ACIDS, AND BASES


b. 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.
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WATER, ACIDS, AND BASES


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-]

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WATER, ACIDS, AND BASES


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) 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.
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WATER, ACIDS, AND BASES


Very important note: Strong acids and bases completely dissociate in water. All molecules of the acid/base are disintegrated into its constituent ions. Weak acids and bases dissociate only partially in water, and thus some of the acid/base still remains: therefore, equilibrium exists in weak acids/bases. Consequently, equilibrium constants for these weak acids/bases exist.
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WATER, ACIDS, AND BASES


Exercises: 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-]
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WATER, ACIDS, AND BASES


c. Conjugate acids and bases Conjugate adj. joined together; coupled. A conjugate acid is the acid minus a proton. (ex. H2CO3 is an acid; HCO3- is its conjugate acid). Inversely related, a conjugate base is a base plus a proton. (NH3 is a base; NH4+ is its conjugate base). Conjugates result from acid/base equilibrium reactions.
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WATER, ACIDS, AND BASES


Exercises: 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?

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WATER, ACIDS, AND BASES


II.kW: Autoionization of Water and Equilibrium 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).
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WATER, ACIDS, AND BASES


The reaction is as follows: H2O + H2O <-> H3O+ + OHThe Keq of water by 25 deg. C is 1.0 x 10-14. This is also called the ion-product constant for water (kW), 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. This is called the neutral pH.
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WATER, ACIDS, AND BASES


III. Ka and Kb: Acid/Base Dissociation Constants
a. 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 acid dissociation is the conjugate acid, while the reactant is obviously the original acid. Ka = [A-][H+] [HA]
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WATER, ACIDS, AND BASES


The base dissociation constant (Kb) can similarly be calculated as follows:

Kb = [HB][OH-] [B-]

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WATER, ACIDS, AND BASES


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-]


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WATER, ACIDS, AND BASES


Exercises (assume all acids and bases are monoprotic): 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?

Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

WATER, ACIDS, AND BASES


b. 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.
Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

WATER, ACIDS, AND BASES


Exercises (assume all acids and bases are monoprotic): 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 formic acid has a pKa of 3.77, find its Kb and %I [H+], considering it is 1M. 5. A 0.75M monoprotic acid has a [H+] of 2.3 x 10-6. Find its Ka. 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, considering it is 1M. 9. A 0.35M base has a pOH of 4.24. Find its OH- concentration, Kb, pKb, pKa, H+ concentration, pH and %I [OH-].
Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

WATER, ACIDS, AND BASES


IV. Common-ion effect on Acid-Base Equilibria 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 Chateliers principle.
Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

WATER, ACIDS, AND BASES


Ex. A 0.5M acetic acid mixed with 0.1M sodium acetate should have what difference in pH compared to that of the acid alone? 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 if 4.04 There is 1.54 units in pH difference.
Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

WATER, ACIDS, AND BASES


Exercises: 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
Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

WATER, ACIDS, AND BASES


V. Buffers and the Henderson-Hasselbach Formula Buffers are systems that limit drastic changes in pH by absorbing produced free hydrogen or hydroxide ions within themselves. This is achieved by mixing an acid with its conjugate base. These two buffer components will then have a specific pH different to the pH of each individual component. 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. Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

WATER, ACIDS, AND BASES


The Henderson-Hasselbach 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]

Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

WATER, ACIDS, AND BASES


Exercises: 1. What is the pH of a 0.2M NH3/NH4CL buffer? Kb NH3 = 1.8 x 10-5 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? Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

END OF REVIEW SUB-PROPER.

Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

IONS AND PRECIPITATES


i. Definition and concepts 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. 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.

Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

IONS AND PRECIPITATES


II. ksp: Solubility and Equilibrium 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

Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

IONS AND PRECIPITATES


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
Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

IONS AND PRECIPITATES


Exercises: 1. AB dissolves into equal portions of A and B ions. Find the Ksp if each ion has a concentration of 5.86 x 10-7 M. 2. If cupric hydroxide dissociates into one cupric ion and two hydroxide ions, and its ksp is 2.2 x 10-20, then what is the concentration of cuprous and hydroxide ions?
Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

IONS AND PRECIPITATES


III. Molar Solubility and 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.
Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

IONS AND PRECIPITATES


Ex. 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 Answers: 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 Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

IONS AND PRECIPITATES


Exercises: 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 = 233 g/n 2. Use the exercise problem #2 for Ksp to find molar solubility and solubility. MM = 97.5 g/n

Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

IONS AND PRECIPITATES


IV. Common-ion effect In a salt solution that is saturated, the ksp will be 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 Chateliers principle. The other ion would have to change quantity to retain the ksp.
Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

IONS AND PRECIPITATES


Exercise: Given that the solution will form a precipitate, the Ksp values for AgI, AgBr and AgCl 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 containining 0.05n of all these anions, which will precipitate first? Which has the greatest molar solubility?

Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

IONS AND PRECIPITATES


V. Precipitate and solubility prediction 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. Because the target salt would have its own ksp, Q and ksp can be compared:
Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

IONS AND PRECIPITATES


If Q > Ksp, precipitation, supersaturation occurs and will proceed the reduction of products. If Q = Ksp, no precipitation, equilibrium is achieved and reaction progress stops. If Q < Ksp, no precipitation, unsaturation occurs and will proceed the addition of products.

Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

IONS AND PRECIPITATES


Ex. 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
Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

IONS AND PRECIPITATES


Exercises: 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?

Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

SLRM2012

END OF REVIEW SUB-PROPER. END OF REVIEW PROPER.

END OF REVIEW.
Scholia Tutorial Club, University of Santo Tomas Faculty of Pharmacy

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