General Chemistry Course

Course 7
Electrolytic dissociation, electrolysis) pH, hydrolysis, tampon systems,

Acids and Bases A group of chemical properties is related to acidity. According to these properties, a substance can be called an acid or a base. The word acid comes from Latin acere meaning sour. A base is an alkaline, which is derived from Arabic alqali. Presence of acids and bases have been recognized by ancient people. Lavoisier named oxygen as the element from which acids are derived. Liebig (German) proposed that an acid contains hydrogen. Many chemical reactions are called acid-base reactions; they are not necessarily neutralizations. The acid-base concept is interesting, especially the way it evolved.

Understand acid or base, important properties of substances.

Answer these questions

Understand important properties of substances

What are acids? What are bases? What are acid-base reactions? What are neutralization reactions? What are the relationships between acids and bases? What is the role of the solvent in acid or base solutions?

How does the acid-base concept evolve and why? What are Arrhenius acid, Bronsted-Lowry acid and Lewis acids? What is the relationship between conjugate acids and bases?
What does pH mean and how is the pH scale related to acidity? What are salts?

Arrhenius acids and bases Sevante Arrhenius proposed that substances exists as ions in solution in his dissertation, which was awarded a fourth class (D) in 1884. He was unable to find a job in his native Sweden. He was awarded the Nobel Prize in 1903 for his electrolytic dissociation theory. The fundamental concept: Acid - any substance which delivers hydrogen ion (H+) to the solution. HA H+ + A Base - any substance which delivers hydroxide ion (OH) to the solution. BOH B+ + OH

Problems with Arrhenius theory

Like Daltons atomic theory, Arrhenius theory have problems today: Acidity did not show in other solvent. What is the solvent role? Some salts produce acidic or basic solutions, not neutral. Why? Which is the base, NH3 or NH4OH? Is OH really the only base? How can H+ be stable? Are proton donated? Some chemists want students to learn Brnsted-Lowry theory of acids and bases before learning Arrhenius theory, because the former is more general.

Question the established theory.

Brnsted-Lowry theory of acids and bases

An acid is a substance from which a proton can be removed. Acids are proton donors. A base is a substance that can remove a proton from an acid. Bases are proton acceptors. Because of strong desire for protons, bases rip protons off acids. Acid-base reactions are competitions for protons. HCl + H2O H3O+ + Cl HNO3 + H2O H3O+ + NO3 HC2H3O2 + H2O H3O+ + C2H3O2 H2O + NH3 NH4+ + OH conjugate acids and bases

Problems with B-L theory

The theory works very nicely in all protic solvent, but fails to explain acid-base behavior in aprotic solvents and non-solvent situations.

A more general concept on acid and base was proposed by G.N. Lewis at about the same time Bronsted-Lowry theory was proposed.

Question the established theory.

Evolution of the acid-base concept

year 1884

thinker Arrhenius

Acid ionize H+ Proton Donor

Base ionize OH proton acceptor

acid-base reaction H+ + OH = HOH

1923

BronstedLowry Lewis

HA + B = HB + A conjugation E + Nu = E:Nu

1923

electrophil nucleophil

Lewis acids and bases

Gilbert Newton Lewis (1875-1946) influential American chemist. His theories include the Lewis dot structure taught in Chem120 and covalent bond theories. Lewis acids are electrophils: H+, Na+, BF3, Lewis bases are nucleophils: NH3, H2O, PH3 Acid base reactions: BF3 + :NH3 F3B:NH3

Lewis at his desk. He generalized an idea.

179

HClO4 H2SO4 HI HBr HCl HNO3 H3O+ HSO4 H2SO3 H3PO4 HNO2 HF HC2H3O2 Al(H2O)63+ H2CO3 H2S

ClO4 HSO4 I Br Cl NO3 H2O SO42 HSO3 H2PO4 NO2 F C2H3O2 Al(OH)(H2O)52+ HCO3 HS

Relative strengths of acids and bases

The stronger the acid, the weaker its conjugate base. HClO HBrO NH4+ HCN HCO3 H2O2 HS H2O ROH ClO BrO NH3 CN CO32 HO2 S2 OH RO

Skills regarding strength of acids

What are strong acids? What are strong bases? Which is the strongest acid, HF, HCl, HBr, or HI? How about HNO3 and HNO2? H2SO4, H2SO3? How about HClO4, HClO3, HClO2, HClO, and HCl?

What is the strongest acid in an aqueous solution? What is leveling effect?

Order a given list according to the strength. Interpret reactions as due to strength of acids and bases. Explain strength with related acids and bases.

Molecular structure and acid strength

A strong acid loses its proton easily. A strong base holds onto a proton tightly. The more polarized is the HX bond in an acid, the easier the molecule releases H+ thus a stronger acid.

The weaker the H X bond, the easier the molecule releases H+ thus a stronger acid.
The bond strength and the polarity are related to electronegativity and electrostatic interactions size of the ions. Able to predict acidity from molecular structure.

Self-ionization of water

Water molecules autoionize

2 H2O (l) = H3O+ (aq) + OH (aq)

[H3O+] [OH] Kc = [H2O] (= 1000/18 = 55.6) Kw = [H2O] Kc = 1e14 only at 25oC, its T dependent. The ion product, Kw increases as T increases, and its value remains the same in the presence of acid or base. The molecule of life, H2O, and its acidity.

Solutions of strong acids and bases

Strong acids and strong bases completely ionize in their solutions. HCl (aq) + H2O (l) H3O+ (aq)+ Cl (aq) KOH (aq) K+ (aq)+ OH (aq) In a 0.100 M HCl or HNO3 solution, [H+] = 0.100 M and [OH] = 1e14 / 0.100 = 1e13 M at 25oC In a 0.100 M NaOH or KOH solution, [OH] = 0.100 M and [H+] = 1e14 / 0.100 = 1e13 M at 25oC

In a 0.010 M Ca(OH)2 solution, [OH] = 2*0.010 = 0.020 M [H+] = 1e14 / 0.020 = 5e13 M at 25oC

Some strong acids and bases

Strong acids Hydrogen halides HCl HBr HI

Strong Bases Hydroxides of alkali metals NaOH KOH CsOH Hydroxides of alkali earth Ca(OH)2 Sr(OH)2

Oxyacids of halogens HClO3 HBrO3 HIO3 HClO4 HBrO4 HIO4 Other oxyacids H2SO4 HNO3

Neutralization Reactions

The neutralization reaction between strong acids and strong bases has the net ionic reaction

H3O+ (aq)+ OH (aq) = 2 H2O

The anions are bystander ions. They do not participate the reaction. These ions are I, Br, Cl, NO3 , HSO4 , CClO4 , Na+, K+, Cs+, Ca2+ etc. When dried, the ions left behind in neutralization reactions form salts.

The pH scale

Sorensen introduced the pH scale in 1909 using the symbol pH. The p is from the German word potenz, power of (10).

pH = log [H+]; pOH = log [OH]; pK = log [K];

[H+] = 10 pH [OH] = 10 pOH K = 10 pK

0.9 0.13

pH = 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 [H+] = 0.79 0.63 0.50 0.40 0.32 0.25 0.20 0.16 (not linear; need not copy, figure out yourself)

For aqueous solution;

Kw = [H+] [OH] - log Kw = pH + pOH = 14 only at 25oC

pH meter and pH electrodes

The pH meter is based on the principle to be discussed in electrochemistry.

This topic is also related to the equilibrium constant K and Gibbs free energy, G.

Neutrality

In a neutral solution, [H+] = [OH]. In an acidic solution, [H+] > [OH], and a basic solution, [H+] < [OH].

In a saturated CaO (same as Ca(OH)2) solution, [OH] = 0.025. Calculate pH, [H+], [Ca2+], and pOH at 25oC. Solution: pOH = log 0.025 = 1.60 pH = 14.00 1.60 = 12.40 only applicable at 25oC [H+] = 1012.40 = 4.0e13 M Note that 4.0e-13*0.025 = 1e-14 [Ca2+] = [OH] / 2= 0.013 M

Answer these questions review

What are acid-base reactions? What are neutralization reactions? What is the role of the solvent in acidity? What does pH mean and how is the pH scale related to acidity? What are salts?

Acid-Base Equilibria

Strong acids and bases completely ionize in their aqueous solutions. HCl H+ + Cl KOH K+ + OH Weak acids and bases ionize but not completely in their solutions. HCH3COO H+ + CH3COO acetic acid, vinegar spirit HNic H+ + Nic HNic = Niacine, C5NH5COOH, a water-soluble vitamin required by the body for

health, growth and reproduction; part of the vitamin B complex. It was first prepared in pure form by oxidizing nicotine using conc. HNO3. Nicotine is a major chemical in tobacco .

CH3
N

<= Nicotine
Niacine => Vitamine B3

N
COOH

Ionization of weak acids

Ionization of acetic acid, HCH3COO, HA

HA = H+ + A
[H+] [A] Ka = [HA]

same as HA + H2O = H3O+ + A

A = CH3COO (acetate)
Ka acid ionization constant, important for an acid Ka equilibrium constant with solvent effect

The pKa is defined similar to the pH, pKa = log Ka

Ka = 10 pKa

Some weak acids and bases

Common Weak Acids Formic acid Acetic acid Trichloroacetic acid Hydrofluoric Hydrocyanic Hydrogen sulfide Water Conjugate acids of weak bases HCOOH CH3COOH CCl3COOH HF HCN H 2S H 2O

Common Weak Bases ammonia trimethyl ammonia pyridine ammonium hydroxide water HS- ion conjugate bases of weak acids e.g.:

NH3 N(CH3)3 C5H5N NH4OH H2O HSHCOO-

NH4+

Determine Ka and percent ionization

Nicotinic acid, HNic, is a monoprotic acid. A solution containing 0.012 M HNic, has a pH of 3.39. What is its Ka? What is the percent of ionization? Solution: HNic = H+ + Nic 0.012-x x x x = [H+] = 103.39 = 4.1e-4 [HNic] = 0.012 0.00041 = 0.012 (4.1e-4)2 Ka = = 1.4e-5 0.012 Degree of ionization = 0.00041 / 0.012 = 0.034 = 3.4%

Application of Ka

The Ka of nicotinic acid, HNic, is 1.4e-5. A solution containing 0.22 M HNic. What is its pH? What is the degree of ionization? Solution: HNic = H+ + Nic 0.22-x x x

x2 Ka = = 1.4e-5 0.22 x (use approximation, small indeed)

x = (0.22*1.4e-5) = 0.0018 pH = log (0.0018) = 2.76 Degree of ionization = 0.0018 / 0.22 = 0.0079 = 0.79% compare with 3.4% when the solution was 0.012 M

pH of a weak acid
The pH of C M acid HA (Ka) solution. Method:

HA = C-x

H+ + A x x

The pOH of C M base BOH (Kb) solution.

Method:
BOH = B+ + OH C-y y y y2 Kb = Cy y 2 + Kb x C Kb = 0 Kb + Kb2 + 4 C Kb y = 2 pOH = -log y

x2 Ka = Cx x 2 + Ka x C Ka = 0 Ka + Ka2 + 4 C Ka x = 2 pH = log x

The Ka of nicotinic acid, HNic, is 1.4e-5. A solution containing 0.00100 M HNic. What is its pH? What is the degree of ionization?

Solution: HNic = H+ + Nic 0.001-x x x x2 Ka = = 1.4e-5 0.00100 x

x 2 + Ka x C Ka = 0
Ka + Ka2 + 4 C Ka x = 2

x2 + 1.4e-5 x 1.4e-8 = 0

1.4e5 + (1.4e5)2 + 4*1.4e-8 x = = 0.000111 M 2

Deg.of ionization 0.22 0.012 0.001 0.79% 3.4 % 11.1 %

pH = log (0.000111) = 3.95 Degree of ionization = 0.000111/ 0.001 = 0.111 = 11.1%

Degree of or percent ionization

% ionization The degree or percent of ionization of a weak acid always decreases as its concentration increases, as shown from the table given earlier.

Deg. of ionization 0.22 0.012 0.001 Concentration of acid 0.79% 3.4 % 11.1 %

Polyprotic acids

Polyprotic acids such as sulfuric and carbonic acids have more than one hydrogen to donate. H2SO4 = H+ + HSO4 HSO4 = H+ + SO42 H2CO3 = H+ + HCO3 HCO3 = H+ + CO32 Ascorbic acid (vitamin C) is a diprotic acid, abundant in citrus fruit. Others: H2S, H2SO3, H3PO4, H2C2O4 (oxalic acid) Ka1 very large completely ionized Ka2 = 0.012 Ka1 = 4.3e-7 Ka2 = 4.8e-11

Base-ionization constant

For a base BOH, BOH = B+ + OH [B+] [OH] Kb = [BOH]

For acid, HA
HA = H+ + A [H+] [A] Ka = [HA] The pKa is defined similar to the pH, pKa = log Ka
From slide 3

The pKb is defined similar to pKa

pKb = log Kb,

Kb =

10pKb

Ka = 10 pKa

Whatever you have learned for weak acids apply to weak bases

Common weak bases

Substance Ammonia aniline dimethylamine ethylamine Hydrozine Hydroxylamine methylamine Pyridine Urea

Formula NH3 C6H5NH2 (CH3)2NH C2H5NH2 N2H4 H2NOH CH3NH2 C5H5N NH2CONH2

Kb 1.8e-5 4.2e-10 5.1e-4 4.7e-4 1.7e-6 1.1e-8 4.4e-4 1.4e-9 1.5e-14

Many drugs are salts of weak bases, such as Advil Pseudoephedrine HCl Buckley's mixture Dextromethorphan hydrobromide
Dristan Traxodone HCl

Hydrolysis of a salt

What it is a salt?
Product BA of neutralization reaction between an acid and a base HA + BOH H2O + BA

What is going on with the salt once we dissolve it in a solvent (water)? 1. BA DISSOCIATES

CH3COONa
CH3COO- + H2O Na+ + 2 H2O

CH3COO- + Na+
CH3COOH + OHNaOH + H3O+

2. Resulting ions interact with the solvent (water) molecules

Of the two above reactions the dominant one determines the pH of the hydrolyzed salt solution.