9 Aqueous Solutions and Chemical Equilibrium

9A The Chemical Composition of Aqueous Solutions

9A-1 Classifying Solutions of Electrolytes
Table 9-1 Classification of Electrolytes
Strong Weak
1. Inorganic acids such as HNO3, 1. Many inorganic acids, including H2CO3,
HClO4, H2SO4, HCl, Hl, HBr, H3PO4, H2S, H2SO3
HClO3, HBrO3 2. Most organic acids
2. Alkali and alkaline-earth 3. Ammonia and most organic bases
hydroxides
4. Halides, cyanides, and thiocyanates of Hg,
3. Most salts Zn, and Cd
Salt: reaction of an acid with a base, NaCl, Na2SO4, and NaOOCCH3

9A-2 Acids and Bases

1923, J. N. Brnsted (Denmark) and J. M. Lowry (England),
Brnsted - Lowry theory:
Acid proton donor
Base proton acceptor.

What are Conjugate Acids and Bases?

Acid1 base1 + proton; Acid1 and base1: conjugate acid/base pair
Base2 proton + Acid2
Acid1 + Base2 base1 + Acid2 neutralization

NH3 + H 2O NH4+ + OH-

base1 Acid2 conjugate acid1 conjugate base2

H 2O + HNO2 H3O+ + NO2-

base1 Acid2 conjugate acid1 conjugate base2

NO2- + H 2O HNO2 + OH-

base1 Acid2 conjugate acid1 conjugate base2
9A-3 Amphiprotic Species
Species that posses both acidic and basic properties are amphiprotic.
Amphiprotic solvent (that can act either as an acid or as a base):
Water, methanol, ethanol, and anhydrous acetic acid.

NH3 + CH3OH NH4+ + CH3O-

base1 Acid2 conjugate acid1 conjugate base2

CH3OH + HNO2 CH3OH2+ + NO2-

base1 Acid2 conjugate acid1 conjugate base2

H2PO4- + H3O+ H3PO4 + H 2O

base1 Acid2 acid1 base2

H2PO4- + OH- HPO42- + H 2O

acid1 base2 base1 Acid2

Zwitterions: a species that bears both a positive and a negative charge.

NH2CH2COOH NH3+CH2COO -
glycine zwitterion

RCOOH + RNH2 RCOO- + RNH3+

acid1 base2 base1 Acid2

9A-4 Autoprotolysis
self-ionization (autoionization) to form a pair of ionic species

base1 Acid2 autoprotolysis acid1 base2

H 2O + H 2O H 3O + + OH-
CH3OH + CH3OH CH3OH2+ + CH3O-
HCOOH + HCOOH HCOOH2+ + HCOO-
NH3 + NH3 NH4+ + NH2-

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9A-5 Stength of Acids and Bases
Strongest acid HClO4 + H2O H3O+ + ClO4- Weakest base
HCl + H2O H3O+ + Cl-
H3PO4 + H2O H3O+ + H2PO4-
Al(H2O)63+ + H2O H3O+ + AlOH(H2O)52+
HC2H3O2 + H2O H3O+ + C2H3O2-
H2PO4- + H2O H3O+ + HPO42-
Weakest acid Strongest base
NH4+ + H2O H3O+ + NH3

Fig. 9-1 Dissociation reactions and relative strengths of some common acids and their
conjugate bases. Note that HCl and HClO4, are completely dissociated in water.

The tendency of a solvent to accept or donate protons determines the strength of a solute
acid or base dissolved in it.
In H2O: HCl and HClO4 strong acid
In anhydrous acetic acid: HClO4 stronger than HCl (dissociation >5000x)

CH3COOH + HClO4 CH3COOH2+ + ClO4-

base1 Acid2 Acid1 Base2

differentiating solvent: Acetic acid

(various acids dissociate to different degree different strength)
in acetic acid: HClO4 > HCl > HNO3 > H2SO4

leveling solvent: Water for HClO4, HCl, HNO3, and H2SO4.

(several acids are completely dissociated the same strength)

9B Chemical Equilibrium
9B-1 The Equilibrium State

H3AsO4 + 3I- + 2H+ H3AsO3 + I3- + H2O (4-5)

orange-red color appear
H3AsO3 + I3- + H2O H3AsO4 + 3I- + 2H+
orange-red color disappear
The Le Chtelier principle: the position of chemical equilibrium always shifts in a
direction as to relieve a stress that is applied to the system.
The mass-action effect: shift in the position of an equilibrium caused by adding one of
the reactants or products to a system.
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Chemical reaction do not cease at equilibrium. Instead, the amounts of reactants and
products are constant because the rates of the forward and reverse processes are
identical.
Thermodynamics: a branch of chemical science, deals with the flow of heat and energy
in chemical reactions. The position of a chemical equilibrium is related to these energy
changes.

9B-2 Equilibrium-Constant expressions

[Y ] y [ Z ] z aYy a Zz
wW + xX yY + zZ K= K=
[W ] w [ X ] x aWw a Xx

9B-3 Types of equilibrium constants encountered in analytical chemistry

Table 9-2 Equilibria and equilibrium constant of importance to analytical chemistry
Type of Names and symbol Typical Equilibrium-constant
equilibrium of equil. const. Example expression
Dissociation of Ion-product const.
2H2O H3O+ + OH- Kw= [H3O+] [OH-]
water Kw
Heterogenous
equilibrium between
Solubility
a slightly soluble BaSO4 Ba2+ + SO42- Ksp= [Ba2+] [SO42-]
product, Ksp
substance and its ions
in a saturated soln
CH3COOH + H2O [H 3O + ][CH 3COO - ]
Ka =
Dissociation Dissociation H3O+ + CH3COO- [CH 3COOH]
of a weak constant, Ka or
acid or base Kb CH3COO- + H2O [OH - ][CH 3COOH ]
Kb =
OH- + CH3COOH [CH COO - ] 3

Formation of Formation [Ni(CN) 24- ]

2+ -
Ni + 4CN Ni(CN) 4 2-
4 =
a complex ion constant, n [Ni 2+ ][CN - ] 4
Oxidation/ [Mn 2 + ][Fe3+ ]5
MnO4 + 5Fe2+ + 8H+ K redox =
reduction Kredox
Mn2+ + 5Fe3+ + H2O [MnO 4 ][Fe2 + ]5 [H + ]8
equilibrium
Distribution equilibrium [I 2 ]org
for a solute between Kd I2(aq) I2(org) Kd =
immiscible solvents [I 2 ]aq

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9B-4 Applying the Ion-Product Constant for Water
2H2O H3O+ + OH- Table 4-3
[H 3 O + ][OH - ] Variation of Kw with Temperature
K= Temperature Kw pKw
[H 2 O] 2
0 0.114 10-14
K[H2O]2 = Kw = [H3O+][OH-] 25 1.01 10-14 (14)
pKw = pH + pOH 50 5.44 10-14
At 25C, pKw = 14.00 100 49 10-14

Ex 9-1 Calculate the [H3O+] and [OH-] of pure water at 25C and 100C.
[H3O+] = [OH-], [H3O+]2 = [OH-]2 = Kw
At 25C, [H3O+] = [OH-] = 1.00 10 14 = 1.00 10 7
At 100C, [H3O+] = [OH-] = 49 10 14 = 7.0 10 7

Ex 9-2 Calculate the [H3O+] and [OH-] and the pH and pOH of 0.200 M aqueous NaOH
at 25C.
[OH-]= 0.200 + [H3O+], [OH-] 0.200, pOH = -log 0.200 =0.699
14
Kw 1.00 10
[H 3 O + ] = -
= = 5.00 10 14 M , pH =-log 5.0010-14 =13.301
[OH ] 0.200

9B-4 Applying the Solubility-Product Constants

Ba(IO3)2(s) Ba2+(aq) + 2IO3-(aq)
[Ba 2+ ][IO 3- ] 2
K= ; K [Ba(IO3)2(s)]= Ksp =[Ba2+][IO3-]2= 1.5710-9
[Ba(IO3 ) 2 ( s )]

Ex 9-3 How many grams of Ba(IO3)2 (487 g/mol) can be dissolved in 500 mL of water
at 25C?
[Ba(IO3)2] = [Ba2+], [IO3-] = 2[Ba2+]
[Ba2+][IO3-]2 = 4[Ba2+]3 = 1.5710-9
2+ 1.57 10 9
solubility = [Ba ] = 3 = 7.32 10 4 M
4
mass Ba(IO3)2 = 7.32 10-4 500 0.487 = 0.178 g

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Ex 9-4 Calculate the [Ba(IO3)2] in a 0.0200 M Ba(NO3)2 solution.
[Ba(IO3)2] = [IO3-], [Ba2+] = 0.0200 + [IO3-] 0.200
[Ba2+][IO3-]2 = (0.0200 + [IO3-])[IO3-]2 = 1.57 10-9
9
0.0200 [IO3-]2 = 1.57 10-9 ; [IO3-] = 1.57 10 = 2.80 10-4 M
0.0200
solubility of Ba(IO3)2 = [IO3-] = (2.80 10-4 M) = 1.40 10-4 M

Ex 9-5 Calculate the molar solubility of [Ba(IO3)2] in a ( 200 mL 0.0100 M Ba(NO3)2 +

100 mL 0.100 M NaIO3) soln.
No. mmol Ba2+ = 200 mL 0.0100 M = 2.00 mmol
No. mmol IO3- = 100 mL 0.100 M = 10.0 mmol
No. mmol excess IO3- = 10.0 2(2.00) = 6.0 mmol
[IO3-] = 6.0 mmol/300 mL = 0.0200 M
molar solubility of Ba(IO3)2 = [Ba2+]
[IO3-] = 0.0200 + 2[Ba2+] 0.0200
1.57 10 9
2+
solubility of Ba(IO3)2 = [Ba ] = 2
= 3.93 10 6 M
0.0200

9B-6 Applying Acid and base Dissociation Constants

HNO2 + H2O H3O+ + NO2- NH3 + H2O NH4+ + OH-
[H 3O + ][ NO 2 ] [ NH +4 ][OH - ]
Ka = Kb =
[HNO 2 ] [ NH 3 ]
Dissociation constants for conjugated acid/base pairs
NH3 + H2O NH4+ + OH- NH4+ + H2O NH3 + H3O+
[ NH +4 ][OH - ] [ NH3 ][H 3O + ] Ka Kb = Kw
Kb = Ka =
[ NH 3 ] [ NH +4 ]

Ex 9-6 What is Kb for the equilibrium CN- + H2O HCN + OH-

K w 1.00 10 14
HCN: Ka = 6.2 10 -10
; Kb = = 10
= 1.61 10 5
Ka 6.2 10

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[H3O+] in a weak acid solution

HA + H2O H3O+ + A- [H 3O + ]2
Ka =
+
[H O ][A ] - C HA [H 3O + ]
Ka = 3
[HA] [H3O+]2 + Ka[H3O+] - KaCHA = 0
2 H2O H3O+ + OH- - K a + K a 2 + 4 K a C HA
+
Kw = [H3O+][OH-] [H 3O ] ==
2
[A-] [H3O+]
[H 3O + ]2
-
CHA = [A ] + [HA] if [H3O+] << CHA, K a =
C HA
= [H3O+] + [HA]
[HA] = CHA - [H3O+] [H 3O + ] = K a C HA

Ex 9-7 Calculate the [H3O+] in 0.120 M nitrous acid

+ -
HNO2 + H2O H3O+ + NO2- K a = [H 3O ][NO 2 ] = 7.1 10 4
[HNO 2 ]
[H3O ] = [NO2 ], [HNO2] = 0.120 - [H3O+]
+ -

[H3O + ]2
= 7.1 10 4
+
if [H3O ] << 0.120
0.120

[H 3O + ] = 0.120 7.1 10 4 = 9.2 10 3 M

Ex 9-8 Calculate the [H3O+] in 2.0 10-4 M aniline hydrochloride, C6H5NH3Cl

C6H5NH3+ + H2O C6H5NH2 + H3O+ [H3O + ][C6 H5 NH 2 ]
Ka = = 2.51 105
[C6 H5 NH3+ ]
[H3O+] = [C6H5NH2], [C6H5NH3+] = 2.0 10-4 - [H3O+]
+ 2
if [H3O+] << 2.0 10-4 [H3O ] = 2.51 105
2.0 10 4
[H 3O + ] = 5.02 109 = 7.09 105 M (not <<<< 2.0 10-4)
[H 3O + ]2
= 2.51 10 5 [H3O ] + 2.5110 [H3O ] 5.0210 = 0
+ 2 -5 + -9

2.0 10 4
+ 2.5110 5 + (2.5110 5 ) 2 + 4 5.02 10 9
[H 3O ] = = 5.94 10 5 M
2

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[H3O+] in a weak base solution
+ -
NH3 + H2O NH4+ + OH- ; K b = [NH 4 ][OH ]
[ NH 3 ]
2H2O H3O + OH ; Kw = [H3O ][OH-]
+ - +

[OH ] = K bC B

Ex 9-9 Calculate the [OH-] in 0.0750 M NH3 solution

NH3 + H2O NH4+ + OH-
[NH +4 ][OH - ] K w 1.0 10 14
Kb = = = = 1.75 10 5 M
[ NH3 ] K a 5.70 10 10

[NH4+]= [OH-], [NH4+]+ [NH3] = C NH 3 = 0.0750M

[OH ]2
= 1.75 10 5
-
[NH3] =0.0750 - [OH ]
-
0.0750 [OH ]
if [OH-] << 0.0750 [OH-]2 0.0750 1.75 10-5
[OH-] = 1.15 10-3 M

Ex 9-10 Calculate the [OH-] in 0.0100 M sodium hypochlorite solution

OCl- + H2O HOCl + OH- HOCl: Ka = 3.0 10-8
[HOCl][OH- ] K w 1.0 10 14
Kb = = = = 3.33 10 7 M
[OCl ] K a 3.0 10 8

[HOCl]= [OH-], [OCl-]+ [HOCl] = 0.0100M

[OCl-] = 0.0100 - [OH-] 0.0100 (assume [OH-] << 0.0100)
[OH ]2
= 3.33 10 7 [OH-] = 5.8 10-5 M
0.0100

9C Buffer Solutions
Buffer: a mixture of a weak acid and its conjugate base or a weak base and its
conjugate acid that resists changes in pH of a solution

9C-1 Calculation of the pH of Buffer Solutions

*Weak Acid/Conjugate Base Buffers

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 HA + H2O H3O+ + A- A- + H2O OH- + HA
[H 3O + ][A - ] K w [OH ][HA]
Ka = Kb = =
[HA] Ka [A - ]
[HA] = CHA - [H3O+] + [OH-], [HA] CHA C
[H 3O + ] = K a HA
[A-] = CNaA + [H3O+] - [OH-], [A-] CNaA C NaA

Ex. 9-11 What is the pH of a solution that is 0.400 M in HCOOH and 1.00 M in
HCOONa?
HCOOH + H2O H3O+ + HCOO- Ka = 1.80 10-4
HCOO- + H2O HCOOH + OH- Kb = K w = 5.56 10-11
Ka
[H 3O + ][HCOO - ] -
Ka = = 1.80 10 4 [HCOO ] CHCOO- = 1.00;
[HCOOH]
0.400
[HCOOH] CHCOOH = 0.400 [H 3O + ] = 1.80 10 4 = 7.20 10 5
1.00
[H3O+] << CHCOOH and [H3O+] << CHCOO- are valid.
pH = -log (7.20 10-5) = 4.14

*Weak Base/Conjugate Acid Buffers

Ex. 9-12 Calculate the pH of a solution that is 0.200 M in NH3 and 0.300 M in
NH4Cl.
NH4+ + H2O NH3 + H3O+ Ka = 5.70 10-10
K w 1.00 10 14
NH3 + H2O NH4+ + OH- Kb = = = 1.75 10-5
Ka 5.70 10-10
[NH4+] = CNH Cl + [OH-] - [H3O+] CNH Cl + [OH-]
4 4

[NH3] = CNH + [H3O ] - [OH ] CNH - [OH-]

+ -
3 3
[NH4+] CNH Cl = 0.300; [NH3] CNH = 0.200
4 3

K a [ NH 4+ ] 5.70 1010 0.300

[H 3O + ] = = = 8.55 1010
[ NH3 ] 0.200
1.00 1014
[OH ] = 10
= 1.17 10 5 << CNH4Cl or CNH3
8.55 10
pH = - log (8.55 10-10) = 9.07

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9C-2 Properties of Buffer solutions

*The Effect of Dilution:

Fig. 9-4 The effect of dilution of the pH of

buffered and unbuffered solutions. The
dissociation constant for HA is 1.00 10-4.
Initial solute concentrations are 1.00 M
Concentration of reagents, M
*The Effect of Added Acids and bases
Ex. 9-13 calculate the pH change that takes place when a 100-mL portion of (a)
0.0500 M NaOH and (b) 0.0500 M HCl is added to 400 mL of the buffer
solution that was described in Ex. 9-12..
(a) Addition of NaOH converts part of the NH4+ in the buffer to NH3:
NH4+ + OH- NH3 + H2O Ka = 5.70 10-10
400 0.200 + 100 0.0500 85.0
C NH 3 = = = 0.170M
500 500
400 0.300 100 0.0500 115
C NH 4 Cl = = = 0.230M
500 500
0.230
[ H 3O + ] = 5.70 10 10 = 7.71 10 10
0.170
pH = - log (7.71 10-10) = 9.11, pH = 9.11 - 9.07 = 0.04

(b) Addition of HCl converts part of the NH3 in the buffer to NH4+:
NH3 + H3O+ NH4+ + H2O
400 0.200 100 0.0500 75.0
C NH 3 = = = 0.150M
500 500
400 0.300 + 100 0.0500 125
C NH 4 Cl = = = 0.250M
500 500
0.250
[H 3O + ] = 5.70 10 10 = 9.50 10 10
0.150
pH = - log (9.50 10-10) = 9.02, pH = 9.02 - 9.07 = - 0.05

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*The Composition of Buffer Solutions as a function of pH; Alpha Values
In a HAc/NaAc buffer solution
[HOAc] [OAc- ]
cT = cHOAc + cNaOAc, 0 = , 1 = , 0 + 1 = 1
CT CT
HOAc + H2O H3O+ + OAc-
[H 3 O + ][OAC - ] K a [ HOAc] [ H 3 O + ][OAC - ]
Ka = , [OAC ] = [ HOAc] =
-
,
[HOAc] [H 3O + ] Ka

K a [ HOAc] [H 3O + ] + K a [HOAc] [H 3O + ]
cT = [ HOAc] + = [ HOAc] 0 = =
[H 3O + ] [H 3O ]
+
CT [H 3 O + ] + K a

[ H 3 O + ][OAc - ] - [H 3 O ] + K a
+
[OAc - ] Ka
cT = + [OAC ] = [OAC ]
-
1 = =
Ka Ka CT [H 3O + ] + K a
Alpha values depend only on [H3O+] and Ka and are independent on cT.

*Buffer Capacity, :
the number of moles of strong acid or strong base that causes 1.00 L of the buffer to
undergo a 1.00-unit change in pH.
dC b dC a
= =
dpH dpH

Fig. 9-6. Buffer capacity as

a function of the ratio
Fig. 9-5. Variation in with pH. Note that most of the
CNaA/CHA.
transition between 0 and 1 occurs within 1 pH unit of
the crossover point of the two curves. The crossover point
where 0 = 1 = 0.5 occurs when pH = pKHOAc = 4.74

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Preparation of Buffers
Ex. 9-14 Describe how you might prepare approximately 500.0 mL or a pH 4.5 buffer
solution from 1.0 M acetic acid (HOAc) and sodium acetate (NaOAc).
pH 4.5 [H3O+] = 10-4.5 = 3.16 10-5 M
[ H 3 O + ][OAC - ] 5 [OAC - ] 1.75 10 5 1.75 10 5
Ka = = 1.75 10 = = = 0.5534
[ HOAc] [HOAc] [H 3 O + ] 3.16 10 5
[OAc-] = 0.5534 1.0 M = 0.5534 M
mass NaOAc = 0.5534 M 0.5 L 82.034 g/mol NaOAc = 22.7 g NaOAc
Dissolve 22.7 g NaOAc in the HOAc solution (in 500 mL volumetric flask). Check
the pH with a pH meter, adjust the pH by adding a small amount of acid or base.

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