Stuff We Should Remember from Gen Chem Which

Has A Useful, But Ugly, Connection to AP Chem

Strong electrolytes ionize completely in water. Weak electrolytes ionize incompletely in water. Strong and weak should not be used to represent concentration, or molarity.

 Binary acids
Composed of hydrogen and some nonmetal Generic formula HX or H2X Strength of binary acids tend to increase across a period and increase down a group

Oxyacids Memorize the strong acids (HCl, HBr, HI, HNO3, H2SO4, and HClO4) and strong bases (all hydroxides or oxides of group 1 and 2 metals except Mg and Be)
Composed of hydrogen, oxygen, and some other element Strength of oxyacids tend to increase across a period and increase up a group For oxyacids with the same other element, more oxygens produce a stronger acid

Acid-Base Equilibria

A Bit of Background
Before we dive right in to acid-base equilibria, lets review general properties of acids and bases. 3 general definitions:
Arrhenius Bronsted-Lowry Lewis

Arrhenius Definitions
An acid is a substance that produces H+ (or H3O+) ions in water. A base is a substance that produces OH- ions in water. A neutralization reaction occurs when an acid and a base combine to form water and a salt. These definitions suck because not all of our observations are supported by these definitions.

Bronsted-Lowry Definitions
An acid is a substance that donates a proton. A base is a substance that accepts a proton. Any acid-base reaction is considered an equilibrium, having both a forward and reverse reaction. Because of this, the concept of conjugate acid-base pairs is important.

Conjugate Acid-Base Pairs

Formic acid, a weak acid, forms an equilibrium in water. HCHO2 (aq) + H2O H3O+ (aq) + CHO2- (aq) In the forward reaction, formic acid donates a proton to the water molecule, hence its termed the acid and water is termed the base. But, what about the reverse reaction? Hydronium donates a proton to the formate ion, so cant it also be called the acid? Thats confusing. Hydronium is called the conjugate acid. Because, in the reverse reaction, formate accepts the proton, it is called the conjugate base. IN GENERAL, THE ACID MEMBER OF A CONJUGATE PAIR HAS ONE MORE H+ THAN THE BASE MEMBER. CONVERSELY, THE BASE MEMBER OF A CONJUGATE PAIR HAS ONE LESS H+ THAN THE ACID MEMBER.

Example 1
Write the conjugate base of nitric acid, HNO3. NO3 Write the conjugate acid of hydrogen sulfate, HSO4-. H2SO4

Your Turn 1
Write the formula for the conjugate base of:
Water Phosphoric acid

Write the formula for the conjugate acid of:

Sulfate Ammonia

Important Vocabulary
What if a single substance can act as either an acid or a base? We call this substance amphoteric, or amphiprotic. Examples include molecules or ions. Water is the most popular amphoteric substance which explains why we love to do acid-base chemistry in solution.

Who Cares About Any of This?

All of this mess brings us to two useful concepts:
1.) The stronger a Bronsted-Lowry acid is, the weaker its conjugate base is and vice versa. 2.) The position of an acid-base equilibrium favors the weaker acid and base.

Example 2
Given the fact that acetic acid is known to be a stronger acid than the hydrogen sulfite ion, predict the position of the equilibrium in the reaction below: HSO3- (aq) + C2H3O2- (aq) HC2H3O2 (aq) + SO32- (aq) In this case, the equilibrium will lie to the left because thats where the weaker acid and base are found.

Your Turn 2
Given that hydrogen sulfate is a stronger acid that hydrogen phosphate, determine the position of the equilibrium in the reaction below: HSO4- (aq) + PO43- (aq) SO42- (aq) + HPO42- (aq)

Strength of Bronsted-Lowry Acids and Bases

The strength of a Bronsted-Lowry acid refers to its ability to donate a proton to a base.
H3O+ is the strongest acid we will ever find in aqueous solution

The strength of a Bronsted-Lowry base refers to its ability to accept and bind a proton.
OH- is the strongest base we will ever find in aqueous solution

Lewis Definitions
An acid is any ionic or molecular species that can accept a pair of electrons in the formation of a coordinate covalent bond. A base is any ionic or molecular species that can donate a pair of electrons in the formation of a coordinate covalent bond. Neutralization is the formation of a coordinate covalent bond between the donor (base) and acceptor (acid).

Substances That Can Act as Lewis Acids or Bases

Lewis Acids
Substances with incomplete valence shells Substances with complete valence shells, but with multiple bonds that can be shifted to accommodate more electrons Substances with central atoms capable of holding extra electrons (generally those jerks in periods 3 through 7)

Lewis Bases
Substances with completed valence shells and unshared pairs of electrons

It is often helpful to draw the Lewis structures when identifying Lewis acids and bases.

Example 3
Identify the Lewis acid and base in the reaction: NH3 + H+ NH4+

Lewis acid = H+ Lewis base = NH3

Your Turn 3
Identify the Lewis acid and base in the reaction: Ag+ + 2NH3 Ag(NH3)2 +

Homework
Pages 839-843 #1, 3, 7, 33, 69

The Nuts and Bolts of Acid-Base Equilibria

Lets start with water since it can be either an acid or a base (remember this as amphoteric, right?) Water is in equilibrium with itself: H2O (l) + H2O (l) H3O+ (aq) + OH- (aq) This is called the self-ionization, or autoionization, of water. Can you write the equilibrium expression for this reaction?

 Water is special. Because of its importance in acid-base reactions, we give its equilibrium constant a special symbol, Kw. This is called the ion product constant of water or the autoionization constant for water. Kw = [H3O+][OH-] = 1.0 x 10-14 @ 25C

In neutral solution, [H3O+] = [OH-] In acidic solution, [H3O+] > [OH-] In basic solution, [H3O+] < [OH-] This is fine and dandy except it is usually very difficult to measure the concentration of hydronium and hydroxide ions in the laboratory. S.P.L. Sorenson, a Danish chemist, saved the day.

The pH Scale
To make comparisons of teeny tiny concentration values much easier, we can use the pH scale. pH = -log[H+] or log[H3O+] Or [H+] = [H3O+] = 10-pH In neutral solution, pH = 7 In acidic solution, pH < 7 In basic solution, pH > 7

P Notation
Sorensons pH scale became so popular that it has been adapted to quantities other than [H+]. We can calculate pOH and pKw as well. pOH = -log[OH-] pKw = -logKw A useful relationship becomes pH + pOH = pKw = 14 @ 25C

Example 1
Water draining from old coal and mineral mines often has pH values of less than 4.0. What are the pOH, [H+], and [OH-] in an acid mine drainage sample that has a pH of 4.25? pOH = 9.75 [H+] = 5.62 x 10-5 M [OH-] = 1.78 x 10-10 M

Your Turn 1
Find the values of [H+] and [OH-] that correspond to each of the following values of pH. State whether each solution is acidic, basic, or neutral.
2.90 10.81 4.61

Acid Dissociation Constants, Ka

We can treat acids like we do water and set up their equilibrium expression to quantify their equilibrium constants. HA (aq) + H2O (l) H3O+ (aq) + A- (aq) Ka = [H3O+][A-] which abbreviates to [H+][A-] [HA] [HA] For weak acids, Ka < 1; reactants are favored and equilibrium lies to the left For strong acids, Ka > 1; products are favored and equilibrium lies to the right

pKa
We can write the pKa of an acid as: pKa = -logKa Strong acids have small pKa values and vice versa.

Base Dissociation Constants, Kb

We can treat bases, either strong or weak, the same way. B (aq) + H2O (l) HB+ (aq) + OH- (aq) Kb = [HB+][OH-] [B] For weak bases, Kb < 1; reactants are favored and equilibrium lies to the left For strong bases, Kb > 1; products are favored and equilibrium lies to the right

pKb
We can write the pKb of a base as: pKb = -logKb Strong bases have small pKb values and vice versa.

An Illustration
Formic acid, HCHO2, is a typical weak acid that ionizes according to the equation: HCHO2(aq) + H2O (l) H3O+ (aq) + CHO2- (aq) Ka = The conjugate base of formic acid, formate, reacts with water according to the equation: CHO2- (aq) + H2O (l) HCHO2 (aq) + OH- (aq) Kb =

 If we multiply the expressions for Ka and Kb, we get:

= [H3O+][OH-] = Kw

Thus, For Any Acid-Base Pair

Ka x Kb = Kw Or pKa + pKb = pKw = 14 @ 25C There is an inverse relationship between the strengths of the acid and base members of a conjugate pair. Sound familiar?

Example 2
The methylammonium ion CH3NH3+ has a Ka of 2.3 x 10-11. What is the Kb for the base methylamine?

4.3 x 10-4

Your Turn 2
The value of Kb for the CHO2- ion is 5.5 x 10-11. What is the value of Ka for HCHO2?

Homework
Pages 840-841 #9, 12*, 15, 23, 27, 29

*If you can show me how you correctly answered #12, I will give you candy.

Back to RICE Tables

So far, weve scratched the surface of acid-base equilibria. Today, well focus on calculating Ka and Kb values from initial concentrations of acids or bases and the pH of the solution. Well also calculate equilibrium concentrations and pH values if were given Ka or Kb and initial concentrations. Table 17.3 on page 808 of your text is your new best friend!

Steps to Solving Acid-Base Equilibria Problems

1.) Write the equation for the ionization of the acid or base. 2.) Write the Ka or Kb expression. 3.) Draw a RICE table. 4.) Use the pH (or pOH) to calculate the [H+] (or [OH-]) concentration AT EQUILIBRIUM. 5.) Solve the RICE table and answer all parts of the question.

Example 1
Lactic acid (HC3H5O3) gives sauerkraut its tartness. In a 0.100 M solution, the pH is 2.44 at 25C. Calculate the Ka and pKa for lactic acid at this temperature.

Your Turn 1
A 0.055 M butanoic acid solution has a pH of 2.72 at 25C. Determine Ka and pKa for butanoic acid (CH3CH2CH2CO2H).

Example 2
Calculate the pH of a 0.100 M solution of hypochlorous acid.

Your Turn 2
Calculate the pH of a 0.020 M solution of benzoic acid.

Your Turn 3
What is the pH of a 0.0010 M solution of formic acid? What is the equilibrium concentration of formic acid?

Your Turn 4
What are the equilibrium concentrations of HF, F- ion, and H3O+ ion in a 0.015 M solution of HF? What is the pH of the solution?

Homework
Complete Acid-Base Equilibria worksheet

Polyprotic Acids
Have you noticed that most of the acids weve looked at thus far have contained one acidic hydrogen, like HCl and HNO3? These are called monoprotic acids because they have the ability to donate only one hydrogen according to the Bronsted-Lowry definition.

 What about an acid like H2CO3? It has two hydrogens to donate, so we call it a diprotic acid (acids with more than 2 hydrogens to donate are called polyprotic acids). However, each hydrogen is donated separately and, therefore, has its own Ka value. We denote them as Ka1 and Ka2.

Check It Out
H2CO3 + H2O H3O+ + HCO3Or H2CO3 H+ + HCO3 Ka1 = = 4.3 x 10-7 HCO3- + H2O H3O+ + CO32Or HCO3- H+ + CO32 Ka2 = = 5.6 x 10-11

 What do you notice about the relative values of Ka1 and Ka2? Each ionization contributes to the overall [H+] in the solution; however, one ionization has a greater impact on the [H+]. Which step is it? How come?

A Gross, But Useful, Oversimplification

Because Ka1 is so much larger (relatively speaking) than Ka2, we can assume that all the H+ in an acid solution comes from the first ionization. This means that we can essentially neglect the change in concentration for the diprotic acid; the equilibrium concentration will be essentially equivalent to the initial concentration and the [H+] at equilibrium will be the same for all successive ionizations. In addition, the equilibrium concentration of the conjugate base for the second ionization will be equivalent to Ka2. Let me show you This is not entirely true, but it makes our lives much easier.

Example 1
Calculate the equilibrium concentrations of carbonic acid, hydrogen ion, hydrogen carbonate, and carbonate ion in a solution of 0.040 M H2CO3 as well as the pH of the solution. Ka1 = 4.3 x 10-7 Ka2 = 5.6 x 10-11

Your Turn 1
Calculate the [H+] and [C6H6O62-] at equilibrium in a solution of 0.10 M H2C6H6O6 as well as the pH of the solution. Ka1 = 8.0 x 10-5 Ka2 = 1.6 x 10-12

Homework
Pgs. 842-843 #65 and 67

Percent Ionization
Recall that weak acids and bases DO NOT ionize completely in water. We can calculate the percent ionization of the substance. In general, the percent ionization of a substance allows us to determine its relative strength. Higher percent ionization means less weak acid (relatively speaking).

Percent Ionization
Percent ionization is calculated as I moles ionized per liter I x 100% I moles available per liter I Another way to look at this is I [X] from RICE table I x 100% I Molarity of X given in problemI

Example 1
Calculate the percent ionization of 1.0 M acetic acid.

Your Turn 1
Calculate the percent ionization of 0.100 M acetic acid.

Other Ways to Use % Ionization

In addition to calculating percent ionization as we just did, we can use a known percent ionization to calculate at least one of the equilibrium concentrations required in a problem. Remember that [X] is equivalent to your percent ionization! Use percent ionization in your C row of your RICE table!

Example 2
In a 0.100 M methylamine solution, CH3NH2, only 6.4% of the base is ionized. What are Kb and pKb of methylamine?

Your Turn 2
In a 0.0100 M solution of butanoic acid, HC4H7O2, 4.0% of the acid is ionized. Calculate Ka and pKa of butanoic acid.

Homework
Complete Percent Ionization Worksheet.

Buffers
A buffer is a solution consisting of mixed solutes which allow the solution to resist large changes in pH when small amounts of strong acid or strong base are added to it. A buffer usually consists of a weak Bronsted acid and its conjugate base. KNOW THIS! THE AP PEOPLE WANT TO TRICK YOU!
If the acid is molecular, the conjugate base is supplied by a soluble salt of the acid.

Common Buffer Systems

Carbonic acid (H2CO3) and bicarbonate ion (HCO3-) in your blood Ammonium (NH4+) and ammonia (NH3) Acetic acid (CH3COOH) and sodium acetate (NaCH3COO)

How Buffers Work

In order to resist changes in pH, a buffer must be able to neutralize a strong acid or a strong base that is added to a solution. It does this twofold: one member of the buffer system neutralizes H+ and the other member of the system neutralizes OH-.
Which member could neutralize H+, the acid or the conjugate base? Which member could neutralize OH-, the acid or the conjugate base?

Calculate the pH of a Buffer System

We can use a RICE table and some of our simplifications to calculate the pH of a buffer system consisting of two solutes.

Example 1
Calculate the pH of a buffer solution containing both 0.110 M NaCH3COO and 0.090 M CH3COOH.

Your Turn 1 (Think About It!)

One liter of buffer solution is made by dissolving 100.0 g of acetic acid and 100.0 g sodium acetate in water. What is the pH of the buffer solution?

Preparing Buffers With a Desired pH

The [H+] of a buffer is controlled by both Ka and the ratio of concentrations (or moles) of the members of the acid-base pair. [H+] = Ka [HA] or [H+] = Ka molHA [A-] molA-

Goldilocks and the Three Bears Analogy

In order to be a buffer system, the mole (or molarity) ratio of ACID to BASE must be between 0.1 and 10.
If the ratio is too low, added base will cause large pH swings. If the ratio is too high, added acid will cause large pH swings. Ratios between 0.1 and 10 are considered just right.
In order to successfully prepare a buffer system, pH = pKa + 1

Example 2
Is it possible to prepare a buffer solution with pH 5.00 from acetic acid and sodium acetate? If so, what is the correct mole ratio that will result in pH 5.00? How many moles of sodium acetate must be added to 1.0 L of a solution that contains 1.0 mol acetic acid to prepare the buffer?

Your Turn 2 (Think About It!)

Is it possible to prepare a buffer solution with pH 3.90 from formic acid and sodium formate? If so, what is the correct mole ratio that will result in pH 3.90? How many grams of sodium formate must be added to a solution that contains 0.10 mol formic acid to prepare the buffer?

The Henderson-Hasselbalch Equation

Sometimes, well want to figure out exactly how much the pH of a buffer solution will change when we add either acid or base. The Henderson-Hasselbalch equation can help us calculate it. It looks like this: pH = pKa + log [A-] [HA]

Example 3

Titrations and pH Curves