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MODULE 4 IONIC EQUILIBRIA: ACIDS & BASES

Some Properties of Acids & Bases Acid sour taste change blue litmus paper to red corrosive & reactive to certain metals (Zn, Fe, etc) to produce H2 gas Base bitter taste change red litmus paper to blue they feel slippery reactive with oils & greases Theories on Acids & Bases 1. Arrhenius Theory (Svante Arrhenius) - all bases contain OH- while all acids contain H+ when ionized in water. - applicable only for aqueous solutions - cannot account for the acidity/basicity of other compounds like NH 3, a weak base ex: HCl(g) + H2O(l) H+(aq) + Cl-(aq) (acid) NaOH(s) + H2O(l) Na+(aq) + OH(base) 2. Bronsted-Lowry Theory (Johannes Niccolaus Bronsted & Thomas Martin Lowry) - acid is a proton donor - base is a proton acceptor ex: (1) NH3 + H2O NH4+ + OHbase acid

H2O acts as an acid since it donates a proton, (H+) to a proton acceptor (NH3) to become NH4+.
(2) NH4+ + OH- NH3 + H2O acid base

NH4+acts as an acid since it donates a proton, (H+) to a proton acceptor (OH-) to become NH3.
-consider reactions (1) & (2) as reversible reactions: NH3 + H2O NH4+ + OHbase(1) acid(2) acid(1) base(2)

NH3/NH4+ & H2O/OH- are conjugate pairs NH4+ is the conjugate acid of NH3 OH- is the conjugate base of H2O

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3. Lewis Theory (Gilbert Lewis) - Lewis acid is a species which accepts an electron pair to form a coordinate bond - Lewis base is a species which donates an electron pair to form a coordinate bond -

acid

base

NH3 is a base since it is an electron pair donor, while BF3 is an acid since it is an electron pair
acceptor (recall coordinate covalent bonding & Lewis structures) Practice Exercise 4.1: Classify each of the following species as Bronsted acid or base, or both: a. HCN b. NO3c. H3O+ d. NH2Practice Exercise 4.2: Identify the conjugate acid/base pairs in each of the reactions: a. CN- + H2O HCN + OHb. HClO + CH3NH2 CH3NH3+ + ClOc. H2PO4- + NH3 HPO42- + NH4+ d. HCO3- + HCO3- H2CO3 + CO32Practice Exercise 4.3: Write the formula of the conjugate bases of the following acids: a. HNO2 b. H2SO4 c. HCOOH d. HCN Practice Exercise 4.4: Write the formula of the conjugate acids of the following bases: a. PO43b. HPO42c. CO32d. HSAcid-Base Properties of Water & the Ion Product Constant Water

can act as either a base or an acid (amphiprotic) it undergoes autoionization/autoprotolysis into hydronium ion and hydroxide ion

H2O + H2O H3O+ + OHacid 1 base 2 acid 2 base 1 the conjugate acid-base pairs are (1) H2O (acid) and OH- (base) and (2) H3O+ (acid) and H2O (base). Kc = [H3O+] [OH-] at 25C in pure water, [H3O+] = [OH-] = 1.0 x 10-7

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the equilibrium constant for the self-ionization of water is called the ion-product constant, Kw at Kw = [H3O+] [OH-] = 1.0 x 10-14 (this applies to all aqueous solutions, not just for pure water)
Practice Exercise 4.5: The concentration of OH- ions in a certain household ammonia cleaning solution is 0.0025 M. Determine the concentration of H + ions. 25C.

Practice Exercise 4.6: Calculate the concentration of OH- ions in a HCl solution whose hydrogen ion concentration is 1.3 M.

pH and pOH pH

potential of hydrogen ion, proposed by Danish Biochemist Soren Sorensen defined as the negative of the logarithm of [H3O+]
pH = -log[H3O+] pOH defined as the negative of the logarithm of [OH-] pOH = -log[OH-] Acidic solutions : Basic solutions : Neutral solutions [H3O+] > 1.0 x 10-7 M, pH < 7.00 [H3O+] < 1.0 x 10-7 M, pH > 7.00 : [H3O+] = 1.0 x 10-7 M, pH = 7.00 pKw = - log 1.0 x 10-14 = 14.00 pKw = pH + pOH = 14.00 Practice Exercise 4.7: Nitric acid is used in the production of fertilizer, dyes, drugs & explosives. Calculate the pH of a HNO3 solution having a hydrogen ion concentration of 0.760 M.

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Practice Exercise 4.8: The OH- ion concentration of a blood sample is 2.5 x 10-7 M. What is the pH of the blood?

Practice Exercise 4.9: The pH of a solution of HCl in water is found to be 2.50. What is the H+ ion concentration?

Classification of Acids & Bases: 1. According to Strength a. Strong Acids - are strong electrolytes which are assumed to completely ionize in water & forms H 3O+ ion b. Weak Acids - are weak electrolytes and ionizes only to a limited extent to form H 3O+ ion c. Strong Bases - are strong electrolytes which are assumed to completely ionize in water & forms OH - ion d. Weak Bases - are weak electrolytes and ionizes only to a limited extent to form OH - ion The Common Strong Acids & Strong Bases Acids HCl HBr HI HClO4 HNO3 H2SO4 Bases LiOH NaOH KOH RbOH CsOH Mg(OH)2 Ca(OH)2 Sr(OH)2 Ba(OH)2

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2. According to the number of Replaceable H+ a. Monoprotic Acid - are acids that when ionized in water yields only one hydrogen ion ex: HNO3(aq) H+(aq) + NO3-(aq) HBr(aq) H+(aq) + Br-(aq) b. Polyprotic Acids - are acids that when ionized in water yields more than one hydrogen ion in a series of steps (diprotic- two H+; triprotic- three H+) ex: H3PO4(aq) H+(aq) + H2PO4-(aq) H2PO4-(aq) H+(aq) + HPO42-(aq) HPO42-(aq) H+(aq) + PO43-(aq) Acid-Base Equilibria Acid base equilibria deals quantitatively with acid and base ionization in water. Ionization of Acids & Bases consider the ionization of an acid, HA(aq) + H2O H3O+ + A-(aq) or HA(aq) H+(aq) + A-(aq) Ka = [H+][A-] [HA] B(aq) + H2O BH+ + OH-(aq) Kb = [BH+][OH-] [B]

consider the ionization of a base,

Ka and Kb are called the acid ionization constant and base ionization constant respectively. Ka and Kb tells us the degree of dissociation of the acid or base in water. It also tells us the

relative strength of the acid or base. the higher the value of Ka (or Kb), the greater its ionization in water, the higher the acidity (or basicity) of the solution.

Practice Exercise 4.10: Butyric Acid, HC4H7O2, is used to make compounds employed in artificial flavorings and syrups. A 0.250 M aqueous solution of butyric acid is found to have a pH of 2.72. Determine Ka for butyric acid?

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Practice Exercise 4.11: The much-abused drug cocaine is an alkaloid. Alkaloids are noted for their bitter taste, which indicates that they are bases. Cocaine, C 17H21O4N, is soluble in water to the extent of 0.17g/100 mL solution, and a saturated solution has a pH of 10.08. What is the Kb for cocaine? C17H21O4N + H2O C17H21O4NH+ + OH-

Practice Exercise 4.12: What is the pH of 0.00250 M HNO2(aq) whose pKa is equal to 3.14?

Percent Ionization gives the proportion of ionized molecules on a percentage basis. determines the strength of an acid or base the greater the percent ionization, the stronger the acid or base. % ionization = equilibrium conc of H+/OH- x 100 initial conc of acid or base Practice Exercise 4.12: What is the percent ionization of 0.010 M acetic acid HC2H3O2? Ka = 1.8 x 10-5

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Practice Exercise 4.13: A 0.0284 M aqueous solution of lactic acid, a substance that accumulates in the blood and muscles during physical activity, is found to be 6.7% ionized. Determine the value of Ka for lactic acid. HC3H5O3 + H2O H3O+ + C3H5O3-

Practice Exercise 4.14: What is the percent ionization of trichloroacetic acid in 0.035 M HC2Cl3O2 solution? HC2Cl3O2 + H2O H3O+ + C2Cl3O2- pKa = 0.52

Solve Problems:.16.3, 16.5, 16.16, 16.17, 16.41, 16.45,16.47 Pages 568 570. General Chemistry: The Essential Concepts, 5th edition by Raymond Chang References: General Chemistry: The Essential Concepts, 5th edition by Raymond Chang Chemistry : 8th edition by Whitten, Davis, Peck and Stanley CHEMISTRY: The Molecular Nature of Matter and Change , 4th ed. by Martin Silberberg

Chemistry: The General Science, 10th ed, by Brown, Le May and Bursten.

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