Chapter 14.

Acids and Bases

Early attributes of acids and bases (1600's)
Acids Taste sour Turn litmus red React with metals React with carbonates Bases Taste bitter Turn litmus blue Feel slippery React with fats

Arrhenius Acids and Bases

Definitions of Svante Arrhenius, 1884 First working theory about acids and bases
Acids contain hydrogen and produce H1+ ions in water. Bases contain hydroxide ions (OH1-) and are soluble in water.

Acids and Bases

Arrhenius Acids and Bases

Acids are molecular compounds; a covalent bond attaches the hydrogen ion to the adjacent atom. Ionization, the separation of the molecule into ions, occurs when the molecule dissolves in water.

Arrhenius Acids and Bases

Bases are ionic compounds; the hydroxide ion exists in the crystal structure of the solid compound. Dissociation occurs when the ionic solid dissolves in water, releasing the ions to move about.

Arrhenius Acids and Bases

Common Acids:
HCl(aq), H2SO4, H3PO4, HNO3

HC2H3O2 = CH3COOH = acetic acid

Common Bases: NaOH, KOH

Bronsted-Lowry Acids and Bases

The Arrhenius definition has some problems:
It's restricted to water.

It doesn't explain why solutions of some molecular compounds (NH3) and salts (Na2CO3) are basic.
It doesn't explain why some salt solutions are acidic (aqueous Al3+, Fe3+ solutions).

Bronsted-Lowry Acids and Bases

Definitions of Brnsted and Lowry, 1923 Most widely used theory of acids and bases Acids are proton donors. Bases are proton acceptors. Reactions:

HCl(aq) + H2O(l) H3O1+(aq) + Cl1-(aq)

H3O1+(aq) + NH3(aq) NH41+(aq) + H2O(l)

Bronsted-Lowry Acids and Bases

Bronsted-Lowry Acids and Bases

Formation of water by the transfer of protons from H3O1+ ions to OH1 ions.

Bronsted-Lowry Acids and Bases

Works in solvents other than water
Solves the base problem:
NH3(aq) + H3O1+(aq) NH41+(aq) + H2O(l)
CO32-(aq) + H3O1+(aq) HCO31-(aq) + H2O(l)

Doesn't solve the acid problem; What is it with Al3+(aq) and Fe3+(aq)?

Lewis Acids and Bases

Definitions of Gilbert Lewis, 1923 Most general theory of acids and bases
Acids are electron pair acceptors. Bases are electron pair donors.

Bronsted-Lowry Acids and Bases

Conjugate acid-base pairs:
A reaction between and acid and a base produces a conjugate acid and a conjugate base HCl(aq) + H2O(l) H3O1+(aq) + Cl1(aq)
Acid Base Conjugate Acid Conjugate Base

H3O1+(aq) + NH3(aq) H2O(l) + NH41+(aq)

Acid Base Conj. Base Conj. Acid

Bronsted-Lowry Acids and Bases

Choose the acid, base, conjugate acid, and conjugate base:
HCOOH(aq) + NH3(aq) HCOO1(aq) + NH41+ (aq) H2PO41(aq) + H2O(l) HPO42(aq) + H3O1+ (aq)

H2O(l) + HPO42(aq) + H3O1+ (aq) + PO43(aq)

Bronsted-Lowry Acids and Bases

Amphoteric substances can act as both acids and bases:
HCOOH(aq) + H2O(l) HCOO1(aq) + H3O1+ (aq)
NH3 (aq) + H2O(l) NH41+ (aq) + OH1(aq)

HPO42(aq) + OH1(aq) PO43(aq) + H2O(l)

HPO42(aq) + H3O1+ (aq) H2PO42(aq) + H2O(l)

Mono-, Di- and Triprotic Acids

Monoprotic acids can transfer one proton
CH3COOH + H2O CH3COO1 + H3O1+

Diprotic acids can transfer two protons

H2CO3 + H2O HCO31 + H3O1+ HCO31 + H2O CO32 + H3O1+

The first proton transfer is complete before the second one starts.

Mono-, Di- and Triprotic Acids

Triprotic acids can transfer three protons
H3PO4 + H2O H2PO41 + H3O1+ H2PO41 + H2O HPO42 + H3O1+

HPO42 + H2O PO43 + H3O1+

The first proton transfer is complete before the second one starts. The second proton transfer is complete before the third one starts.

Strengths of Acids and Bases

Acids differ in the extent of ionization when they are put in solution
Strong acids ionize completely. There are only a few strong acids. Weak acids do not ionize completely. Most acids are weak acids. The equilibrium constant, Ka, is a measure of the strength of an acid.

The Strong Acids

Formula HCl(aq) HBr(aq) HI(aq) HNO3 HClO4 HClO3 H2SO4 Name Hydrochloric acid Hydrobromic acid Hydriodic acid Nitric acid Perchloric acid Chloric acid Sulfuric acid* *first proton

Some Weak Acids

Formula HSO41 C9H8O4 HCOOH HC3H5O3 CH3COOH H2CO3 H2S(aq) HCN(aq) C6H5OH Name Hydrogen sulfate Acetylsalicylic acid Formic acid Lactic acid Acetic acid Carbonic acid Hydrosulfuric acid Hydrocyanic acid Phenol Ka 1.2 x 102 3.0 x 104 1.8 x 104 1.4 x 104 1.8 x 105 4.3 x 107 1.0 x 107 4.9 x 1010 1.3 x 1010

A comparison of the number of H3O1+ ions present in strong acid and weak acid solutions of equal concentration.

The Strong Bases

Soluble compounds that contain OH1Group 1A Hydroxides LiOH NaOH KOH RbOH CsOH Group 2A Hydroxides

Ca(OH)2 Sr(OH)2 Ba(OH)2

The Weak Bases

Ammonia:
NH3 + H2O NH41+ + OH1 Kb = 1.8 x 105 NH41+ + H2O NH3 + H3O1+ Ka = 5.6 x 1010

The Weak Bases

Anions from weak acids:

CH3COO1 + H2O CH3COOH + OH1

CO32- + H2O HCO31- + OH1

Salts
A salt is a compound containing a metal or polyatomic cation, and a nonmetal or polyatomic anion (except OH1).
NaCl, NH4Cl, BaSO4, CaCO3, Al2(SO4)3

Neutralization reactions between an acid and a base produce a salt and water.
HCl(aq) + NaOH(aq) H2O(l) + NaCl(aq) 2 Al(OH)3(s) + 3 H2SO4(aq) 6 H2O + Al2(SO4)3 (aq)

Hydrolysis of Salts
Hydrolysis is a reaction of a substance with water. Salts may hydrolyze to form H3O1+ or OH1 along with other products.

Hydrolysis of Salts
The salt of a weak acid and a strong base gives a weakly basic aqueous solution.
NaOH + HC2H3O2 NaC2H3O2 + H2O
NaC2H3O2 + H2O HC2H3O2 + OH1 + Na1+

Reestablishes equilibrium between acetate anion and acetic acid.

Hydrolysis of Salts
The salt of a weak base and a strong acid gives a weakly acidic aqueous solution.
NH3 + HCl NH4Cl NH4Cl + H2O NH3 + H3O1+ + Cl1

Hydrolysis of Salts
The salt of a weak base and a weak acid can give a weakly acidic, neutral, or weakly basic aqueous solution, depending on acid strengths.
NH4C2H3O2 + H2O HC2H3O2 + NH3

The salt of a strong acid and a strong base give a neutral solution.
NaCl + H2O Na1+ + Cl1 + H2O

Hydrolysis of Salts
Some metal ions, if they're small and have a high charge, give acidic solutions. Al3+ + 2 H2O AlOH2+ + H3O1+ Keq = 1.4 x 105 Fe3+ + 2 H2O FeOH2+ + H3O1+ Keq = 6.3 x 103 Cr3+ + 2 H2O CrOH2+ + H3O1+ Keq = 1.6 x 104

Net Ionic Equations

2 Al(OH)3(s) + 3 H2SO4(aq) 6 H2O(l) + Al2(SO4)3(aq) 2 HCl(aq) + CaCO3(s) 2 CaCl2(aq) + CO2(g) + H2O(l) Ionic Equations show dissolved ionic substances as ions rather than as compounds. Net Ionic Equations show only the participating species. "Spectator" ions are not shown.

Net Ionic Equations

Ionic Equations
2 Al(OH)3(s) + 6 H1+(aq) + 3 SO42(aq) 6 H2O(l) + 2 Al3+(aq) + 3 SO42(aq) 2 H1+(aq) + 2 Cl2(aq) + CaCO3(s) Ca2+(aq) + 2 Cl2(aq) + CO2(g) + H2O(l)

Net Ionic Equations (NIE's)

2 Al(OH)3(s) + 6 H1+ 6 H2O(l) + 2 Al3+
2 H1+ + CaCO3(s) Ca2+ + CO2(g) + H2O(l)

Self-Ionization of Water
The self-ionization of water is an acid-base reaction in which one water molecule transfers a proton to another.

2 H2O H3O1+ + OH1

Kw = 1.0 x 1014

Self-Ionization of Water
2 H2O H3O1+ + OH1 Kw = 1.0 x 1014

Kw = ion product constant for water Kw = 1.0 x 1014 = [H3O1+] [OH1]

In pure water, [H3O1+] = [OH1] = 1.0 x 107M

The relationship between [H3O1+] and [OH1] in aqueous solution is an inverse proportion; when [H3O1+] is increased, [OH1] decreases, and vice versa.

Self-Ionization of Water
An acidic solution has [H3O1+] > 1.0 x 107 M [OH1] < 1.0 x 107 M
A basic solution has [OH1] > 1.0 x 107 M [H3O1+] < 1.0 x 107 M A neutral solution has [H3O1+] = [OH1] = 1.0 x 107 M

Self-Ionization of Water
Examples:
In a 0.015 M solution of HCl, what is the concentration of OH1? Is the solution acidic or basic? [OH1] is 4.0 x 105. What is [H3O1+]? Is the solution acidic or basic?

The pH Scale
[H3O1+] can vary over a wide range, and is often low. Often, you need scientific notation to express it. This isn't always convenient. A simpler way to write [H3O1+] is pH

pH = log [H3O1+]
[H3O1+] = 10pH

Common (base 10) Logarigthms

A logarithm is the power to which a base, such as 10, must be raised to produce a given number. Number 0.010 = 1.0 x 10-2 1.0 = 1.0 x 100 10 = 1.0 x 101
Coefficient Exponent

Logarithm -2.00 0.00 1.00

Characteristic Mantissa

Base 10 logarithm
0 1 2 3 4 5 6 7 8

0.E+00 1.E+05 2.E+05 3.E+05 4.E+05 5.E+05 6.E+05 7.E+05 8.E+05 9.E+05 1.E+06

Powers of 10 and their logarithms

Power of 10

Common (base 10) Logarigthms

What happens if the coefficient of the number isnt 1.0? Number Logarithm

0.050 = 5.0 x 10-2 5.0 = 5.0 x 100 50 = 5.0 x 101

Coefficient Exponent

-1.30 0.70 1.70

Characteristic Mantissa

Integers and their logarithms

1 0.9

Base 10 logarithm

0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0

Integer

10

Common (base 10) Logarigthms

How logarithms simplify mathematics:
2.594 x 103 x 6.022 x 1023 = 1.562 x 1027
log(2.594e3) + log(6.022 e23) = log(1.562e27)

3.4140 + 23.7797 = 27.1937 antilog(27.1937) = 1027.1937 = 1.562 x 1027

Common (base 10) Logarigthms

How logarithms simplify mathematics: Slide rules use logarithmic scales for multiplication and division.

The pH Scale
An acidic solution has [H3O1+] > 1.0 x 107 M pH < 7.0
A basic solution has [OH1] > 1.0 x 107 M pH > 7.0 A neutral solution has [H3O1+] = [OH1] = 1.0 x 107 M pH = 7.0

A pH meter is used to measure pH values. The pH of vinegar is 2.32 (left). The pH of milk of magnesia in water is 9.39 (right).

The pH Scale
Give the pH for [H3O1+] = = = = = 0.010 M 4.2 x 103 M 1.0 x 107 M 6.8 x 1010 M 1.0 x 1012 M

Are the solutions acidic or basic?

The pH Scale
Give [H3O1+] for pH = = = = = 3.00 4.50 6.85 7.00 10.75

Are the solutions acidic or basic?

Buffers
A buffer is a solution that resists major changes in pH when acids or bases are added to it.

A buffer contains
A weak acid to react with added base A weak base to react with added acid Most often, the acid and base are conjugate pairs

Buffers
A buffer made of equimolar amounts of a weak acid and its conjugate base will have a pH equal to log Ka. log Ka = pKa
Adding a acid will shift the pH of the buffer down, adding base will shift the pH of the buffer up.

Buffers
Examples: What is the pH of a buffer made of 0.10 mole of CH3COOH and 0.10 mole of NaCH3COO? What is the pH of a buffer made with 1.0 mole of ammonia and 1.0 mole of ammonium chloride?

Buffers
A buffer is made with 0.10 mole of CH3COOH and 0.10 mole of NaCH3COO.
What component of the buffer reacts with added H3O1+? What component of the buffer reacts with added OH1?

Buffers
A buffer is made with 1.0 mole of NH3 and 1.0 mole of NH4Cl.
What component of the buffer reacts with added H3O1+? What component of the buffer reacts with added OH1?

Acid-Base Titrations
In an acid-base titration, a measured volume of an acid or base of known concentration is reacted with a measured volume of a base or acid of unknown concentration.
The reaction is conducted in a way that exactly equimolar amounts of H3O1+ and OH1 are combined.

Acid-Base Titrations
A student titrates 2.00 mL of vinegar (acetic acid in water) with 15.85 mL of 0.1048 M NaOH. What is the concentration of acetic acid in the vinegar? Calculate both molarity and mass percent. The density of vinegar is 1.05 g/mL. CH3COOH(aq) + NaOH(aq) CH3COONa(aq) + H2O(l)