Jean-Louis Burgot

Ionic

Equilibria Chemistry

in

Analytical

4^

Springer

Contents

Part I

General Considerations of Solutions

SolventsComposition
1.1 1.2 1.3 Definitions

3 3 3

Molecular Solvents Solvation of Solutes in Water

1.4.1 1.4.2
as a

Molecular Solvent

1.4

Solvent
to

5 Give H B onds
5 Moment 5 7 7 7

Ability
High

Value of Its

Dipolar

1.4.3
1.5 1.6 1.7

Dissociating
of
a

Power of Water

Definition of the Solution

Composition

Quantity
Different 1.7.1

Substance

Expressions

Composition Expressed
The Molar

Composition in Quantity Composition

of the

8
of
a

Substance: 8 8 9

1.7.2 1.7.3 1.8

Molality
Molar Fraction

Calculation of the

Molality

and the

Molarity

of

Solution 9 13 13

from Its Molar Fraction 2

Thermodynamics
2.1 2.2 Gibbs Free

and

Equilibrium
and Useful Work

Chemical Potential

Energy Change AGsyst

Available from the Process

2.3 2.4 Molar Reaction Gibbs Function

16 18

2.5 2.6
2.7 2.8

Evolving Reactions and Equilibrium Conditions Equilibrium Conditions and Mass Law
Chemical Potentials and Standard States
Redox Reaction: Redox Brief Daniell's Galvanic Cell

19
21 24 25

Couples

Description of an Electrochemical Cell:

26

ix

Contents

2.9

Electromotive Force of

Galvanic Cell, Cell Potential

a

Difference,
28 30

Maximum Work Available from

Chemical Reaction, and Nernst's

Equation
2.10 Electrode Potentials 2.11 Addition of Free

Enthalpies

and Calculation of Standard Electrode 32 37 37 37 38

Potentials from Other Standard Electrode Potentials 3 Activities and Activity Coefficients 3.1 3.2 3.3 3.4 Chemical On the

Equilibrium. Mass Law and Species Activities Physical Meaning of An Activity

Ionic Strength of a Solution Link Between Activities and Concentrations: The Activity Coefficients Standard States and Activity Coefficients Different Ways
to Write the Mass Law

40 40 41 42

3.5

3.6 3.7 3.8

Usual Conventions for Activities Determination of Activities

44
44 44 44

3.9

3.10 Part II 4

Uncharged Solutes 3.8.2 Activity of Anion: Activity of the Whole Electrolyte Calculation of Activity Coefficients and of Activities 3.9.1 Activity Calculation of Uncharged Species 3.9.2 Calculation of Activity Coefficients and Activities of Justification of Debye-Hiickel's Theory
3.8.1
Acids and Bases

44
Ions
..

44 47

EquilibriaAnalytical Applications
Strength
of Acids and Bases
51 51 52

Definitions of Acids and Bases: 4.1 4.2 4.3 4.4 Arrhenius Definition

Br0nsted-Lowry Definition
Inexistence of the Proton in Solution

53 54 55 and Br0nsted Theories in 55

Br0nsted Acidity and

Nature of the Nomenclature About the

Basicity

in Water:

Hydrated Proton in Water

4.5 4.6

Equivalence of the Arrhenius

of Acids and Bases

Aqueous Solutions
4.7

Other Theories

57
the

4.8
4.9

Qualitative Considerations Concerning

of Acids and Bases in Water

Strength
57

Quantitative
4.9.1 4.9.2

Considerations

Quantifying

of Acids and Bases: Dissociation Acids' Bases'

Strengths Acid Constants Ka and pKa

the

58 58 60 60 61 62

Strength Strength

4.10 Water Dissociation 4.11 Uselessness of the Kb Notion

4.12 A Brief View of the

Concept of pH

Contents

xi

4.13 The Poly acid Case

4.14 Distribution

62 63
Constants

Diagrams

4.15

Macroscopic and Microscopic Equilibrium

66
68

4.16 Predominant Species Area

4.17 Prevision of Acid-Base Reactions: of Acid-Base Reaction 4.18 4.19 5

Equilibrium

Constant 69 70 72 77 77 78

Acidity Leveling

Scale in Water of Acids and Bases in Water

Calculations of 5.1 5.2 5.3

pH Values in Aqueous Solutions Analytical Concentration pH of Pure Water Calculation of pH in Solutions of Strong Acids
5.3.1 5.3.2 5.3.3 General Relation

78
78

Simplified Equations

79 80
81 and Bases 82 82 83 the Calculation 83 84 86 88

5.4 5.5

Logarithmic Diagram pH in Solutions of Strong Bases pH in Solutions of Salts of Strong Acids

Ostwald's Dilution Law

5.6 5.7

pH

in Solutions of Weak Acids

5.7.1 5.7.2 5.7.3 5.8

General Equation

pH pH Calculations by Approximations Calculations with Hiigg's Diagrams

a

Permitting

pH

in

Weak Base Solution

The Base Concentration Is

5.8.1
5.8.2 5.9 5.10 5.11

High

88 89 91 92

The Basic Solution Is

Highly Diluted

pH of a Mixture of Strong Acids pH of a Mixture of Strong Bases pH of a Mixture of a Strong and a Weak Acid: Ionization Repression
pH pH
and of of
a a

92 93

5.12 5.13

Mixture of

Strong

and

Weak Base
a

an

Equimolecular Mixture

of

Weak Base

Weak Acid

93 94 95
96 100

5.14 5.15

5.16 5.17 5.18

5.19 6

pH Poly acid and Polybase Solutions of a Monosalt of a Diacid SolutionpH of an pH Ampholyte Solution pH of a Solution of an Amino-Acid pH of a Mixture of Two Weak Acids pH of a Mixture of a Weak Acid and a Weak B ase in Any Proportion: Interest in the Principal Reaction Concept pH Calculations Taking Activities into Account

of

100 104 107

Buffer Solutions

6.1 6.2

pH of
Acid

Buffer Solution Before Addition of Base

Strong
107 109

or a

pH

of

Buffer Solution After

Proton Addition

xii

Contents

6.3

Mechanism of the Buffer Effect 6.3.1

110 110 110 Ill Ill 113 114 115 116 119

6.4

Standpoint 6.3.2 Mathematical Standpoint Buffer CapacityBuffer Index

Mathematical Expression
Buffer of the Buffer Index

Chemical

6.5
6.6 6.7 6.8 6.9 7

Range

Mixtures of Several Buffers Buffer

Capacity

of

Polyacid

Some Buffers

Some General Points Concerning Titrations

7.1 7.2 7.3 7.4 7.5 General

Principle Terminology
Titration Error

of Titrimetric Methods

119
120

120 121 122 123 123 125 125

127 127 128 Indicators 130 130 131 131

Equivalents Types of

and Normal Solutions

Some Titration Forms Chemical Reactions Used in Titrations and Titration

7.6
7.7

Designations Conditions That the Titration Reaction Must Fulfill

Glassware Used in

7.8 7.9
8

Titrimetry

Titrations and Microinformatics: Current Trends

or

Neutralization 8.1 8.2 8.3

8.4

Acid-Base Indicators
on

General Considerations

Neutralization Indicators

Origin of the Color Change Categories of Neutralization

Some Indicators

8.5

Conditions for Use of Color Indicators 8.5.1 8.5.2

Color-Change
on

Interval

Influence of the Indicator Concentration

8.5.3

Color-Change Interval pH Change of the Solution Under Study by

of the Indicator Ionic

the

132 Addition 132 133 134 134 134 135 135

8.5.4

Strength

of the Solution

8.5.5
8.5.6

Nature of the Other Substances Present in Solution

Temperature

8.6
9

Uses of Neutralization Indicators

Acid-Base Titration Curves 9.1 9.2 9.3

Terminology

of Acid-B ase Titrati ons

General Considerations Fraction Titrated Neutralization of and Vice Versa 9.3.1

a

Concerning Acid-Base
a

Titration Curves: 135

Strong Acid with

Strong

Base

136 136

Shape of the Titration Curve

Contents

xiii

9.3.2 9.3.3 9.3.4 9.3.5 9.3.6

Justifications
Practical Conclusion: Choice of the Indicator Titration Error Titration of
a

138 140 140 Base with

a

Strong

Strong

Acid

141

Concentration Conditions That Must Be

to Obtain

Satisfactory

Titrations of

Respected Strong Acids

142

and Bases 9.4

Neutralization Titration Curve of a Weak Acid

with 9.4.1 9.4.2 9.4.3 9.4.4 9.4.5
a

Strong Base Shape of the Curve

Justifications Practical Conclusions: Choice of the Indicator Titration Error Conditions That Must be Fulfilled for

142 142 144 145 145

Satisfactory
146 146
148
a

Titrations 9.5
9.6

Titration of Titration of
Titration of

a
a

Weak Base with Weak Acid with

a a

Strong Acid
Weak Base

9.7
9.8

Mixture of
Mixture of and

Strong Strong

Acids with
Acid and

Strong

Base and 148

Inversely
Titration of with 9.9
a a a a Weak Acid

Strong Base
a a

Inversely
a

149

Titration of

Mixture of Weak Acids with

Strong

Base

150 151

9.10 Titration of

Polyacid

with

a a

Strong
Diacid

Base

9.11 Titration of the Monosalt of

155
157 with
a

10 Acid-Base Titrations: Further Theoretical Studies

10.1 Exact Equation of the Titration Curve of Base and

a

Strong Acid

Strong
157

Conversely;

Formula

Giving

the Titration Error

a

10.2 Exact Equation of the Titration Curve of

Weak Acid with 159

Strong Base and Conversely: Titration Error

etc

10.3 Exact Equations of the Titration Curves of Mixtures of Acids,

Bases, Polyacids, Polybases,

Index 10.5

160

10.4 Precision of Acid-Base Titrations Related to the

Sharpness
160

Expressions

of the

Sharpness Index
a a a a

161
a

10.5.1 Titration of 10.5.2 Titration of 10.5.3 Titration of 10.5.4 Titration of 10.7 Gran's

Strong Acid

with
a

Strong Base
B
ase

162 162 162 162

163 165

Weak Acid with Weak Base with Weak Acid with

Strong

a a

Strong Acid
Weak Base

10.6 Extent of the Titration Reaction

Diagram

11 Acid-Base Reactions and Chemical Analysis 11.1 The Concept of pH

11.2 11.3

169
169 169

Analytical Operations and pH Acidity of a Medium as an Index

of Its

Purity

170

xiv

Contents 11.4 On the Choice of 11.6 Direct Titrations

11.5 Direct Titrations of Acid

Examples of Acid-Base Titrations Compounds of Derivatives Exhibiting a Basic Character

Chemical Reaction (After Transformation)

170 171 176 179

11.7

Back Titrations
a

11.8 Titrations After Part III

181

Redox Phenomena and

Analytical Applications
193 193 197 199
and 200 201 205

12 Generalities

on

Oxidation-Reduction

12.1 Definitions 12.2 Oxidation Numbers 12.3 Redox Titrations and Oxidation Numbers

12.4 Particular Cases of Redox Reactions:

Disproportionation

Retrodisproportionation Reactions 12.5 Equilibration of Redox Reactions

13 Redox Reactions and Electrochemical Cells 13.1 Electrochemical Cells and Redox Reactions: Daniell's Galvanic Cell 13.1.1 13.1.2 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 13.10 Galvanic Cell

Example

of 205 206 207

Electrolytic

Cell
an

Nature of the Electrical Current in The

Electrochemical Cell

208 210 211 212 213 214 216 217

Hydrated

Electron

Cathode, Anode, and Charges of Electrodes

Electrochemical Cells and Classes of Electrodes Shorthand Notation for Electrochemical Cells Some

Reversibility

Examples

of Cells

Electrode Potentials: Nernst's Law Standard Electrode Potentials and Standard Reduction Potentials

of Some Redox Couples 13.12 Formal Potentials 14

at 298 K

220

13.11 Zero-Current Electrochemical Cell PotentialsConvention

223
225

Predicting Redox Reactions

14.1 14.2
Redox Phenomena and

229 229 233

or

Redox Phenomena,

Acidity Complexation, and Precipitation 14.2.1 The Stabilization of a Redox Couple by Complexation Precipitation of One of Its Members 14.2.2 The Increase or Decrease in the Oxidizing Strength
of One of Its Ox
or

234 235 239

Red Forms

14.3

Qualitative Prediction
Potentials

of Redox Reactions After Standard

Contents

xv

14.4

Drawbacks of the Prediction Rule Based

of Standard Potentials

on

the Sole Consideration 240

14.5 14.6

Quantitative

Character of

Redox Reaction
Redox Reactions Means

242 245

Kinetic Considerations

Concerning

15

Predicting Redox Reactions by Graphical

15.1 15.2 15.3
15.4 15.5 Predominance Areas of
a

247 247

Redox

Couple Knowledge

Qualitative
Frost

Prediction of Redox Reactions from the

of the Predominance Areas

250 253 257 in

Diagrams 7pH Diagrams or Pourbaix Diagrams An Example of Application of Pourbaix Diagrams

Chemistry
Extension of Pourbaix

Analytical
261 263

15.6 16

Diagrams Containing Several

Calculating Equilibrium
Redox 16.1 16.2 16.3 16.4 16.5

Potentials of Solutions

Couples
Equilibrium Potentials
Potential of
a

265 and Electrode Potentials

265 266 266

269

Containing Only One Redox Couple General Case: Equilibrium Potential of a Solution Containing Two Redox Couples Determining the Ox and Red Concentrations of a Couple from the Known Equilibrium Potential by Graphical Means A Particular Case: The Exchange of Electrons is Accompanied by an Exchange of Protons or by an Exchange of Ligands
Case in Which One of the

Solution

270 271

16.6 16.7

Species

Redox is

Polynuclear

16.8

Equilibrium Potential of a Solution When it Contains an Ampholyte Potential of a Solution Containing a Mixture of the Reduced Polyfunctional Member of a Couple and of the Oxidized
Member of Another

272

Couple
Containing
a

274

16.9

Potential of of
a

Solution

Mixture of an Oxidized Form 276

277

16.10 16.11 16.12

Belonging to Two Couples General Considerations Concerning Redox Titrations Thermodynamic Condition for a Redox Titration Reaction Kinetic Conditions in Order to Achieve a Satisfactory Redox
Other Different Redox Titration Reaction Detection of the

First

Couple

and of Two Reduced Forms

277 278

16.13 16.14 16.15

Equivalence
on

Point of

Redox Titration

279 279
280 280 282 283 283

General Considerations

Internal Redox Indicators

Some Internal Redox Indicators

16.15.1
16.15.2

UO-Phenanthroline

16.15.3 16.15.4

Diphenylamine Methylene Blue Diphenylpyrazine

xvi 17 A Study of Some Redox Titration Curves 17.1

Contents

285 285

Titration of the Ferrous Ion

by

the Ceric Ion, One of the

Simplest Examples
17.1.1 17.1.2 17.2 Common

of

Redox Titration

Simplified Theoretical

Study
Titrations:

286 289

Further Considerations Titration Error 17.2.1 17.2.2 17.2.3

Rigorous Study Concerning Symmetrical

Consideration 1

290 290 290 291

Consideration 2 Consideration 3
Consideration 4 Consideration 5 Consideration 6 Consideration 7 of the Titration Curve of Stannic Ions

17.2.4
17.2.5 17.2.6 17.2.7 17.3

292 292 292 293

Study

IonsGeneralization to All 17.4 Redox Titrations in Which of Electrons and Protons 17.5 Cases in Which the Titration of the
or

by Asymmetrical Titrations a Simultaneous Exchange

Other Particules Exists

Chromous 294

297
on

Equivalence

Potential Values Depend

the 298 302 303 306 306

Concentration of One of the Reactants 17.6

Hypovanadous Ion by the Permanganate Ion

17.6.1 17.6.2 17.6.3 17.7

First Equivalence Point Second Equivalence Point

Third
a

Equivalence

Point

Titration of

Mixture

308 313 313

the Use 314 315 315 for Its Use 317 317 317 317

18 Oxidoreductimetry: Direct and Indirect Iodometries

18.1 18.2

Oxidoreductimetry
Nomenclature of the Titration Methods of Iodine
or

Involving

the Formation of Iodine

18.3 18.4 18.5

Physicochemical Properties Species of Iodine Exhibited Features by the Couple I2/I~ Interesting in Titrimetry 18.5.1 Stability
Some Predominance Areas of Some

of Iodine

18.5.2 18.5.3 18.5.4 18.5.5

18.5.6

Coloration
Solubilities Standard Potential Values of The Influence of

I2/I~ Couples

317 319

pH

Existence of the Fundamental Reaction of Direct and Indirect Iodometries 319

18.5.7 18.6 18.7 18.8

Detection of the

Equivalence Point

319 319 321 323

The Fundamental Reaction of Iodometries Iodine Solutions Thiosulfate Solutions

Contents

xvii

18.9

Examples of Titration by
18.9.1 18.9.2 18.9.3
18.9.4 18.9.5 18.9.6 18.9.7 18.9.8 and Sulfites

Direct

Iodometry Hydrogen Sulfites,

325

Determination of Sulfurous Acid,

325

Determination of Hydrogen Sulfide, Hydrogen Sulfides, and Sulfides Determination of Alkaline Cyanides: Fordos and Gelis's Method
Determination of

326

326 327 328

Hydrazine

and Its Derivatives

Determination of Arsenicals
Determination of Derivatives of Determination of Stannous Tin Determination of Mercurous Salts: Extension to the Determination of Mercuric Salts and to That of

Antimony+III

328 328

Reducing
329 330 330 331 332
333

Organic
18.9.9

Substances

Determination of

Thiocyanates

18.9.10 Determination of Thiols 18.9.11 Determination of Determination 18.9.12 Determination

Xanthogenates and Derivatives: of Hydrazoic Acid and of Azides of Hydroquinol

18.9.13 Determination of Vitamin C 18.10

Examples
18.10.1 18.10.2 18.10.3 18.10.4
18.10.5

of Titrations by Indirect Iodometry Recall of Information Titration of Nitrous Acid and Nitrites Determination of Determination of

336
336 336 337 337
'

Halogens Hypochlorites
at

Determination of Halogens

Oxidation Numbers +HI,

+V,+VII
18.10.6 18.10.7 Determination of Metallic Salts "at Their Maximum" Determinations of Arsenic and State +V 18.10.8 Determination of Salts 18.10.9 Determination of
..

340 340 342

Antimony

at

Oxidation

Hydrogen

Peroxide and of Peroxy

343

Aqueous Dioxygen
344

by
18.10.10
18.10.11 19

Winkler's Method

Determination of Peroxides and Determination of Diverse

Hydroperoxides Organic Compounds

344
344

Iodometry in Alkaline Medium, Iodatometry, Periodimetry, and Bromometry 19.1 Iodometry in Alkaline Medium
19.1.1 19.1.2 19.2 General Considerations

347 347

347 351 352 352 355

358

Applications
General Considerations

Iodatometry
19.2.1 19.2.2

Applications

19.3

Periodimetry

xvjjj

Contents

19.4

Bromatometry, Hypobromomctry,
19.4.1 19.4.2 19.4.3 General Considerations Oxidization Reactions Determinations

and

Bromometry

-^66 366 368

by Fixing

bromine into
or

an

Organic

Substrate Either by Substitution 20 Oxidizations with 20.1

by

Addition Ions

373

Some Titration Methods

Permanganate, Dichromate, and Ceric Involving a Reduction Reaction Oxidization with Permanganate Ions
20.1.1
20.1.2

377 377
377 382

General Considerations

20.2

Manganimetry in Acidic Medium 20.1.3 Manganimetry in Neutral and Weakly Alkaline Media.... 20.1.4 Manganimetry in Strongly Alkaline Medium 20.1.5 Determination of Organic Matters in Water Titrations with Dichromate Ions: Chromimetry

Applications

of

386 388 389

390

20.2.1 20.2.2

Definition General Considerations

390
390 393

20.2.3 20.3
20.3.1 20.3.2

Applications
Properties Advantages of Cerimetry
Standardized Solutions Some of Cerous and Ceric Salts

Titrations with Ceric Ions

394 395 396

397

20.3.3 20.3.4 20.4

20.4.1 20.4.2

Applications

Some Other

Cerimetry Oxydoreductimetric Titration

of

398
Methods 402 402 403 403 405 405 405

Titrations with Titanium HI Salts Titrations with Chromium II Salts Titrations with Ascorbic Acid Reactions in

20.4.3
21 Some 21.1

Applications of Redox Organic Analysis

21.1.1

Qualitative Analysis

Colorimetric

Analysis
Equivalence
a

21.1.2 Detection in Chromatography 21.1.3 21.1.4 21.2

Part IV Titration Reactions for Which the Detected Point Is
...

410
Redox Reaction

Through

the Occurrence of

411
412 412

Functional

Analysis

Inorganic Analysis
Complexation ReactionsAnalytical Applications

22 General Definitions and 22.1 22.2

Concerning Complexes

Rules of Nomenclature 423

Writing
General Definition of

Complexes

as

Complexes Compounds Resulting from

423 the Interaction of

Electron-Donating and Electron-Accepting Species

22.3 Limits of the Set of Complexes

424 425

Contents 22.4 and

xix

Writing

22.5

Electrical

Systematic Nomenclature of Complexes Charge of an Ion Complex

the

427 428

23 Some Elements
23.1 23.2

Concerning

Chemistry of Complexes

429 429
430

Attaining Complexes Some Ligands Found

23.3 23.4 24

Complexes 23.2.1 Some Monodentate Ligands 23.2.2 Some Polydentate Ligands Some Aspects of the Chemistry of Complexes State of the Ions in Aqueous Solution and Consequences
of

in Classical

430 431
433

436

Stability
24.1 24.2 24.3 24.4 24.5

Complexes: Some

Elements

Concerning

the 439

Kinetics of Their Formation Definition of

Complexes

in the Context of

Analysis

439 440

Stability of Complexes: Perfect and Imperfect Complexes Formation or Stability Constants of Complexes
General Some

441 442 444 446 448

449 453 456
..

Determining Stability Constants Examples of Calculations Carried Out with Stability

Methodology

of

Constants 24.6 24.7

Distribution Diagrams Formation Curve

The Factors

24.8 24.9

Complexes as Particle Donors Influencing the Stability of Complexes 24.10 Stability of Chelates: Chelate and Macrocyclic Effects 24.11 Kinetics of Complexes'Formation: Labile and Inert Complexes
25 Superimposition of Varied Equilibria to
25.1 25.2

459
461

Complexation Equilibria Superimposition of Several Complexation Equilibria An Important Particular Case of Parasitic Reactions:
Formation of the the

...

461

Complexes Hydroxo, Oxo, Hydrolysis of Metallic Ions 25.2.1 Hydrolysis of Metallic Ions
25.2.2 25.2.3
25.3 25.4

and

so

Forth from 462 462

Competition
Ligands

Between the Hydroxo Complexes and Other

464

ComplexationPrecipitation

Interaction: Formation
468 476

of Insoluble Oxides and Hydroxides Formation of Polynuclear Complexes; Polymerization Ability of Ligands to Complex Metallic Ions and Acidity of Solution
26

480 485
a

Conditional
26.1

Stability Constants Species Existing in Solution When

with EDTA

Metallic Ion Is Titrated

485
486

26.2

Conditional Constants, Parasitic Reaction Coefficients, and Apparent Concentrations

XX

Contents

26.3

26.4
26.5

Examples of Conditional Constants' Calculations Quantitative Changes in Coefficients a

Conditional Constants,

489 491 493

494 497 Constants

Masking, and Selective Complexations

in the Presence of Several Metallic Ions

26.6
26.7

Conditional Constants and Calculation of the Concentrations of the Different

Species in Solution Concept of Conditional Stability Concept of Conditional Constants

Case of Metal Indicators

26.8 26.9
27

Extension of the

499
500

About the Interest in the

Complexometry I: Mercurimetry (Votocek-Dubsky's Method) 27.1 The Major Difficulty Encountered During Complexometric
Titrations 27.2

503
503 505 506 507 510 511 513 513 514

Mercurimetry. Votocek-Dubsky's Method 27.2.1 Principle 27.2.2 Equivalence Point

27.2.3 27.2.4

Standard Solutions

Applications

28

Complexometry II: Titrations with EDTA 28.1 Some Properties of EDTA

28.1.1 28.1.2 28.1.3 28.2 Acid Dissociation Constants of EDTA EDTA: A

Very

Powerful

Chelating Agent

515 516 517

Formation Reactions of Metal-EDTA Chelates

a

Direct Titration Curve of

Metallic Ion with EDTA

29

Complexometry
Titrations
29.1

III: Metal Cation Indicators and Types of EDTA

525 Indicators
Function 525

Some Metal Ion

29.1.1

Possessing a Phenol 29.1.2 Triphenylmethane Derivatives

29.2

Azo Derivatives

525 527 529 530

530 531 532 533 534

29.1.3 Derivatives of Miscellaneous Structures

Types of EDTA Titrations

29.2.1
29.2.2 29.2.3 29.2.4 29.2.5 29.2.6 Direct Titrations Back Titrations Titrations with Indirect Metal Indicators

Replacement

or

Substitution Titrations

Alkalimetric Titrations

Sequential Titrations and Demasking Complexones

of Mixtures,

Selectivity, Masking,
535 539 540 543 543 544

29.3 29.4

Determination of Anions with EDTA Other

30

Applications of the Formation of Complexes in Inorganic Analysis 30.1 Qualitative Inorganic Analysis
30.1.1 Cations' Characterization

...

30.1.2 Anions'Characterization

563

Contents

xxi

30.2

Quantitative Inorganic Analysis 30.2.1 Titration of Ca2+

30.2.2 30.2.3 30.2.4 30.2.5 30.2.6 Titration of

568 568 569 570 570 571 571

Mg2+

Titration of Lead Titration of Bismuth Titration of Aluminum Miscellaneous Titrations

Part V 31

Precipitation PhenomenaAnalytical Applications

of the Formation of

Applications
31.1 31.2
31.3

Complexes Cu2+

in

Formation of Formation of

Formation of
Formation of

31.4
31.5 31.6

Formation of

Complexes Complexes Complexes Complexes Complexes

with Fe3+ and with with with with

Organic Analysis Fe2+

575 575 590 597

599 601

Ag+
Co2+

Hg2+

Formation of Miscellaneous Complexes and Analytical

Applications
32

603

Intrinsic, Ionic, Precipitation

32.1 32.2

and Total

Solubilities; Solubility Product and

609
609

32.3
32.4

Solubility Product and Intrinsic Solubility Generalization of the Concept of Solubility Product Thermodynamic Justification of the Concept of Solubility
Product Intrinsic

610
612

Solubility,

Total

Solubility, and

Ionic Product

613
617

32.5

Difficulties Encountered in the Calculations of Solubilities

33 Dependence of the Solubility on the Solution's Ionic Strength and on the Presence of Common Ions: Superimposition of Several

Precipitation Equilibria
33.1
33.2 33.3

619
on

Influence of the Ionic Strength The Common Ion Effect

the

Solubility

619 622

Superimposition Precipitation
and

of Two

Precipitation Equilibria: Separation by

628

34

Solubility
34.1

pH Solubility of Acidic
34.1.1 34.1.2 34.1.3 The Diacid The

633
and Basic Solutes
or as a

Function of

pH

633 633 636 637

The Monoacid
or

Monobasic Case

Dibase Case
Function of

34.2

Ampholyte Case Solubility of Poorly Soluble Salts 34.2.1 Qualitative Aspect

34.2.2 Acid-Base Medium:

as a

pH
a

639 639

Equilibria and Precipitation Quantitative Aspect

of

in

Buffered 640
..

34.2.3

Solubility

Poorly Soluble Salts

in Unbuffered Media

642

xxii 34.3

Contents

Fractional

Precipitation

of Ions

as a

Function of the Solution's

pH

Value

648 648
of Metallic Ions of Metallic Ions
as

34.3.1 34.3.2 34.3.3

34.3.4

Qualitative Aspects Fractional Precipitation Fractional Precipitation as Hydroxides Fractional Precipitation

Sulfides

649 654

of Metallic Ions

as

Oxinates

656
659

35 Precipitation and Complexation

35.1 Dissolution of
a

Precipitate by Complexation

of the Metal Cation 659

Constituting
35.2

it: Generalities
a

Dissolution of

Precipitate by Complexation: Quantitative

660

Aspects
35.3 Dissolution of
a

Precipitate by Complexation:
662
a

Further Calculations 35.3.1 Dissolution of Silver Bromide with

Sodium Thiosulfate 663

Solution

35.4 35.5

Precipitate Precipitating Reagent 35.3.3 Precipitation of Metallic Sulfides Destruction of a Complex by Formation of a Precipitate Separation by Complexation and Precipitation
35.3.2
an

Dissolution of a
of

with

Excess

664 668
672

676
679

36 Theoretical 36.1

Study of Some Precipitation Titration

a

Curves

Case of 36.1.1 36.1.2 36.1.3

36.1.4

Symmetric
and

Titration: Titration of A Halide

by Silver Ions

Inversely
of the Titration Curve

679 679 680 682 682

683 684 685 686

Titration Reaction

General Equation

Shape

of the Titration Curve of the Titration Curve

Simplified Equations
Titration Error

36.1.5
36.1.6 36.1.7 36.2

Inflection Point of the Titration Curve Inverse Titration Titrations

Dissymmetric

37 Titrimetric Methods Involving 37.1

Precipitation

689 689 689 689

Argentometry
37.1.1 37.1.2 Definitions

Generalities
in Acidic Medium:

37.2

Argentometry
Method 37.2.1 37.2.2 37.2.3

Charpentier-Volhard's
690 690

Principle
Theoretical Justification of the Method

690
691

Conditions in Which the Titration Must Be Carried Out 692

37.2.4 Titration Error

Contents

xxiii

37.3

Argentometry in
Method 37.3.1 37.3.2 37.3.3 37.3.4

Neutral

or

Weakly

Alkaline Medium: Mohr's 693

Principle
Mechanism of the Endpoint Indication: Titration Error pH Conditions
or
...

693 694

695 696

37.4

Applications Argentometry in Weakly Acidic Fajans' Method 37.4.1 Principle

37.4.2 37.4.3 Indication Mechanism

Neutral Medium: 696 696 696 697 697 697 698

698 700

37.5

Experimental Conditions Liebig-DenigeV Method

37.5.1 37.5.2 Definitions

37.5.3
37.5.4

Principle of Liebig's Method Equations of the Titration Curve

Titration Error Drawback to

37.5.5 37.5.6

Liebig's

Method

700 700

Deniges'Modification 37.5.7 Applications and Extensions

Method 37.5.8
37.6 38

of

Liebig-DenigeV
702 702

Standard Solutions

Some Other

Precipitation

Methods

703 705 705

Gravimetry by Precipitation 38.1 Principle and Some Definitions

38.2 Conditions for the Success of Determination 38.3 38.4
a

Gravimetry by Precipitation
706
707

Insolubility

Precipitate Composition Precipitate; Impurities of the Precipitate 38.4.1 Impurities by Coprecipitation 38.4.2 Impurities by a Lack of Selectivity of the Precipitation
of the Reaction

of the

in the Medium

708
708

710 712 712 712 714

38.5

Obtaining a Suitable Precipitate 38.5.1 Purity of Precipitates and Size of Particules

38.5.2 Size of Particules from

38.6 38.7

Precipitation

Homogeneous Solution

The Gravimetric Factor

716 718 719 719 719 719 719

720

38.8
38.9

Sensitivity of Gravimetry Some Experimental Details

38.9.1 38.9.2 38.9.3
38.9.4

Quantitative Filtration

Drying

of

Precipitates

Precision Balances Thermobalances

38.10 Some Characteristics of

Gravimetry by Precipitation

xxiv

Contents

39 Some and 39.1

Applications of the Precipitation Phenomenon in Inorganic Organic Qualitative and Quantitative Analysis Titrations Involving the Precipitation of Insoluble Silver Salts
39.1.1 39.1.2

721

721
721

Organic Halogens Determination of Hydrochlorides, Hydrobromides, and Hydroiodides

Determination of Some

723 723

39.1.3 39.1.4

Examples

Zeisel's Method: Determination of

Methoxy

and

Ethoxy
726 727

39.1.5
39.2

Groups Prototropic Titrations in

the Presence of Silver Ions

Other Titrimetric Methods Phenomenon

Involving a Precipitation
729 731 732

39.3

Gravimetry
39.3.1 39.3.2 39.3.3
39.3.4

Gravimetric Assays Involving Ignition Gravimetric Assays Extraction

Involving

Prior Solvent
732

Assay Involving Constant Weight

of
a

Solvent Extraction and

Drying

to

733 the Formation 733 with

39.4

39.5 39.6

Involving Precipitate that Is Weighed Determination of Inorganic Ions After Precipitation Precipitants Qualitative Organic Analysis Inorganic Qualitative Analysis
A The Chain Rule
or

Gravimetric Determinations

Organic
734 736

740

Appendix
of
a

Differentiating

Function 743

Function B

Appendix
with
a

Sharpness Index for

Base

the Titration of

Strong Acid
745

Strong

Appendix C Sharpness Index for the Titration of a Weak Acid with a Strong Base and Conversely
Appendix
Acid with D
a

747

Sharpness

Index for the Titration of

Weak 749

Weak Base

Appendix
Fraction
a

Finding

an

Approximate Expression of

the 751 753 763 765

of the Added Titrant That Has Reacted

Appendix

F A

Study

of Liebig-Deniges's Titration Curves

Bibliography
Index