Chapter 18

Acid-Base Equilibria

18-1

Acid-Base Equilibria
18.1 Acids and Bases in Water

18.2 Autoionization of Water and the pH Scale

18.3 Proton Transfer and the Brønsted-Lowry Acid-Base Definition

18.4 Solving Problems Involving Weak-Acid Equilibria

18.5 Weak Bases and Their Relation to Weak Acids

18.6 Molecular Properties and Acid Strength

18.7 Acid-Base Properties of Salt Solutions
18.8 Generalizing the Brønsted-Lowry Concept: The Leveling
Effect
18.9 Electron-Pair Donation and the Lewis Acid-Base Definition

18-2

Table 18.1 Some Common Acids and Bases and their
Household Uses.

18-3

Arrhenius Acid-Base Definition
This is the earliest acid-base definition, which classifies
these substances in terms of their behavior in water.

An acid is a substance with H in its formula that dissociates
to yield H3O+.

A base is a substance with OH in its formula that
dissociates to yield OH-.
When an acid reacts with a base, they undergo
neutralization:
H+(aq) + OH-(aq) → H2O(l) H°rxn = -55.9 kJ

18-4

[HA][H2O] 18-5 . Strong and Weak Acids A strong acid dissociates completely into ions in water: HA(g or l) + H2O(l) → H3O+(aq) + A-(aq) A dilute solution of a strong acid contains no HA molecules. [H3O+][A-] Kc = has a very small value. most HA molecules are undissociated. A weak acid dissociates slightly to form ions in water: HA(aq) + H2O(l) H3O+(aq) + A-(aq) In a dilute solution of a weak acid.

Strong acid: HA(g or l) + H2O(l) → H3O+(aq) + A-(aq) There are no HA molecules in solution.1A The extent of dissociation for strong acids. 18-6 . Figure 18.

18-7 .1B The extent of dissociation for weak acids. Weak acid: HA(aq) + H2O(l) H3O+(aq) + A-(aq) Most HA molecules are undissociated. Figure 18.

since [H3O+] is much higher. Zinc reacts rapidly with the strong acid. 1 M HCl(aq) 1 M CH3COOH(aq) 18-8 . Figure 18.2 Reaction of zinc with a strong acid (left) and a weak acid (right).

Ka HA(aq) + H2O(l) H3O+(aq) + A-(aq) [H3O+][A-] [H3O+][A-] Kc = Kc[H2O] = Ka = [HA][H2O] [HA] The value of Ka is an indication of acid strength. Stronger acid higher [H3O+] larger Ka Weaker acid lower % dissociation of HA smaller Ka 18-9 . The Acid Dissociation Constant.

Table 18.2 Ka Values for some Monoprotic Acids at 25°C 18-10 .

. which have the general formula RCOOH (eg. HClO. – acids in which H is not bonded to O or to a halogen (eg.) 18-11 . HCN).. HNO 2). Classifying the Relative Strengths of Acids • Strong acids include – the hydrohalic acids (HCl. HBr. and HI) and – oxoacids in which the number of O atoms exceeds the number of ionizable protons by two or more (eg. and – carboxylic acids... H2SO4. CH3COOH and C6H5COOH. HNO3. – oxoacids in which the number of O atoms equals or exceeds the number of ionizable protons by one (eg.) • Weak acids include – the hydrohalic acid HF. HClO4.

Na. • Weak bases include – ammonia (NH3). Classifying the Relative Strengths of Bases • Strong bases include – water-soluble compounds containing O 2. Sr. – The cations are usually those of the most active metals: • M2O or MOH. 18-12 . Ba). K.ions. Cs) • MO or M(OH)2 where M = group 2A(2) metal (Ca. which have the general formula – The common structural feature is an N atom with a lone electron pair. – amines. where M = Group 1A(1) metal (Li.or OH. Rb.

Particular points to note for acids are the numbers of O atoms relative to ionizable H atoms and the presence of the –COOH group. or weak base. 18-13 . using the text descriptions. note the nature of the cation or the presence of an N atom that has a lone pair.1 Classifying Acid and Base Strength from the Chemical Formula PROBLEM: Classify each of the following compounds as a strong acid. SOLUTION: (a) Strong base: KOH is one of the group 1A(1) hydroxides. weak acid. Sample Problem 18. strong base. For bases. (a) KOH (b) (CH3)2CHCOOH (c) H2SeO4 (d) (CH3)2CHNH2 PLAN: We examine the formula and classify each acid or base.

18-14 . (d) Weak base: (CH3)2CHNH2 has a lone pair of electrons on the N and is an amine. The –COOH proton is the only ionizable proton in this compound. (c) Strong acid: He2SO4 is an oxoacid in which the number of atoms exceeds the number of ionizable protons by two.1 (b) Weak acid: (CH3)2CHCOOH is a carboxylic acid. Sample Problem 18. as indicated by the –COOH group.

2H2O (l) H3O+ (aq) + OH. Autoionization of Water Water dissociates very slightly into ions in an equilibrium process known as autoionization or self-ionization.(aq) 18-15 .

18-16 .0x10-14 (at 25°C) In pure water.0x10-7 (at 25°C) Both ions are present in all aqueous systems. The Ion-Product Constant for Water (Kw) 2H2O (l) H3O+ (aq) + OH.(aq) [H3O+][A-] Kc = [H2O]2 Kc[H2O]2 = Kw = [H3O+][OH-] = 1. [H3O+] = [OH-] = = 1.

[H3O+] > [OH-] In a neutral solution. and vice versa.ions: In an acidic solution. Higher [H3O+] lower [OH-] Higher [OH-] lower [H3O+] We can define the terms “acidic” and “basic” in terms of the relative concentrations of H3O+ and OH. A change in [H3O+] causes an inverse change in [OH-]. [H3O+] = [OH-] In basic solution. [H3O+] < [OH-] 18-17 .

18-18 . Figure 18.3 The relationship between [H3O+] and [OH-] and the relative acidity of solutions.

0x10-14 = [H3O+] [OH-] so Kw 1.2 Calculating [H3O+] or [OH-] in an Aqueous Solution PROBLEM: A research chemist adds a measured amount of HCl gas to pure water at 25°C and obtains a solution with [H3O+] = 3.0x10-14 [OH-] = = = 3. or basic? PLAN: We use the known value of Kw at 25°C (1. Is the solution neutral.0x10-4 M. 18-19 . Sample Problem 18. or neutral. basic.0x10-4 [H3O+] is > [OH-] and the solution is acidic.3x10-11 M [H3O+] 3. SOLUTION: Kw = 1. Calculate [OH-]. We can then compare [H3O+] with [OH-] to determine whether the solution is acidic.0x10-14) and the given [H3O+] to solve for [OH-]. acidic.

the lower the [H3O+] and the less acidic the solution. pH < 7. pH > 7. 18-20 .00 In a neutral solution. The pH Scale pH = -log[H3O+] The pH of a solution indicates its relative acidity: In an acidic solution. pH = 7.00 In basic solution.00 The higher the pH.

pH = -log [H3O+] 18-21 .4 The pH values of some familiar aqueous solutions. Figure 18.

8x10-5 4.1x10-4 3.0x10-10 10.3 The Relationship between Ka and pKa Acid Name (Formula) Ka at 25°C pKa Hydrogen sulfate ion (HSO4-) 1.00 pKa = -logKa A low pKa corresponds to a high Ka. Table 18.15 Acetic acid (CH3COOH) 1.99 Nitrous acid (HNO2) 7.3x10-9 8.0x10-2 1. 18-22 .64 Phenol (C6H5OH) 1.75 Hypobromous acid (HBrO) 2.

the values of pH.00 at 25°C pOH = -log[OH-] pH + pOH = pKw for any aqueous solution at any temperature. [OH-] decreases (and vice versa). pOH. and pKw Kw = [H3O+][OH-] = 1. pOH.0x10-14 at 25°C pH = -log[H3O+] pKw = pH + pOH = 14. • If pH increases. 18-23 . pH. pOH decreases (and vice versa). [H3O+]. Since Kw is a constant. and [OH-] are interrelated: • If [H3O+] increases.

Figure 18.5 The relations among [H3O+], pH, [OH-], and pOH.

18-24

Sample Problem 18.3 Calculating [H3O+], pH, [OH-], and pOH

PROBLEM: In an art restoration project, a conservator prepares
copper-plate etching solutions by diluting concentrated
HNO3 to 2.0 M, 0.30 M, and 0.0063 M HNO3. Calculate
[H3O+], pH, [OH-], and pOH of the three solutions at 25°C.
PLAN: HNO3 is a strong acid so it dissociates completely, and [H 3O+]
= [HNO3]init. We use the given concentrations and the value of
Kw at 25°C to find [H3O+] and [OH-]. We can then calculate pH
and pOH.
SOLUTION:
Calculating the values for 2.0 M HNO3:
[H3O+] = 2.0 M pH = -log[H3O+] = -log(2.0) = -0.30
Kw 1.0x10 -14
[OH-] = = = 5.0x10-15 M
[H3O+] 2.0
pOH = -log[OH-] = -log(5.0x10-15) = 14.30

18-25

Sample Problem 18.3

Calculating the values for 0.30 M HNO3:
[H3O+] = 0.30 M pH = -log[H3O+] = -log(0.30) = 0.52
Kw 1.0x10 -14
[OH-] = = = 3.3x10-14 M
[H3O+] 0.30
pOH = -log[OH-] = -log(3.3x10-14) = 13.48

Calculating the values for 0.0063 M HNO3:
[H3O+] = 0.0063 M pH = -log[H3O+] = -log(0.30) = 2.20
Kw 1.0x10 -14
[OH-] = = = 1.6x10-12 M
[H3O+] 0.0063
pOH = -log[OH-] = -log(1.6x10-12) = 11.80

18-26

Figure 18.6 Methods for measuring the pH of an aqueous solution.

pH paper

pH meter

18-27

A base is a proton acceptor. any species that donates an H+ ion. An acid-base reaction is a proton-transfer process. • An acid must contain H in its formula. Brønsted-Lowry Acid-Base Definition An acid is a proton donor. • A base must contain a lone pair of electrons to bond to H+. 18-28 . any species that accepts an H+ ion.

Figure 18. H+ donor) (base. H+ acceptor) (acid.7 Dissolving of an acid or base in water as a Brønsted- Lowry acid-base reaction. H+ donor) 18-29 . Lone pair binds H+ (acid. H+ acceptor) Lone pair binds H+ (base.

In the reverse reaction: NH4+ donates a H+ to form NH3. Conjugate Acid-Base Pairs In the forward reaction: NH3 accepts a H+ to form NH4+. H2S + NH3 HS. 18-30 .+ NH4+ HS. H2S + NH3 HS.accepts a H+ to form H2S.+ NH4+ H2S donates a H+ to form HS-.

is the conjugate base of the acid H2S. A Brønsted-Lowry acid-base reaction occurs when an acid and a base react to form their conjugate base and conjugate acid.+ NH4+ H2S and HS. respectively.are a conjugate acid-base pair: HS. NH3 and NH4+ are a conjugate acid-base pair: NH4+ is the conjugate acid of the base NH3. acid1 + base2 base1 + acid2 18-31 . Conjugate Acid-Base Pairs H2S + NH3 HS.

4 The Conjugate Pairs in some Acid-Base Reactions Conjugate Pair Acid + Base Base + Acid Conjugate Pair Reaction 1 HF + H2O F. + H2O Reaction 5 H2SO4 + N2H5+ HSO4. + N2H62+ Reaction 6 HPO42.+ HCN Reaction 3 NH4+ + CO32. + SO32. + H3O+ Reaction 2 HCOOH + CN. HPO42. PO43. + OH. NH3 + HCO3- Reaction 4 H2PO4. + HSO3- 18-32 . HCOO. Table 18.

(a) H2PO4-(aq) + CO32-(aq) HPO42-(aq) + HCO3-(aq) (b) H2O(l) + SO32-(aq) OH-(aq) + HSO3-(aq) PLAN: To find the conjugate pairs.4 Identifying Conjugate Acid-Base Pairs PROBLEM: The following reactions are important environmental processes.and CO32-/HCO3-. 18-33 . The acid donates an H+ to becomes its conjugate base. we find the species that donated an H+ (acid) and the species that accepted it (base). and the base accepts an H+ to becomes it conjugate acid. SOLUTION: (a) H2PO4-(aq) + CO32-(aq) HPO42-(aq) + HCO3-(aq) acid1 base2 base1 acid2 The conjugate acid-base pairs are H2PO4-/HPO42. Identify the conjugate acid-base pairs. Sample Problem 18.

Sample Problem 18.and SO32-/HSO3-. 18-34 .4 (b) H2O(l) + SO32-(aq) OH-(aq) + HSO3-(aq) acid1 base2 base1 acid2 The conjugate acid-base pairs are H2O/OH.

A reaction will favor the formation of the weaker acid and base. 18-35 . + NH4+ stronger acid weaker base stronger base weaker acid This reaction favors the formation of the products. Net Direction of Reaction The net direction of an acid-base reaction depends on the relative strength of the acids and bases involved. H2S + NH3 HS.

The stronger the acid is. 18-36 . When an acid reacts with a base that is farther down the list. the reaction proceeds to the right (Kc > 1).8 Strengths of conjugate acid-base pairs. Figure 18. the weaker its conjugate base.

8 to see which acid and base are stronger. 18-37 .5 Predicting the Net Direction of an Acid- Base Reaction PROBLEM: Predict the net direction and whether Kc is greater or less than 1 for each of the following reactions (assume equal initial concentrations of all species): (a) H2PO4-(aq) + NH3(aq) HPO42-(aq) + NH4+(aq) (b) H2O(l) + HS-(aq) OH-(aq) + H2S(aq) PLAN: We identify the conjugate acid-base pairs and consult figure 18. SOLUTION: (a) H2PO4-(aq) + NH3(aq) HPO42-(aq) + NH4+(aq) stronger acid stronger base weaker base weaker acid The net direction for this reaction is to the right. The reaction favors the formation of the weaker acid and base. Sample Problem 18. so Kc > 1.

18-38 . so Kc < 1. Sample Problem 18.5 (b) H2O(l) + HS-(aq) OH-(aq) + H2S(aq) weaker acid weaker base stronger base stronger acid The net direction for this reaction is to the left.

which scene best represents the final mixture after equimolar solutions of HX and Y.are mixed? PLAN: A stronger acid and base yield a weaker acid and base.52. so we have to determine the relative acid strengths of HX and HY to choose the correct molecular scene.10 M of HX (blue and green) has a pH of 2. Sample Problem 18. so we can recognize the stronger acid by comparing the pH values of the two solutions.10 M HY (blue and orange) has a pH 3.6 Using Molecular Scenes to Predict the Net Direction of an Acid-Base Reaction PROBLEM: Given that 0. The concentrations of the acid solutions are equal.88. and 0. 18-39 .

6 SOLUTION: The HX solution has a lower pH than the HY solution. which would occur if HY were the stronger acid. The reaction of HX and Y- has a Kc > 1. 18-40 . so HX is the stronger acid and Y. Scene 1 has equal numbers of HX and HY.is the stronger base. because it contains more HY than HX. Scene 2 shows fewer HY than HX. which could occur if the acids were of equal strength. which means the equilibrium mixture will contain more HY than HX. Scene 3 is consistent with the relative acid strengths. Sample Problem 18.

5. 6.Write an expression for Ka.Write a balanced equation.Make assumptions that simplify the calculation. 7. 3.Check that the assumptions are justified. 2. 4.Define x as the change in concentration that occurs during the reaction. 18-41 .Substitute values into the Ka expression and solve for x. Solving Problems Involving Weak-Acid Equilibria Problem-solving approach 1.Construct a reaction table in terms of x.

[HA] ≈ [HA]init. • A weak acid has a small Ka and its dissociation is negligible. • A bracketed formula with no subscript indicates an equilibrium concentration. Solving Problems Involving Weak-Acid Equilibria The notation system • Molar concentrations are indicated by [ ]. 18-42 . The assumptions • [H3O+] from the autoionization of H2O is negligible.

SOLUTION: HPAc(aq) + H2O(l) H3O+(aq) + PAc-(aq) Ka = [H3O+][PAc-] [HPAc] 18-43 . causes mental retardation and death. We assume that [H3O+] from H2 is negligible and use the given pH to find [H3O+]. A study of the acid shows that the pH of 0.7 Finding Ka of a Weak Acid from the Solution pH PROBLEM: Phenylacetic acid (C6H5CH2COOH. What is the Ka of phenylacetic acid? PLAN: We start with the balanced dissociation equation and write the expression for Ka.62. if untreated. Sample Problem 18. We assume that [HPAc] ≈ [HPAc]init because HPAc is a weak acid. simplified here as HPAc) builds up in the blood of persons with phenylketonuria. an inherited disorder that. which equals [PAc-] and [HPAc]dissoc.12 M HPAc is 2.

assumption is justified). -3 0.4x10-3 M [HPAc]dissoc = 2.4x10-3 M ≈ [H3O+] ≈ [PAc-] [HPAc] = 0. 2 2.12 .4x10-3) So Ka = = 4.4x10-3) (2. Sample Problem 18. + x +x Equilibrium 0.12 Checking the assumptions by finding the percent error in concentration: 1x10-7 M [H3O ]from H O = + x 100= 4x10-3 % (<5%.12 .x ≈ 0.4x10 M x 100 = 2.7 Concentration (M) HPAc(aq) + H2O(l) H3O+(aq) + PAc-(aq) Initial 0.4x10-3 M which is >> 10-7 (the [H3O+] from water) x ≈ 2. x x [H3O+] = 10-pH = 2.12 M 18-44 .12 . 0 0 Change - x . assumption is justified).12 M (2.8x10-5 0.0 % (<5%.x .

Sample Problem 18.e. which we simplify as HPr) is a carboxylic acid whose salts are used to retard mold growth in foods. We know [HPr]init but not [HPr] (i. since HPr has a small Ka value. We define x as [HPr]dissoc and set up a reaction table.10 M HPr (Ka = 1.8 Determining Concentration from Ka and Initial [HA] PROBLEM: Propanoic acid (CH3CH2COOH. We assume that. it dissociates very little and therefore [HPr] ≈ [HPr]init. SOLUTION: HPr(aq) + H2O(l) H3O+(aq) + Pr−(aq) Ka = [H3O+][Pr−] [HPr] 18-45 . What is the [H3O+] of 0.3x10−5)? PLAN: We write a balanced equation and the expression for Ka. the concentration at equilibrium)..

1x10-3 M = [H3O+] 1.10 .10 .) 0.10 M 18-46 . +x +x Equilibrium 0.8 Concentration (M) HPr(aq) + H2O(l) H3O+(aq) + Pr-(aq) Initial 0. assumption is justified.1x10-3 M Check: [HPr]diss = x 100 = 1.1% (< 5%.10 and [HPr] ≈ 0.10 x= = 1. Sample Problem 18.x . x x Since Ka is small. [H3O+][Pr-] x2 Ka = 1.10 M.3x10 = -5 = [HPr] 0. 0 0 Change −x . we will assume that x << 0.

even though the actual [HA]dissoc decreases. causing a shift towards the products. HA(aq) + H2O(l) H3O+(aq) + A-(aq) A decrease in [HA]init means a decrease in [HA]dissoc = [H3O+] = [A-]. the percent dissociation of the acid increases. 18-47 . The fraction of ions present increases. Concentration and Extent of Dissociation [HA]dissoc Percent HA dissociated = x 100 [HA]init As the initial acid concentration decreases.

and we know that the percent dissociation increases as the acid is diluted. we calculate the percent dissociation of each diluted sample and see which is greater than 33%.15 M solution of acid HA (blue and green) is 33% dissociated. Which scene best represents a sample of the solution after it is diluted with water? PLAN: We are given the percent dissociation of the original HA solution (33%).9 Using Molecular Scenes to Determine the Extent of HA Dissociation PROBLEM: A 0. Sample Problem 18. Thus. 18-48 .

% dissociated = 3/(6 + 3) x 100 = 33% Scene 1 represents the diluted solution.9 SOLUTION: In each case. % dissociated = 4/(5 + 4) x 100 = 44% Solution 2. % dissociated = 2/(7 + 2) x 100 = 22% Solution 3. remember that each unit of H3O+ is produced from one unit of HA. Sample Problem 18. 18-49 . so [HA]init = [HA] + [H3O+]. [H3O+] x 100 % dissociation = [HA] + [H3O+] Solution 1.

2x10-13 [HPO42-] Ka1 > Ka2 > Ka3 We usually neglect [H3O+] produced after the first dissociation.3x10-8 [H2PO ]4 - [H3O+][PO43-] HPO (aq) + H2O(l) 4 2- PO (aq) + H3O (aq) 4 3. Polyprotic Acids A polyprotic acid is an acid with more than one ionizable proton.2x10-3 [H3PO4] [H3O+][HPO42-] H2PO4-(aq) + H2O(l) HPO42-(aq) + H3O+(aq) Ka2 = = 6. 18-50 . + Ka1 = = 7. + Ka3 = = 4. each dissociation step has a different value for Ka: [H3O+][H2PO4-] H3PO4(aq) + H2O(l) H2PO4 (aq) + H3O (aq) . In solution.

Table 18.5 Successive Ka values for Some Polyprotic Acids at 25°C 18-51 .

and solve for [H3O+] and [HAsc-]. Sample Problem 18.0x10-5 [H2Asc] [Asc2-][H3O+] HAsc-(aq) + H2O(l) Asc2-(aq) + H3O+(aq) Ka2 = = 5x10-12 [HAsc-] 18-52 . we can assume that the first dissociation produces almost all the H3O+. [HAsc-]. SOLUTION: [HAsc-][H3O+] H2Asc(aq) + H2O(l) HAsc (aq) + H3O (aq) .0x10-5 and Ka2 = 5x10-12) found in citrus fruit. with x equal to [H2Asc]dissoc.10 Calculating Equilibrium Concentrations for a Polyprotic Acid PROBLEM: Ascorbic acid (H2C6H6O6. We set up a reaction table for the first dissociation. the amount of H2ASc that dissociates can be neglected. and the pH of 0. since Ka1 is small. known as vitamin C. [Asc2-]. H2Asc for this problem). Also.050 M H2Asc. Since Ka1 >> Ka2. PLAN: We first write the dissociation equations and the associated Ka expressions. Calculate [H2Asc]. is a diprotic acid (Ka1 = 1. + Ka1 = = 1.

x x [HAsc-][H3O+] x2 x2 Ka1 = = 1.1x10-4 M pH = -log[H3O+] = -log(7. +x +x Equilibrium 0.0x10-5 = ≈ [H2Asc] 0.1x10-4) = 3.050 .10 Concentration (M) H2Asc(aq) + H2O(l) HAsc-(aq) + H3O+(aq) Initial 0.x 0. Sample Problem 18.15 18-53 .050 .050 x = [H3O+] = [Asc-] = = 7. 0 0 Change -x .x .050 .

[H2Asc]dissoc << [H2Asc]init: 7.050 M 18-54 .1x10-4 M x 100 = 1. so the assumption is justifed. assumption is justified). 0. [H3O+] << [H3O+] from HAsc - from H2Asc : For any second dissocation. from H2O 2. [H3O+] ≈ = = 6x10-8 M from HAsc- This is even less than [H3O+] .4% (< 5%. Sample Problem 18.10 Checking assumptions: 1.

For a weak base that dissolves in water: B(aq) + H2O(l) BH+(aq) + OH-(aq) The base-dissociation or base-ionization constant is given by: [BH+][OH-] Kb = [B] Note that no base actually dissociates in solution. but ions are produced when the base reacts with H2O. Weak Bases A Brønsted-Lowry base is a species that accepts an H+. 18-55 .

Lone pair of N pair binds H+ 18-56 . Figure 18.9 Abstraction of a proton from water by the base methylamine.

6 Kb Values for Some Molecular (Amine) Bases at 25°C 18-57 . Table 18.

Since Kb is small. so [(CH3)2NH] ≈ [(CH3)2NH]init.11 Determining pH from Kb and Initial [B] PROBLEM: Dimethylamine. we can assume that the amount of amine reacting is also small. has a Kb of 5. the [OH-] from H2O is neglible. We then write the expression for Kb. From [OH-] we can calculate [H3O+] and pH. remembering that it is a weak base. SOLUTION: (CH3)2NH(aq) + H2O(l) (CH3)2NH2+(aq) + OH-(aq) [(CH3)2NH2+][OH-] Kb = [(CH3)2NH] 18-58 . set up a reaction table and solve for [OH-].5 M (CH3)2NH? PLAN: We start with the balanced equation for the reaction of the amine with H2O. Sample Problem 18. a key intermediate in detergent manufacture.9x10-4. Since Kb >> Kw. We make similar assumptions to those made for weak acids. What is the pH of 1. (CH3)2NH.

5 x = [OH-] = 3.0x10-2 M Check assumption: 3.9x10-4 ≈ [(CH3)2NH] 1. assumption is justified).50 [(CH3)2NH2+][OH-] x 2 Kb = = 5. +x +x Equilibrium 1.50 . 1.x .0% (< 5%. Sample Problem 18. 0 0 Change -x .0x10-2 M x 100 = 2.5 M 18-59 .50 and 1. x x Since Kb is small.50 .50 – x ≈ 1. x << 1.11 Concentration (M) (CH3)2NH(aq) + H2O(l) (CH3)2NH2+(aq) + OH-(aq) Initial 1.

11 Kw 1.48 18-60 . 3. Sample Problem 18.3x10-13 M [OH ] .0x10 -14 [H3O+] = = = 3.3x10-13) = 12.0x10-2 pH = -log (3.

while a solution of A. 2 the solution is therefore acidic. 18-61 . Anions of Weak Acids as Weak Bases The anions of weak acids often function as weak bases. and [H3O+]from HF >> [OH-] from H O. so this equilibrium lies to the left. HF(aq) + H2O(l) H3O+(aq) + F-(aq) HF is a weak acid. [HF] >> [F-]. [HA][OH-] A-(aq) + H2O(l) HA(aq) + OH-(aq) Kb = [A-] A solution of HA is acidic.is basic.

- 2 the solution is therefore basic. and F- can act as a weak base: F-(aq) + H2O(l) HF(aq) + OH-(aq) HF is a weak acid. If NaF is dissolved in H2O. it dissolves completely.] >> [HF]. [F. and [OH. so this equilibrium also lies to the left.] from F >> [H3O+ ] from H O . 18-62 .

+ H2O HA + OH- 2H2O H3O+ + OH- Kc for the overall equation = K1 x K2. Ka and Kb for a Conjugate Acid-Base Pair HA + H2O H3O+ + A- A. 18-63 . so [H3O+][A-] x [HA][OH-] = [H3O+][OH-] [HA] [A-] Ka x Kb = Kw This relationship is true for any conjugate acid-base pair.

What is the pH of 0. SOLUTION: Ac-(aq) + H2O(l) HAc(aq) + OH-(aq) [HAc][OH-] Kb = [Ac-] 18-64 . or NaAc for this problem) has applications in photographic development and textile dyeing. We write the base dissociation equation and the expression for Kb. PLAN: Sodium salts are soluble in water and acetate is the anion of HAc so it acts as a weak base.12 Determining the pH of a Solution of A- PROBLEM: Sodium acetate (CH3COONa.25 M. so [Ac-]init = 0.25 M NaAc? Ka of acetic acid (HAc) is 1. Sample Problem 18. We recall that any soluble ionic salt dissociates completely in solution.8x10-5. and solve for [OH-].

25 . +x +x Equilibrium 0.0x10-14 Kb = = = 5.12 Concentration (M) Ac-(aq) + H2O(l) HAc(aq) + OH-(aq) Initial 0. x x Kw 1.6x10 -10 M Ka 1. 0 0 Change -x . assumption is justified) 1.25 .8x10-3% (<5%.x . Sample Problem 18.6x10 -10 = ≈ so x = [OH-] = 1.8x10 -5 [HAc][OH-] x2 Kb = 5.0x10-14 x 100 = 4.25 Checking the assumption: 1.2x10-5 18-65 .2x10-5 M [Ac ] - 0.

3x10-10) = 9. Sample Problem 18.12 Kw 1.08 18-66 . 1.3x10-10 M [OH ] .0x10 -14 [H3O+] = = = 8.2x10-5 pH = -log (8.

and • the strength of the E-H bond. so the acidity of E-H increases. Down a group. acid strength increases. Electronegativity increases across a period. acid strength increases. Acid Strength of Nonmetal Hydrides For nonmetal hydrides (E-H). Across a period. 18-67 . acid strength depends on: • the electronegativity of the central nonmetal (E). The length of the E-H bond increases down a group and its bond strength therefore decreases.

Figure 18. 6A(16) 7A(17) Electronegativity H2O HF increases.10 The effect of atomic and molecular properties on nonmetal hydride acidity. so acidity H2S HCl Bond strength increases H2Se HBr H2Te HI 18-68 . so acidity increases decreases.

Acid Strength of Oxoacids All oxoacids have the acidic H bonded to an O atom. For oxoacids with the same number of O atoms. acid strength increases with the number of O atoms. acid strength increases as the electronegativity of E increases. and • the number of O atoms around E. 18-69 . Acid strength of oxoacids depends on: • the electronegativity of the central nonmetal (E). For oxoacids with different numbers of O atoms.

A Electronegativity increases.11 The relative strengths of oxoacids. B Number of O atoms increases. so acidity increases. 18-70 . so acidity increases. Figure 18.

Mn+: Mn+(aq) + H2O(l) → M(H2O)xn+(aq) If Mn+ is small and highly charged. These metal ions will form acidic solutions. Hydrated Metal Ions Some hydrated metal ions are able to transfer an H+ to H2O. Consider a metal ion in solution. it will withdraw enough e- density from the O-H bonds of the bound H2O molecules to release H+: M(H2O)xn+(aq) + H2O(l) M(H2O)x-1OH(n-1)(aq) + H3O+(aq) 18-71 .

Figure 18.12 The acidic behavior of the hydrated Al3+ ion. 18-72 .

because neither Na+ nor NO3. NaNO3 Na+ is the cation of NO3.will react with H2O to any great extent. 18-73 . a strong acid. Salts that Yield Neutral Solutions A salt that consists of the anion of a strong acid and the cation of a strong base yields a neutral solution. a strong base.is the anion of NaOH. HNO3. This solution will be neutral.

a strong acid. because NH4+ will react with H2O to produce H3O+: NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq) 18-74 . NH4Cl NH4 + is the cation of Cl. a weak base. Salts that Yield Acidic Solutions A salt that consists of the anion of a strong acid and the cation of a weak base yields an acidic solution. This solution will be acidic.is the anion of NH3. HCl.

CH3COONa CH3COO. because CH3COO.is the anion of Na+ is the cation of CH3COOH. a strong base. Salts that Yield Basic Solutions A salt that consists of the anion of a weak acid and the cation of a strong base yields a basic solution.will react with H2O to produce OH-: CH3COO-(aq) + H2O(l) CH3COOH(aq) + OH-(aq) 18-75 . a weak acid. This solution will be basic. NaOH.

or neutral. basic. acidic (weak-base cation with strong-acid anion). Depending on an ion’s ability to react with water. 18-76 .13 Predicting Relative Acidity of Salt Solutions from Reactions of the Ions with Water PROBLEM: Predict whether aqueous solutions of the following are acidic. the solution will be neutral (strong-acid anion with strong-base cation). Cr(NO3)3 PLAN: We identify the cation and anion from the formula for each salt. SOLUTION: (a) K+ is the cation of a strong base (KOH) while ClO4. KClO4 (b) Sodium benzoate. This solution will be neutral. or basic (weak-acid anion and strong-base cation). C6H5COONa (c) Chromium(III) nitrate. Sample Problem 18.is the anion of a strong acid (HClO4). and write an equation for the reaction of any ion with water: (a) Potassium perchlorate.

(c) NO3. 18-77 . Cr3+ is a small metal cation with a fairly high charge density. It will become hydrated and the hydrated ion will react with H2O to form H3O+ ions: Cr(H2O)63+(aq) + H2O(l) Cr(H2O)5OH2+(aq) + H3O+(aq) This solution will be acidic.is the anion of a strong acid (HNO3) and will not react with H2O to any great extent. Sample Problem 18.ions: C6H5COO-(aq) + H2O(l) C6H5COOH(aq) + OH-(aq) This solution will be basic.13 (b) Na+ is the cation of a strong base (NaOH) while the benzoate anion (C6H5COO-) is the anion of a weak acid (benzoic acid). The benzoate ion will react with H2O to produce OH.

Salts of Weakly Acidic Cations and Weakly Basic Anions If a salt that consists of the anion of a weak acid and the cation of a weak base. weak acid. the pH of the solution will depend on the relative acid strength or base strength of the ions. HCN. NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq) CN-(aq) + H2O(l) HCN(aq) + OH-(aq) 18-78 .is the anion of a weak base. NH3. NH4CN NH4+ is the cation of a CN.

0x10 -14 Kb of CN = - = = 1.6x10-5 Ka of HCN 6. A solution of NH4CN will be basic.2x10-10 Since Kb of CN. Kw 1. CN. 18-79 .> Ka of NH4+.0x10-14 Ka of NH4 = + = = 5. The reaction that proceeds farther to the right determines the pH of the solution.7x10-10 Kb of NH3 1.is a stronger base than NH4+ is an acid. so we need to compare the Ka of NH4+ with the Kb of CN-.76x10-5 Kw 1.

7 The Acid-Base Behavior of Salts in Water 18-80 . Table 18.

0x10-14 Kb of HCOO =- = = 5. Zn(HCOO)2. therefore the solution is acidic. or neutral.6x10-11 Ka of HCOOH 1. Both will react with H2O. while HCOO . Sample Problem 18. so to determine the acidity of the solution we must compare the Ka of the hydrated Zn2+ ion with the Kb of the HCOO. highly charged metal cation. at 25°C is acidic.) Kw 1.ion. SOLUTION: Zn(H2O)62+(aq) + H2O(l) Zn(H2O)5OH+(aq) + H3O+(aq) HCOO-(aq) + H2O(l) HCOOH(aq) + OH-(aq) Ka of Zn(H2O)62+ = 1x10-9 (from Appendix C. basic. 18-81 .8x10 -4 Ka for Zn(H2O)62+ >> Kb HCOO-.14 Predicting the Relative Acidity of Salt Solutions from Ka and Kb of the Ions PROBLEM: Determine whether an aqueous solution of zinc formate.is the anion of a weak acid. PLAN: Zn2+ is a small.

while all strong bases dissociate completely to form OH-. the strongest acid possible is H3O+ and the strongest base possible is OH-. 18-82 . H2O exerts a leveling effect on any strong acid or base. The Leveling Effect All strong acids and bases are equally strong in water. In water. All strong acids dissociate completely to form H3O+.

The Lewis Acid-Base Definition A Lewis base is any species that donates an electron pair to form a bond. The Lewis definition views an acid-base reaction as the donation and acceptance of an electron pair to form a covalent bond. A Lewis acid is any species that accepts an electron pair to form a bond. 18-83 .

Any substance that is a Brønsted-Lowry base is also a Lewis base. Lewis Acids and Bases A Lewis base must have a lone pair of electrons to donate. A Lewis acid must have a vacant orbital (or be able to rearrange its bonds to form one) to accept a lone pair and form a new bond. Many substances that are not Brønsted-Lowry acids are Lewis acids. 18-84 . The Lewis definition expands the classes of acids.

Electron-Deficient Molecules as Lewis Acids B and Al often form electron-deficient molecules. and these atoms have an unoccupied p orbital that can accept a pair of electrons: BF3 accepts an electron pair from ammonia to form a covalent bond. 18-85 .

18-86 . Lewis Acids with Polar Multiple Bonds Molecules that contain a polar multiple bond often function as Lewis acids: The O atom of an H2O molecule donates a lone pair to the S of SO2. forming a new S‒O σ bond and breaking one of the S‒O  bonds.

Metal Cations as Lewis Acids A metal cation acts as a Lewis acid when it dissolves in water to form a hydrated ion: The O atom of an H2O molecule donates a lone pair to an available orbital on the metal cation. 18-87 .

18-88 . Figure 18.13 The Mg2+ ion as a Lewis acid in chlorophyll.

+ BCl3 BCl4. Sample Problem 18. (b) BCl3 accepts an electron pair from Cl-. (c) An O atom from each H2O molecule donates an electron pair to K+.15 Identifying Lewis Acids and Bases PROBLEM: Identify the Lewis acids and Lewis bases in the following reactions: (a) H+ + OH. H+ is the Lewis acid and OH.is the Lewis base. 18-89 .is the Lewis base and BCl3 is the Lewis acid. H2O (b) Cl.(c) K+ + 6H2O K(H2O6)+ PLAN: We examine the formulas to see which species accepts the electron pair (Lewis acid) and which donates it (Lewis base) in forming the adduct. Cl. SOLUTION: (a) The H+ ion accepts the electron pair from OH-. H2O is therefore the Lewis base. and K+ is the Lewis acid.