Acid Base Equilibria

ACID BASE EQUILIBRIA
ANORGANIC CHEMISTRY
ASEP MUHAMAD SAMSUDIN, S.T., M.T.
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Chapter 18
Acid-Base Equilibria
18-2
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 Brnsted-Lowry Acid-Base Definition
18.4 Solving Problems Involving Weak-Acid Equilibria
18.5 Weak Bases and Their Relations to Weak Acids
18.6 Molecular Properties and Acid Strength
18.7 Acid-Base Properties of Salt Solutions
18.8 Electron-Pair Donation and the Lewis Acid-Base Definition
18-3
Introduction
Acids and bases have been used as laboratory chemicals since the time of the
alchemists, and they remain indispensable, not only in academic and industrial
labs, but in the home as well.
An acid was any substance that had a sour taste; reacted with active metals,
such as aluminum and zinc, to produce hydrogen gas; and turned certain
organic compounds characteristic colors.
A base was any substance that had a bitter taste and slippery feel and turned
the same organic compounds different characteristic colors.
Moreover, it was known that when acids and bases react, each cancels the
properties of the other in a process called neutralization.
But definitions in science evolve because, as descriptions become too limited,
they must be replaced by broader ones.
18-4
18-5
18.1 Acids and Bases in Water
Water is a product in all reactions between strong acids and strong

bases.
The net ionic equation of this reaction shows water is the product:
Furthermore, whenever an acid dissociates in water, solvent molecules

participate in the reaction:
The hydrated proton is usually shown in the text as H3O+(aq), although in

some cases this hydrated species is shown more simply as H+(aq).
18-6
Classical Acids- Bases Definition
The earliest and simplest definition of acids and bases that reflects
their molecular nature was suggested by Svante Arrhenius.
In the classical (or Arrhenius) acid-base definition, acids and bases are
classified in terms of their formulas and their behavior in water:
An acid is a substance that has H in its formula and dissociates in water
to yield H3O+(aq). Examples : HCl, HNO3 and HCN,
A base is a substance that has OH in its formula and dissociates in
water to yield OH-. Examples : NaOH, KOH, and Ba(OH)2.
In the Arrhenius sense, neutralization occurs when the H+ ion from the
acid and the OH- ion from the base combine to form H2O.
18-7
Variation in Acid Strength: The Acid-Dissociation Constant (Ka)
Acids and bases differ greatly in their strength in water, that is, in the
amount of H3O+ or OH- produced per mole of substance dissolved.
Acids and bases are electrolytes in water, so this classification of acid
and base strength correlates with our earlier classification of
electrolyte strength: strong electrolytes dissociate completely, and
weak electrolytes dissociate partially.
18-8
Figure 18.2 The extent of dissociation for strong acids.
Strong acid: HA(g or l) + H2O(l) H3O+(aq) + A-(aq)
18-9
Figure 18.3 The extent of dissociation for weak acids.
Weak acid: HA(aq) + H2O(l) H3O+(aq) + A-(aq)
18-10
Strong acids dissociate completely into ions in water.
HA(g or l) + H2O(l) H3O+(aq) + A-(aq) Kc >> 1
Weak acids dissociate very slightly into ions in water.
HA(aq) + H2O(l) H3O+(aq) + A-(aq) Kc << 1
The Acid-Dissociation Constant
[H3O+][A-] Larger Ka higher [H3O+]

Kc =
[H2O][HA] Strong acid
[H3O+][A-]
Kc[H2O] = Ka =
[HA] smaller Ka lower [H3O+]
weaker acid
18-11
The Acid-Dissociation Constant
18-12
18-13
Classifying the Relative Strengths of Acids and Bases
18-14
Classifying the Relative Strengths of Acids and Bases
18-15
SAMPLE PROBLEM 18.1 Classifying Acid and Base Strength from the
Chemical Formula
PROBLEM: Classify each of the following compounds as a strong acid,

weak acid, strong base, or weak base.
(a) H2SeO4 (b) (CH3)2CHCOOH (c) KOH (d) (CH3)2CHNH2
PLAN: Pay attention to the text definitions of acids and bases. Look at O for
acids as well as the -COOH group; watch for amine groups and
cations in bases.
SOLUTION: (a) Strong acid - H2SeO4 - the number of O atoms exceeds

the number of ionizable protons by 2.
(b) Weak acid - (CH3)2CHCOOH is an organic acid having a -COOH group.
(c) Strong base - KOH is a Group 1A(1) hydroxide.
(d) Weak base - (CH3)2CHNH2 has a lone pair of electrons on the N and
is an amine.
18-16
18.2 Autoionization of Water and the pH Scale
H2O(l) H2O(l)
H3O+(aq) OH-(aq)
18-17
H2O(l) + H2O(l) H3O+(aq) + OH-(aq)
[H3O+][OH-]
Kc =
[H2O]2
The Ion-Product Constant for Water
Kc[H2O]2 = Kw = [H3O+][OH-] = 1.0 x 10-14 at 250C
A change in [H3O+] causes an inverse change in [OH-].
In an acidic solution, [H3O+] > [OH-]

In a basic solution, [H3O+] < [OH-]
In a neutral solution, [H3O+] = [OH-]
Both ions are present in all aqueous systems.
18-18
The relationship between [H3O+] and [OH-] and the

Figure 18.4
relative acidity of solutions.
[H3O+] Divide into Kw [OH-]
[H3O+] > [OH-] [H3O+] = [OH-] [H3O+] < [OH-]
ACIDIC NEUTRAL BASIC

SOLUTION SOLUTION SOLUTION
18-19
SAMPLE PROBLEM 18.2 Calculating [H3O+] and [OH-] in an Aqueous

Solution
PROBLEM: A research chemist adds a measured amount of HCl gas to pure

water at 250C and obtains a solution with [H3O+] = 3.0x10-4M.
Calculate [OH-]. Is the solution neutral, acidic, or basic?
PLAN: Use the Kw at 250C and the [H3O+] to find the corresponding [OH-].
SOLUTION: K = 1.0x10-14 = [H O+] [OH-] so

w 3
[OH-] = Kw/ [H3O+] = 1.0x10-14/3.0x10-4 = 3.3x10-11M
[H3O+] is > [OH-] and the solution is acidic.
18-20
Figure 18.5
The pH values of
some familiar
aqueous solutions.
pH = -log [H3O+]
18-21
Table 18.1 The Relationship Between Ka and pKa
Acid Name (Formula) Ka at 250C pKa
Hydrogen sulfate ion (HSO4-) 1.02x10-2 1.991
7.1x10-4 3.15
Nitrous acid (HNO2)
1.8x10-5 4.74
Acetic acid (CH3COOH)
Hypobromous acid (HBrO) 2.3x10-9 8.64
Phenol (C6H5OH) 1.0x10-10 10.00
18-22
Figure 18.6 The relations among [H3O+], pH, [OH-], and pOH.
18-23
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 2.0M,
0.30M, and 0.0063M HNO3. Calculate [H3O+], pH, [OH-], and
pOH of the three solutions at 250C.
PLAN: HNO3 is a strong acid so [H3O+] = [HNO3]. Use Kw to find the [OH-]
and then convert to pH and pOH.
SOLUTION: For 2.0M HNO3, [H3O+] = 2.0M and -log [H3O+] = -0.30 = pH
[OH-] = Kw/ [H3O+] = 1.0x10-14/2.0 = 5.0x10-15M; pOH = 14.30
For 0.3M HNO3, [H3O+] = 0.30M and -log [H3O+] = 0.52 = pH

[OH-] = Kw/ [H3O+] = 1.0x10-14/0.30 = 3.3x10-14M; pOH = 13.48
For 0.0063M HNO3, [H3O+] = 0.0063M and -log [H3O+] = 2.20 = pH

[OH-] = Kw/ [H3O+] = 1.0x10-14/6.3x10-3 = 1.6x10-12M; pOH = 11.80
18-24
Figure 18.7 Methods for measuring the pH of an aqueous solution.
pH (indicator) paper
pH meter
18-25
18.3 Brnsted-Lowry Acid-Base Definition
An acid is a proton donor, any species which donates a H+.
A base is a proton acceptor, any species which accepts a H+.
An acid-base reaction can now be viewed from the standpoint

of the reactants AND the products.
An acid reactant will produce a base product and the two will
constitute an acid-base conjugate pair.
18-26
18-27
Figure 18.8 Proton transfer as the essential feature of a Brnsted-

Lowry acid-base reaction.
Lone pair
binds H+
+ +
HCl H 2O Cl- H 3 O+
(acid, H+ donor) (base, H+ acceptor)
Lone pair
binds H+
+ +
NH3 H 2O NH4+ OH-

(base, H+ acceptor) (acid, H+ donor)
18-28
Table 18.2 The Conjugate Pairs in Some Acid-Base Reactions

Conjugate Pair
Acid + Base Base + Acid
Conjugate Pair
Reaction 1 HF + H2O F- + H3O+
Reaction 2 HCOOH + CN- HCOO- + HCN
Reaction 3 NH4+ + CO32- NH3 + HCO3-
Reaction 4 H2PO4- + OH- HPO42- + H2O
Reaction 5 H2SO4 + N2H5+ HSO4- + N2H62+
Reaction 6 HPO42- + SO32- PO43- + HSO3-
18-29
SAMPLE PROBLEM 18.4 Identifying Conjugate Acid-Base Pairs
PROBLEM: The following reactions are important environmental processes.

Identify the conjugate acid-base pairs.
(a) H2PO4-(aq) + CO32-(aq) HPO42-(aq) + HCO3-(aq)
(b) H2O(l) + SO32-(aq) OH-(aq) + HSO3-(aq)
PLAN: Identify proton donors (acids) and proton acceptors (bases).

conjugate pair conjugate pair2
1
SOLUTION: (a) H2PO4-(aq) + CO32-(aq) HPO42-(aq) + HCO3-(aq)

proton proton proton proton
donor acceptor acceptor donor
conjugate pair1 conjugate pair2
(b) H2O(l) + SO32-(aq) OH-(aq) + HSO3-(aq)

proton proton proton proton
donor acceptor acceptor donor
18-30
SAMPLE PROBLEM 18.5 Predicting the Net Direction of an Acid-Base

Reaction
PROBLEM: Predict the net direction and whether Ka 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: Identify the conjugate acid-base pairs and then consult Figure 18.10
(button) to determine the relative strength of each. The stronger the
species, the more preponderant its conjugate.
SOLUTION: (a) H2PO4-(aq) + NH3(aq) HPO42-(aq) + NH4+(aq)

stronger acid stronger base weaker base weaker acid
Net direction is to the right with Kc > 1.
(b) H2O(l) + HS-(aq) OH-(aq) + H2S(aq)
weaker acid weaker base stronger base stronger acid
Net direction is to the left with Kc < 1.
18-31
Figure 18.9
Strengths of
conjugate acid-
base pairs.
18-32
Table 18.4 Solving Problems Involving Weak-acid Equilibria
In general, there are two general types of equilibrium problems

involving weak acids and their conjugate bases:
1. Given equilibrium concentrations, find Ka.

2. Given Ka and some concentration information. find the other
equilibrium concentrations.
18-33
SAMPLE PROBLEM 18.6 Finding the Ka of a Weak Acid from the pH of

Its Solution
PROBLEM: Phenylacetic acid (C6H5CH2COOH, simplified here as HPAc)

builds up in the blood of persons with phenylketonuria, an
inherited disorder that, if untreated, causes mental retardation
and death. A study of the acid shows that the pH of 0.12M
HPAc is 2.62. What is the Ka of phenylacetic acid?
PLAN: Write out the dissociation equation. Use pH and solution concentration
to find the Ka.
Assumptions: With a pH of 2.62, the [H3O+]HPAc >> [H3O+]water.

[PAc-] [H3O+];
since HPAc is weak, [HPAc]initial [HPAc]initial - [HPAc]dissociation
SOLUTION: HPAc(aq) + H2O(l) H3O+(aq) + PAc-(aq)
Ka = [H3O+][PAc-]
[HPAc]
18-34
SAMPLE PROBLEM 18.6 Finding the Ka of a Weak Acid from the pH of

Its Solution
continued
Concentration(M) HPAc(aq) + H2O(l) H3O+(aq) + PAc-(aq)
Initial 0.12 - 1x10-7 0

Change -x - +x +x
Equilibrium 0.12-x - x +(<1x10-7) x
[H3O+] = 10-pH = 2.4x10-3 M which is >> 10-7 (the [H3O+] from water)
x 2.4x10-3 M [H3O+] [PAc-] [HPAc]equilibrium = 0.12-x 0.12 M
(2.4x10-3) (2.4x10-3)
So Ka = = 4.8 x 10-5
0.12
1x10-7M
Be sure to check for % error. [H3 O+] from water; x100 = 4x10-3 %
2.4x10-3M
[HPAc]dissn; 2.4x10-3M
x100 = 2.0 %
0.12M
18-35
SAMPLE PROBLEM 18.7 Determining Concentrations from Ka and

Initial [HA]
PROBLEM: Propanoic acid (CH3CH2COOH, which we simplify and HPr) is

an organic acid whose salts are used to retard mold growth in
foods. What is the [H3O+] of 0.10M HPr (Ka = 1.3x10-5)?
PLAN: Write out the dissociation equation and expression; make whatever
assumptions about concentration which are necessary; substitute.
Assumptions: For HPr(aq) + H2O(l) H3O+(aq) + Pr-(aq)
x = [HPr]diss = [H3O+]from HPr= [Pr-] Ka = [H3O+][Pr-]
SOLUTION: [HPr]
Concentration(M) HPr(aq) + H2O(l) H3O+(aq) + Pr-(aq)
Initial 0.10 - 0 0
Change -x - +x +x
Equilibrium 0.10-x - x x
Since Ka is small, we will assume that x << 0.10
18-36
SAMPLE PROBLEM 18.7 Determining Concentrations from Ka and

Initial [HA]
continued
[H3O+][Pr-] (x)(x)
1.3x10-5 = =
[HPr] 0.10
x (0.10)(1.3x105 ) = 1.1x10-3 M = [H3O+]
Check: [HPr]diss = 1.1x10-3M/0.10 M x 100 = 1.1%
18-37
[HA]dissociated
Percent HA dissociation = x 100
[HA]initial
Polyprotic acids
acids with more than more ionizable proton
-(aq)
[H3O+][H2PO4-]
H3PO4(aq) + H2O(l) H2PO4 + H3 O+(aq) Ka1 =
[H3PO4]
= 7.2x10-3
H2PO4 -(aq) + H2O(l) HPO4 2-(aq) + H3 O+(aq) [H3O+][HPO42-]

Ka2 =
[H2PO4-]
= 6.3x10-8
2-(aq) 3-(aq)
[H3O+][PO43-]
HPO4 + H2O(l) PO4 + H3 O+(aq) Ka3 =
[HPO42-]
= 4.2x10-13
Ka1 > Ka2 > Ka3
18-38
18-39
SAMPLE PROBLEM 18.8 Calculating Equilibrium Cocentrations for a

Polyprotic Acid
18-40

Polyprotic Acid
18-41

Polyprotic Acid
18-42
18.5 Weak Bases and Their Relation to Weak Acids
A base is any species that accepts a proton; to do so, the base

must have a lone electron pair.
B(aq) + H2O(aq) BH+(aq) + OH-(aq)
Kb = base-dissociation constant (or base-ionization constant)

In aqueous solution, the two large classes of weak bases are
nitrogen-containing molecules, such as ammonia and the
amines, and the anions of weak acids.
18-43
Molecules as Weak Bases: Ammonia and the Amines
Ammonia is the simplest nitrogen-containing compound

that acts as a weak base in water:
If one or more of the H atoms in NH3 is replaced by an organic

group (designated as R), an amine results: RNH2, R2NH, or R3N
The key structural feature of these organic compounds, as in all
Bronsted-Lowry bases, is a lone pair of electrons that can bind
the proton donated by the acid.
18-44
Figure 18.10 Abstraction of a proton from water by methylamine.

Lone pair
binds H+
CH3NH2 H2O
methylamine
CH3NH3+ OH-
methylammonium ion
18-45
18-46
SAMPLE PROBLEM 18.8 Determining pH from Kb and Initial [B]
PROBLEM: Dimethylamine, (CH3)2NH, a key intermediate in detergent

manufacture, has a Kb of 5.9x10-4. What is the pH of 1.5M
(CH3)2NH?
PLAN: Perform this calculation as you did those for acids. Keep in mind that
you are working with Kb and a base.
(CH3)2NH(aq) + H2O(l) (CH3)2NH2+(aq) + OH-(aq)
Assumptions: Kb >> Kw so [OH-]from water is neglible
[(CH3)2NH2+] = [OH-] = x ; [(CH3)2NH]init - x [(CH3)2NH]initial
SOLUTION:
Concentration (CH3)2NH(aq) + H2O(l) (CH3)2NH2+(aq) + OH-(aq)

Initial 1.50M - 0 0
Change -x - +x +x
Equilibrium 1.50 - x - x x
18-47
SAMPLE PROBLEM 18. 8 Determining pH from Kb and Initial [B]
continued
[(CH3)2NH2+][OH-]
Kb = 5.9x10-4 =
[(CH3)2NH]
(x) (x)
5.9x10-4 = x = 3.0x10-2M = [OH-]
1.5M
Check assumption: 3.0x10-2M/1.5M x 100 = 2%
[H3O+] = Kw/[OH-] = 1.0x10-14/3.0x10-2 = 3.3x10-13M
pH = -log 3.3x10-13 = 12.48
18-48
Anions of Weak Acids as Weak Bases
The Relation Between Ka and Kb of a Conjugate Acid-Base Pair
18-49
SAMPLE PROBLEM 18.9 Determining the pH of a Solution of A-
PROBLEM: Sodium acetate (CH3COONa, or NaAc for this problem) has

applications in photographic development and textile dyeing.
What is the pH of 0.25M NaAc? Ka of acetic acid (HAc) is
1.8x10-5.
PLAN: Sodium salts are soluble in water so [Ac-] = 0.25M.
Write the association equation for acetic acid; use the Ka to find the Kb.
SOLUTION:
Concentration Ac-(aq) + H2O(l) HAc(aq) + OH-(aq)

Initial 0.25M - 0 0
Change -x - +x +x
Equilibrium 0.25M-x - x x
[HAc][OH-] Kw 1.0x10-14
Kb = = Kb = = 5.6x10-10M
[Ac-] Ka 1.8x10-5
18-50
SAMPLE PROBLEM 18.9 Determining the pH of a Solution of A-
continued
[Ac-] = 0.25M-x 0.25M

[HAc][OH-]
Kb =
[Ac-] 5.6x10-10 = x2/0.25M
x = 1.2x10-5M = [OH-]
Check assumption: 1.2x10-5M/0.25M x 100 = 4.8x10-3 %
[H3O+] = Kw/[OH-] = 1.0x10-14/1.2x10-5 = 8.3x10-10M
pH = -log 8.3x10-10M = 9.08
18-51
Molecular Properties and Acid Strength
Trends in Acid Strength of Nonmetal Hydrides
Trends in Acid Strength of Oxoacids
Acidity of Hydrated Metal Ions
18-52
Trends in Acid Strength of Nonmetal Hydrides
Figure 18.11 The effect of atomic and molecular properties on

nonmetal hydride acidity.
6A(16) 7A(17)
Electronegativity increases,
acidity increases
H 2O HF
Bond strength decreases,
acidity increases
H 2S HCl
H2Se HBr
H2Te HI
18-53
Trends in Acid Strength of Oxoacids
Two factors determine the acid strength of oxoacids: the

electronegativity of the central nonmetal (E) and the number of
O atoms.
1. For oxoacids with the same number of oxygens around E, acid
strength increases with the electronegativity of E.
2. For oxoacids with different numbers of oxygens around a given

E, acid strength increases with number of O atoms.
18-54
Figure 18.12 The relative strengths of oxoacids.
H O I < H O Br < H O Cl

O
H O Cl << H O Cl O

O
18-55
Acidity of Hydrated Metal Ions
The aqueous solutions of certain metal ions are acidic because

the hydrated metal ion transfers an H+ ion to water.
If the metal ion, Mn+ , is small and highly charged, it has a high
charge density and withdraws sufficient electron density from the
O-H bonds of these bonded water molecules for a proton to be
released.
18-56
Figure 18.13 The acidic behavior of the hydrated Al3+ ion.
Electron density Nearby H2O acts

drawn toward Al3+ as base
H 2O H 3 O+
Al(H2O)63+ Al(H2O)5OH2+
18-57
18-58
Acid-base Properties of Salt Solutions

Salts that Yield Neutral Solutions
A salt consisting of the anion of a strong acid and the cation of

a strong base yields a neutral solution because the ions do not
react with water.
The anions of strong acids are the halide ions, except F-, and
those of strong oxoacids, such as NO3- and ClO4-.
The cations of strong bases are those from Group IA(1) and
Ca2+, Sr 2+, and Ba 2 + from Group 2A(2). Salts containing only
these ions, such as NaCl and Ba(N0 3 h. yield neutral solutions
because no reaction with water takes place.
18-59
Salts That Yield Acidic Solutions
A salt consisting of the anion of a strong acid and the cation of a weak
base yields an acidic solution because the cation acts as a weak acid,
and the anion does not react.
Small, highly charged metal ions make up another group of cations

that yield H3O+ in solution. For example, Fe(NO)3 produces an acidic
solution because the hydrated Fe3+ ion acts as a weak acid, whereas the
NO3- ion, the anion of a strong acid, does not react:
18-60
Salts That Yield Acidic Solutions
A third group of salts that yield H3O+ ions in solutions consists of

cations of strong bases and anions of polyprotic acids that still have one
or more ionizable protons.
For example, NaH2PO4 yields an acidic solution because Na+, the
cation of a strong base, does not react, while H2PO4-, the first anion of
the weak polyprotic acid H3PO4 , is also a weak acid:
18-61
Salts That Yield Basic Solutions
A salt consisting of the anion of a weak acid and the cation of a strong
base yields a basic solution in water because the anion acts as a weak
base, and the cation does not react. The anion of a weak acid accepts
a proton from water to yield OH- ion.
Sodium acetate, for example, yields a basic solution because the Na+
ion, the cation of a strong base, does not react with water, and the
CH3COO- ion, the anion of the weak acid CH3COOH, acts as a weak
base:
18-62
Table 18.3
18-63
SAMPLE PROBLEM 18.10 Predicting Relative Acidity of Salt Solutions
PROBLEM: Predict whether aqueous solutions of the following are acidic,

basic, or neutral, and write an equation for the reaction of any
ion with water:
(a) Potassium perchlorate, KClO4 (b) Sodium benzoate, C6H5COONa
(c) Chromium trichloride, CrCl3 (d) Sodium hydrogen sulfate, NaHSO4
PLAN: Consider the acid-base nature of the anions and cations. Strong
acid-strong base combinations produce a neutral solution; strong
acid-weak base, acidic; weak acid-strong base, basic.
SOLUTION: (a) The ions are K+ and ClO4- , both of which come from a strong
base(KOH) and a strong acid(HClO4). Therefore the solution will be neutral.
(b) Na+ comes from the strong base NaOH while C6H5COO- is the anion of a
weak organic acid. The salt solution will be basic.
(c) Cr3+ is a small cation with a large + charge, so its hydrated form will react
with water to produce H3O+. Cl- comes from the strong acid HCl. Acidic solution.
(d) Na+ comes from a strong base. HSO4- can react with water to form H3O+.
So the salt solution will be acidic.
18-64
Salts of Weakly Acidic Cations and Weakly Basic Anions
If salts consisting of a cation that acts as a weak acid and an anion

that acts as a weak base. In these cases. and there are quite a few, both
ions react with water.
It makes sense, then, that the overall acidity of the solution will depend
on the relative acid strength or base strength of the separated ions.
which can be determined by comparing their equilibrium constants.
For example, will an aqueous solution of ammonium hydrogen sulfide,
NH4HS, be acidic or basic? First, we write equations for any reactions
that occur between the separated ions and water.
Ammonium ion is the conjugate acid of a weak base, so it acts as a
weak acid:
Hydrogen sulfide ion is the anion of the weak acid HzS, so it acts as a
weak base:
18-65
Salts of Weakly Acidic Cations and Weakly Basic Anions
We must compare the Ka of NH4+ with the Kb of HS-. Recall that only
molecular compounds are listed in Ka and Kb tables, so we have to
calculate these values for the ions:
The difference in magnitude of the equilibrium constants (Kb = 200 Ka)

tells us that the acceptance of a proton from H2O by HS- proceeds
further than the donation of a proton to H2O by NH4+. In other words,
because Kb of HS- > Ka of NH4+, the NH4HS solution is basic.
18-66
SAMPLE PROBLEM 18.11 Predicting the Relative Acidity of Salt

Solutions from Ka and Kb of the Ions
PROBLEM: Determine whether an aqueous solution of zinc formate,

Zn(HCOO)2, is acidic, basic, or neutral.
PLAN: Both Zn2+ and HCOO- come from weak conjugates. In order to find
the relatively acidity, write out the dissociation reactions and use the
information in Tables 18.2 and 18.7.
SOLUTION:
Zn(H2O)62+(aq) + H2O(l) Zn(H2O)5OH+(aq) + H3O+(aq)
HCOO-(aq) + H2O(l) HCOOH(aq) + OH-(aq)
Ka Zn(H2O)62+ = 1x10-9
Ka HCOO- = 1.8x10-4 ; Kb = Kw/Ka = 1.0x10-14/1.8x10-4 = 5.6x10-11
Ka for Zn(H2O)62+ >>> Kb HCOO-, therefore the solution is acidic.
18-67
Molecules as Lewis Acids

An acid is an electron-pair acceptor.
A base is an electron-pair donor.
Lewis Acids with Electron-Deficient Atoms
F F
H H
B + N B N
F F HH F F HH
acid base adduct
18-68
Lewis Acids with Polar Multiple Bonds
18-69
Metal Cations as Lewis Acids
18-70
SAMPLE PROBLEM 18.12 Identifying Lewis Acids and Bases
PROBLEM: Identify the Lewis acids and Lewis bases in the following reactions:
(a) H+ + OH- H2O

(b) Cl- + BCl3 BCl4-
(c) K+ + 6H2O K(H2O)6+
PLAN: Look for electron pair acceptors (acids) and donors (bases).
SOLUTION: acceptor
(a) H+ + OH- H2O
donor
donor
(b) Cl- + BCl3 BCl4-
acceptor
acceptor
(c) K+ + 6H2O K(H2O)6+
donor
18-71
18-72
18-73

Acid Base Equilibria

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Acid Base Equilibria

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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 Brnsted-Lowry Acid-Base Definition

18.4 Solving Problems Involving Weak-Acid Equilibria

18.5 Weak Bases and Their Relations to Weak Acids

18.6 Molecular Properties and Acid Strength

18.7 Acid-Base Properties of Salt Solutions

18.8 Electron-Pair Donation and the Lewis Acid-Base Definition

18.1 Acids and Bases in Water

Water is a product in all reactions between strong acids and strong

Furthermore, whenever an acid dissociates in water, solvent molecules

The hydrated proton is usually shown in the text as H3O+(aq), although in

Classical Acids- Bases Definition

Variation in Acid Strength: The Acid-Dissociation Constant (Ka)

Figure 18.2 The extent of dissociation for strong acids.

Strong acid: HA(g or l) + H2O(l) H3O+(aq) + A-(aq)

Figure 18.3 The extent of dissociation for weak acids.

Weak acid: HA(aq) + H2O(l) H3O+(aq) + A-(aq)

Strong acids dissociate completely into ions in water.

HA(g or l) + H2O(l) H3O+(aq) + A-(aq) Kc >> 1

Weak acids dissociate very slightly into ions in water.

HA(aq) + H2O(l) H3O+(aq) + A-(aq) Kc << 1

The Acid-Dissociation Constant

[H3O+][A-] Larger Ka higher [H3O+]

The Acid-Dissociation Constant

Classifying the Relative Strengths of Acids and Bases

Classifying the Relative Strengths of Acids and Bases

PROBLEM: Classify each of the following compounds as a strong acid,

SOLUTION: (a) Strong acid - H2SeO4 - the number of O atoms exceeds

(c) Strong base - KOH is a Group 1A(1) hydroxide.

18.2 Autoionization of Water and the pH Scale

H2O(l) + H2O(l) H3O+(aq) + OH-(aq)

The Ion-Product Constant for Water

Kc[H2O]2 = Kw = [H3O+][OH-] = 1.0 x 10-14 at 250C

A change in [H3O+] causes an inverse change in [OH-].

In an acidic solution, [H3O+] > [OH-]

The relationship between [H3O+] and [OH-] and the

[H3O+] Divide into Kw [OH-]

[H3O+] > [OH-] [H3O+] = [OH-] [H3O+] < [OH-]

ACIDIC NEUTRAL BASIC

SAMPLE PROBLEM 18.2 Calculating [H3O+] and [OH-] in an Aqueous

PROBLEM: A research chemist adds a measured amount of HCl gas to pure

SOLUTION: K = 1.0x10-14 = [H O+] [OH-] so

[OH-] = Kw/ [H3O+] = 1.0x10-14/3.0x10-4 = 3.3x10-11M

[H3O+] is > [OH-] and the solution is acidic.

Table 18.1 The Relationship Between Ka and pKa

Acid Name (Formula) Ka at 250C pKa

Hydrogen sulfate ion (HSO4-) 1.02x10-2 1.991

Hypobromous acid (HBrO) 2.3x10-9 8.64

Phenol (C6H5OH) 1.0x10-10 10.00

SAMPLE PROBLEM 18.3 Calculating [H3O+], pH, [OH-], and pOH

PROBLEM: In an art restoration project, a conservator prepares copper-

For 0.3M HNO3, [H3O+] = 0.30M and -log [H3O+] = 0.52 = pH

For 0.0063M HNO3, [H3O+] = 0.0063M and -log [H3O+] = 2.20 = pH

Figure 18.7 Methods for measuring the pH of an aqueous solution.

18.3 Brnsted-Lowry Acid-Base Definition

An acid is a proton donor, any species which donates a H+.

A base is a proton acceptor, any species which accepts a H+.

An acid-base reaction can now be viewed from the standpoint

Figure 18.8 Proton transfer as the essential feature of a Brnsted-

NH3 H 2O NH4+ OH-

Table 18.2 The Conjugate Pairs in Some Acid-Base Reactions

Acid + Base Base + Acid