ANORGANIC CHEMISTRY
ASEP MUHAMAD SAMSUDIN, S.T., M.T.
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Chapter 18
Acid-Base Equilibria
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Acid-Base Equilibria
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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.
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The net ionic equation of this reaction shows water is the product:
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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.
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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.
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[H3O+][A-]
Kc[H2O] = Ka =
[HA] smaller Ka lower [H3O+]
weaker acid
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SAMPLE PROBLEM 18.1 Classifying Acid and Base Strength from the
Chemical Formula
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.
(d) Weak base - (CH3)2CHNH2 has a lone pair of electrons on the N and
is an amine.
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H2O(l) H2O(l)
H3O+(aq) OH-(aq)
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[H3O+][OH-]
Kc =
[H2O]2
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PLAN: Use the Kw at 250C and the [H3O+] to find the corresponding [OH-].
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Figure 18.5
The pH values of
some familiar
aqueous solutions.
pH = -log [H3O+]
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7.1x10-4 3.15
Nitrous acid (HNO2)
1.8x10-5 4.74
Acetic acid (CH3COOH)
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Figure 18.6 The relations among [H3O+], pH, [OH-], and pOH.
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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
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pH (indicator) paper
pH meter
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+ +
HCl H 2O Cl- H 3 O+
(acid, H+ donor) (base, H+ acceptor)
Lone pair
binds H+
+ +
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Conjugate Pair
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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)
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.
Figure 18.9
Strengths of
conjugate acid-
base pairs.
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PLAN: Write out the dissociation equation. Use pH and solution concentration
to find the Ka.
Ka = [H3O+][PAc-]
[HPAc]
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[H3O+] = 10-pH = 2.4x10-3 M which is >> 10-7 (the [H3O+] from water)
(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
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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]
Initial 0.10 - 0 0
Change -x - +x +x
Equilibrium 0.10-x - x x
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[H3O+][Pr-] (x)(x)
1.3x10-5 = =
[HPr] 0.10
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[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
2-(aq) 3-(aq)
[H3O+][PO43-]
HPO4 + H2O(l) PO4 + H3 O+(aq) Ka3 =
[HPO42-]
= 4.2x10-13
Ka1 > Ka2 > Ka3
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CH3NH2 H2O
methylamine
CH3NH3+ OH-
methylammonium ion
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continued
[(CH3)2NH2+][OH-]
Kb = 5.9x10-4 =
[(CH3)2NH]
(x) (x)
5.9x10-4 = x = 3.0x10-2M = [OH-]
1.5M
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SOLUTION:
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continued
x = 1.2x10-5M = [OH-]
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6A(16) 7A(17)
Electronegativity increases,
acidity increases
H 2O HF
Bond strength decreases,
acidity increases
H 2S HCl
H2Se HBr
H2Te HI
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H O I < H O Br < H O Cl
O
H O Cl << H O Cl O
O
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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.
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H 2O H 3 O+
Al(H2O)63+ Al(H2O)5OH2+
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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.
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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:
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Table 18.3
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Hydrogen sulfide ion is the anion of the weak acid HzS, so it acts as a
weak base:
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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:
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SOLUTION:
Zn(H2O)62+(aq) + H2O(l) Zn(H2O)5OH+(aq) + H3O+(aq)
Ka Zn(H2O)62+ = 1x10-9
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F F
H H
B + N B N
F F HH F F HH
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PROBLEM: Identify the Lewis acids and Lewis bases in the following reactions:
SOLUTION: acceptor
(a) H+ + OH- H2O
donor
donor
(b) Cl- + BCl3 BCl4-
acceptor
acceptor
(c) K+ + 6H2O K(H2O)6+
donor
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