Chapter 8 Acid Base Equilibrium

The Nature of Acid Base Equilibria

- Acid: - conducts electricity. - turns blue litmus red. - corrodes metal. - Base: - conducts electricity. - turns red litmus blue. - feels slippery. - these are old definitions - Arrhenius Acids & Bases: - developed by Svante Arrhenius (1884). - Acids produce hydrogen ions (H+). - Bases produce hydroxide ions (OH-). - ex. HCl(aq) H+(aq) + Cl-(aq) NaOH (aq) Na+(aq) + OH-(aq) - can now quantitatively measure levels of acidity ([H+]) and alkalinity ([OH-]). - problems: - only applies to aqueous solutions. - H+ not responsible for acid characteristics H+ is very reactive and will form H-bond with H2O H3O+ (hydronium ion). - cant explain certain acid base reactions: NH3(g) + H2O(l) NH4+(aq) + OH-(aq) - Brnsted-Lowry Acids & Bases: - developed by J.N. Brnsted & T.M. Lowry (1923). - acid: - any substance that gives up hydrogen ion (proton) proton donor. - all formulas contain hydrogen. - base: - any substance able to accept a proton proton acceptor - all substances have an available, unshared pair of electrons. - able to overcome Arrhenius weaknesses. - must classify Brnsted acids and bases according to the reaction they are involved in.

- ex. H2O can be Brnsted acid or Brnsted base: HCl(g) + H2O(l) H3O+(aq) + Cl-(aq) (proton acceptor = base) NH3(g) + H2O(l) NH4+(aq) + OH-(aq) (proton donor = acid) - Conjugate Acid-Base Pairs: - Brnsted acid-base reactions are equilibrium systems involving two acid-base pairs, each that have formulas that differ by one H+ unit. - a Brnsted acid reactant will form Brnsted base product and visa versa. - ex: NH4+(aq) +
acid

H2O(aq)
base

H3O+(aq) +
conjugate acid of H2 O

NH3(aq)
conjugate base of + NH4

- Sample Problem 1 Write the formula of the conjugate base of each molecule or ion below. a) HF(aq) b) HCO3-(aq) c) H2SO4(aq) d) N2H5+(aq)

- Sample Problem 2 Write the formula for the conjugate acid of each molecule or ion below. a) NO3-(aq) b) H2O(l) c) OH-(aq) d) HCO3-(aq)

- Sample Problem 3 When perchloric acid, HClO4(aq), dissolved in water, the following reaction occurs: HClO4(aq) + H2O(l) H3O+(aq) + ClO4-(aq)

Identify the conjugate acid-base pairs in the reaction above. - Sample Problem 4 Identify the conjugate acid-base pairs in the following reaction: HS-(aq) + H2O(l)

H2S(aq) + OH-(aq)

- Strong and Weak Acids: - strong acids are good proton donors and strong electrolytes they completely dissociate in H2O to produce hydronium ions. - dissociation is complete, therefore, not an equilibrium reaction. - Ex. >99% HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq) - there are a few strong acids (HCl(aq), HBr(aq), H2SO4(aq), HNO3(aq), H3PO4(aq)) - weak acids are poor proton donors and weak electrolytes dissociation is incomplete, therefore, equilibrium is achieved. - Ex. 1.3% CH3COOH(aq) + H2O(l)

H3O+(aq) + CH3COO-(aq)

- in general, the stronger an acid, the weaker its conjugate base, and conversely, the weaker an acid, the stronger its conjugate base. - General Acid Ionization Reaction where HA(aq) is an acid, and A-(aq) is its conjugate base: HA(aq) + H2O(l) H3O+(aq) + A-(aq) - this is often abbreviated to: HA(aq) H+(aq) + A-(aq) - Strong and Weak Bases: - strong base readily accepts protons. - weak bases do not readily accept protons, creating an equilibrium system.

Ion Concentration and pH:

- Water Dissociation Constant: - H2O is amphiprotic (proton donor and proton acceptor) and will sometimes react with itself to produce hydronium and hydroxide ions: H2O(l) + H2O(l) H3O+(aq) + OH-(aq) - this water equilibrium obeys the equilibrium law. - since the concentration of H2O is constant, it is not included in the equation. Kw = [H3O+][ OH-] = 1.0 x 10-14 (at 25oC) (for any aqueous solution)

Sample Problem 1 The concentration of hydroxide ions, OH-(aq), of household window cleaner is 0.0020 mol/L at 25C. What is the concentration of hydronium ions in the sample? Is the window cleaner acidic, basic, or neutral? Explain your answer. Solution:

- Sample Problem 2 A solution of lithium hydroxide, LiOH(aq) is made by placing 2.00 mol of the base in 1.50 L of solution. What is the concentration of hydronium ions in the solution at 25C? Is the solution acidic, basic or neutral? Explain your answer. - Solution:

- Sample Problem 3 Calculate the hydrogen ion concentration in a 0.045 mol/L solution of calcium hydroxide, a strong base. - Solution:

- pH Scale: - expresses and compares concentration of hydronium ions in aqueous solutions. [H3O+] = [OH-] neutral [H3O+] > [OH-] acidic [H3O+] < [OH-] basic - pH scale: - expresses acidity levels (potency of hydrogen) - ranges between 0 14 - 7 = neutral - 0 7 = acidic - 7 14 = basic - [H3O+] = 10-pH mol/L - pH = -log [H3O+] - pOH refers to [OH-] [OH-] = 10-pOH mol/L pOH = -log [OH-] at 25oC pH + pOH = 14

- Sample Problem 1 - What is the pH of a 0.01 M HNO3 solution? (Assume 100 % dissociation of HNO3) - Solution:

- Sample Problem 2 What is the hydrogen ion concentration of a solution with a pH of 9.45? - Solution:

- Sample Problem 3 A solution is prepared with [H3O+] of 0.50 mol/L. Calculate the pH, pOH, and [OH-] of the solution at 25C. - Solution:

- Measuring pH: - can use acid-base indicators (a chemical substance that changes colour when the pH of the system changes), or pH meters (an electronic instrument that measures the voltage between electrodes in a solution and displays this measurement as a pH value).

Percent Ionization of Weak Acids:

- weak acids ionize less than 50% and have pHs closer to 7. - percent ionization (p) = concentration of acid ionized x 100% concentration of acid solute - for the general weak acid ionization reaction: HA(aq) H+(aq) + A-(aq) p = [H+] 100 [HA]

- Sample Problem The pH of a 0.10 mol/L methanoic acid solution is 2.38. Calculate the percent ionization of the methanoic acid. - Solution:

Weak Acids and Bases:

- strong acids and bases show almost complete dissociation. - weak acids do not completely dissociate, therefore, use acid dissociation constant (Ka) to measure strength of weak acids. - ex. HX(aq) + H2O(l) H3O+(aq) + X-(aq) Ka =
[H3O ][ X ] [HX]

- Ka only applies to weak acid solutions. - as Ka , acid strength

- Sample Problem 1 Calculate the Ka of hydrofluoric acid, HF(aq), if a 0.100 mol/L solution at equilibrium and SATP has a percent ionization of 7.8%. - Solution:

- Sample Problem 2 What will be the acid-dissociation constant for propanoic acid, C2H5COOH(aq), when a 0.10 molL solution is prepared and the final pH is found to be 2.96? What is the percent dissociation of this weak acid? - Solution:

- solutions of weak bases must use the base dissociation constant, Kb, to measure strength. - ex. B(aq) + H2O(l) HB+(aq) + OH-(aq) Kb = [HB+] [OH-] [B]

[H2O] is not considered

- The Relationship Between Ka and Kb: Kw = Ka x Kb (for any conjugate acid-base pair)

- this is an important relationship because Kb can be used to find Ka and vice versa. - Sample Problem The Kb for hydrazine, N2H4(aq), is 1.7 x 10-6. What is the Ka of its conjugate acid, N2H5+(aq)? - Solution:

Calculations Involving Acidic Solutions:

- Sample Problem 1 The standard value for the Ka of hydrofluoric acid, HF(aq), is 6.6 x 10-4. Calculate the pH of a 1.00 mol/L solution of hydrofluoric acid. - Solution:

- Sample Problem 2 Calculate the pH of a 0.100 mol/L solution of hypochlorous acid, HClO(aq). Ka for this weak acid is 3.5 x 10-8. - Solution:

- Sample Problem 3 A 0.050 mol/L solution of nicotinic acid, HC2H6NO2(aq), has a pH of 3.08. Calculate Ka for nicotinic acid. - Solution:

Polyprotic Acids:
- able to donate more than one proton. - each are donated one step at a time. - calculate separate equilibrium constants for each one. - Ka1 first ionization reaction - Ka2 second ionization reaction - Ex. H2C2O4(aq) H+(aq) + HC2O4(aq) Ka1 = [H+] [HC2O4-] [H2C2O4] HC2O4-(aq) H+(aq) + C2O42-(aq) Ka2 = [H+] [C2O42-] [HC2O4-] - Ka1 is significantly greater than Ka2. - For most polyprotic acids the initial acid is the strongest and each subsequent acid gets weaker. (Ka2 = 5.4 x 10-5) (Ka1 = 5.4 x 10-2)

Calculations Involving Basic Solutions:

to determine the value of Kb when it is not listed in a reference table, use the relationship Kw = Ka x Kb

- Sample Problem Calculate the pH of a 1.50 mol/L solution of ethanoate, C2H3O2-(aq). The Ka of ethanoic acid is 1.8 x 10-5. - Solution:

Acid-Base Properties of Salt Solutions:

- salts are ionic compounds made of a positive ion (cation) and a negation ion (anion). - salts are highly soluble in water and when dissolved can easily dissociate into ions that may or may not affect the pH of a solution. - acidic salts when dissolved in water, increase the concentration of hydrogen ions. - basic salts when dissolved in water, increase the concentration of hydroxide ions. - neutral salts when dissolved in water, produce neither hydrogen nor hydroxide ions. - Neutral Salts: NaCl(s) Na+(aq) + Cl-(aq)

Since Na+(aq) is the cation of a strong base (NaOH(aq)), Na+(aq) does not react with water to form NaOH(aq) and H+(aq)

Since Cl-(aq) is the anion of a strong acid (HCl(aq)), Cl-(aq) does not react with water to form HCl(aq) and OH-(aq)

The pH of this solution is found to be 7 (Neutral Solution)

- Basic Salts: KC2H3O2(aq) K+(aq) + C2H3O2-(aq)

Since K+(aq) is the cation of a strong base (KOH(aq)), K+(aq) does not react with water to form KOH(aq) and H+(aq)

Since C2H3O2-(aq) is the anion of a weak acid (HC2H3O2-(aq)), C2H3O2-(aq) is a sufficiently strong base to react with water to produce HC2H3O2(aq) and OH-(aq)

C2H3O2-(aq) + H2O(l)
(aq)

HC2H3O2(aq) + OH-

Basic Solution - Acidic Salts: NH4Cl(s) NH4+(aq) + Cl-(aq)

Since NH4+(aq) is the conjugate acid of a weak base (NH3(aq)), NH4+(aq) is a sufficiently strong acid to react with water and produce NH3(aq) and H3O+(aq)

Since Cl-(aq) is the anion of a strong acid (HCl(aq)), Cl-(aq) does not react with water to form HCl(aq) and OH-(aq)

NH4+(aq) + H2O(l)

NH3aq) + H3O+(aq)

Acidic Solution - hydrolysis a chemical reaction of an ion with water to produce an acidic or basic solution by the production of the hydronium ion or hydroxide ion.

- Sample Problem 1 Calculate the pH of a 0.30 mol/L solution of sodium nitrite, NaNO2(aq). - Solution:

- Sample Problem 2 Calculate the pH of a 0.10 mol/L solution of NH4Cl(aq). - Solution:

- Sample Problem 3 Calculate the pH of a 0.35 mol/L solution of sodium methanoate, NaCHO2(aq). - Solution:

Acid Base Titrations:

- a neutralization reaction where small amounts of base are added in a controlled manner to an unknown concentration of acid (or vice versa) until endpoint is reached (i.e. indicator changes colour). - used to determine unknown concentrations.

- Sample Problem 1 What volume of 3.00 mol/L hydrochloric acid, HCl(aq), must be added to a 15.0 mL sample of a 2.50 mol/L sodium hydroxide solution to reach equivalence point? - Solution:

- Sample Problem 2 Calculate the volume of titrant needed to reach the equivalence point in the titration of a 25.0 mL sample of 0.50 mol/L NaOH(aq) by 0.10 mol/L HCl(aq). - Solution:

- Sample Problem 3 In a titration, a 25.00 mL sample of 0.350 mol/L hydrochloric acid is titrated with standardized 0.500 mol/L sodium hydroxide solution. Determine the amount of unreacted hydrogen ions and the pH of the sample after 10.00 mL of NaOH is added. - Solution:

- Sample Problem 4 For the titration in sample problem 3 (above), a) what is the concentration of unreacted H+(aq) and the pH of the solution after 5.0 mL of sodium hydroxide solution, NaOH(aq), has been added? - Solution:

b) what is the amount (in moles) of unreacted H+(aq) and the pH of the solution after 20.0 mL of the sodium hydroxide solution has been added? - Solution: