CRITICAL
`STABILITY
`CONSTANTS
`Volume 4: Inorganic Complexes
`
`Mylan Ex 1056, Page 1
`
`

`

`CRITICAL STABILITY CONSTANTS
`
`Volume 1 • Amino Acids
`Volume 2 • Amines
`Volume 3 • Other Organic Ligands
`Volume 4 •
`Inorganic Complexes
`
`Mylan Ex 1056, Page 2
`
`

`

`CRITICAL
`STABILITY
`CONSTANTS
`Volume 4: Inorganic Complexes
`
`by Robert M. Smith
`and Arthur E. Martell
`
`Department of Chemistry
`College of Science
`Texas A & M University
`College Station, Texas
`
`SPRINGER SCIENCE+BUSINESS MEDIA, LLC
`
`Mylan Ex 1056, Page 3
`
`

`

`Library of Congress Cataloging in Publication Data
`
`Martell, Arthur Earl, 1916-
`Critical stability constants.
`
`On voI. 2 and 4 Smith's name appears first on t.p.
`Includes bibliographical references.
`CONTENTS: v. 1. Amino acids.-v. 2. Amines.-v. 3. Other organic
`ligands-v. 4. Inorganic complexes.
`1. Chemical equilibrium-Tables, etc. 2. Complex compounds-Tables,
`etc. 1. Smith, Robert Martin, 1927-
`joint author. II. Title. [DNLM:
`1. Amino acids. 2. Chemistry, Physical. 00503 M376cl
`74-10610
`OD503.M37
`541'.302
`ISBN 978-1-4757-5508-4
`ISBN 978-1-4757-5506-0 (eBook)
`DOI 10.1007/978-1-4757-5506-0
`
`© 1976 Springer Science+Business Media New York
`Originally published by Plenum Press, New York in 1976
`Softcover reprint of the hardcover 1 st edition 1976
`
`AII rights reserved
`
`No part of this book may be reproduced, stored in a retrieval system, or transmitted,
`in any form or by any means, electronic, mechanical, photocopying, microfilm ing,
`recording, or otherwise, without written permission from the Publisher.
`
`Mylan Ex 1056, Page 4
`
`

`

`PREFACE
`
`Over the past fifteen years the Commission on Equilibrium Data of the Analytical Division of the I nter(cid:173)
`national Union of Pure and Applied Chemistry has been sponsoring a noncritical compilation of metal
`complex formation constants and related equilibrium constants. This work was extensive in scope and
`resulted in the publication of two large volumes of Stability Constants by the Chemical Society
`(London). The first volume, edited by L. G. Si"en (for inorganic ligands) and by A. E. Marte" (for
`organic ligands), was published in 1964 and covered the literature through 1962. The second volume,
`subtitled Supplement No.1, edited by L. G. Si"en and E. Hogfeldt (for inorganic ligands) and by A. E.
`Marte" and R. M. Smith (for organic ligands), was published in 1971 and covered the literature up to
`1969. These two large compilations attempted to cover a" papers in the field related to metal complex
`equilibria (heats, entropies, and free energies). Since it was the policy of the Commission during that
`period to avoid decisions concerning the quality and reliability of the published work, the compilation
`would frequently contain from ten to twenty values for a single equilibrium constant. In many cases
`the values would differ by one or even two orders of magnitude, thus frustrating readers who wanted
`to use the data without doing the extensive literature study necessary to determine the correct value of
`the constant in question.
`
`Because of difficulties of this nature, and because of the general lack of usefulness of a noncritical
`compilation forteaching purposes and for scientists who are not sufficiently expert in the field of equi(cid:173)
`librium to carry out their own evaluation, we have decided to concentrate our efforts in this area
`toward the development of a critical and unique compilation of metal complex equilibrium constants.
`Although it would seem that decisions between available sets of data must sometimes be arbitrary and
`therefore possibly unfair, we have found the application of reasonable guidelines leads directly to the
`elimination of a considerable fraction of the published data of doubtful value. Additional criteria and
`procedures that were worked out to handle the remaining literature are described in the Introduction
`of this book. Many of these methods are quite similar to those used in other compilations of critical
`data.
`
`In cases where a considerable amount of material has accumulated, it is felt that most of our critical
`constants wi" stand the test of time. Many of the data listed, however, are based on only one or a very
`few literature references and are subject to change when better data come along. It should be fully
`understood that this compilation is a continually changing and growing body of data, and will be
`revised from time to time as new results of these systems appear in the literature.
`
`The scope of these tables includes the heats, entropies, and free energies of a" reactions involving
`organic and inorganic ligands. The magnitude of the work is such that far more than a thousand book
`pages will be required. In order that the material be available in convenient form, the amino acid
`complexes are presented in Volume 1 and amine complexes (which do not contain carboxylic acid
`functions) are included in Volume 2. The remaining organic complexes are the subject of Volume 3.
`Volume 4 comprises the inorganic complexes.
`
`v
`
`Mylan Ex 1056, Page 5
`
`

`

`vi
`
`PREFACE
`
`We are grateful to Sten Ahrland, Charles F. Baes, Jr., Gregory R. Choppin, George H. Nancollas, and
`Reino Nasanen for reviewing portions of the manuscript and making valuable comments. We are also
`indebted to Charles F. Baes, Jr. for a prepublication copy of his book on the hydrolysis of cations
`(76BM).
`
`Texas A&M University
`College Station, Texas
`
`Robert M. Smith
`Arthur E. Martell
`
`Mylan Ex 1056, Page 6
`
`

`

`CONTENTS
`
`I.
`
`Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`
`ix
`
`II.
`
`Inorganic ligands
`
`A. Water
`1. Hydroxide ion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`
`1
`
`B. Transition metal ligands
`.. 15
`2. Hydrogen vanadate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`.. 17
`3. Hydrogen chromate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`.. 18
`4. Hydrogen molybdate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`.. 19
`5. Hydrogen wolframate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`6. Rhenate(V II) ion ................................................ , 20
`7. Hydrogen hexacyanoferrate( II) .................. , . . . . . . . . . . . . . . . . .
`.. 21
`8. Hexacyanoferrate( III) ion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`.. 22
`9. Hexacyanocobaltate( III) ion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`.. 24
`
`C. Group III ligands
`10. Hydrogen borate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`
`.. 25
`
`D. Group IV ligands
`.. 26
`11. Hydrogen cyanide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`12. Hydrogen cyanate ............................................... , 28
`13. Hydrogen thiocyanate ............................................ , 29
`14. Selenocyanate ion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`.. 35
`15. Tricyanomethane ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`.. 36
`16. Dicyanimide ion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`.. 36
`17. Hydrogen carbonate ............................................. , 37
`18. Hydrogen sil icate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`.. 39
`
`E. Group V ligands
`.. 40
`19. Ammonia. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`.. 43
`20. Hydrazine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`.. 44
`21. Hydroxylamine. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`.. 45
`22. Hydrogen azide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`23. Hydrogen nitrite ................................................ , 47
`24. Nitrate ion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`.. 48
`25. Hydrogen hyponitrite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`.. 53
`26. Hydrogen hypophosphite ......................................... , 54
`27. Hydrogen phosphite ............................................ "
`55
`28. Hydrogen phosphate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`.. 56
`29. Hydrogen diphosphate ........................................... , 59
`
`vii
`
`Mylan Ex 1056, Page 7
`
`

`

`~ij
`
`CONTENTS
`
`30. Hydrogen triphosphate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`31. Hydrogen tetraphosphate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`32. Hydrogen trimetaphosphate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`33. Hydrogen tetrametaphosphate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`34. Hydrogen hexametaphosphate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`35. Hydrogen octametaphosphate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`36. Hydrogen imidodiphosphate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`37. Hydrogen diimidotriphosphate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`38. Cyclo-tri-Jl-imidotris(dioxophosphate). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`39. Hydrogen diphosphate (III, V) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`40. Hydrogen hypophosphate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`41. Hydrogen peroxodiphosphate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`42. Hexafluorophosphate ion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`43. Hexafluoroarsenate ion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`
`F. Group VI ligands
`44. Hydrogen peroxide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`45. Hydrogen sulfide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`46. Hydrogen sulfite. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`47. Hydrogen sulfate ion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`48. Hydrogen thiosulfate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`49. Selenosulphate ion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`50. Hydrogen amidosulphate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`51. Hydrogen peroxodisulfate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`52. Hydrogen selenide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`53. Hydrogen selenite. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`54. Hydrogen selenate ion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`55. Hydrogen telluride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`56. Hydrogen tellurite. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`
`.. 63
`.. 66
`.. 68
`.. 69
`.. 70
`.. 70
`.. 71
`.. 71
`.. 72
`.. 72
`.. 73
`.. 73
`.. 74
`.. 74
`
`.. 75
`.. 76
`.. 78
`.. 79
`.. 86
`.. 88
`.. 88
`.. 89
`.. 90
`.. 91
`.. 93
`.. 94
`.. 95
`
`G. Group VII ligands
`.. 96
`57. Hydrogen Fluoride. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`58. Chloride ion .................................................... 104
`59. Chlorate ion .................................................... 113
`60. Perchlorate ion .................................................. 114
`61. Bromide ion ....... ' ............................................. 115
`62. Bromate ion .................................................... 121
`63.
`Iodide ion ...................................................... 122
`64. Hydrogen iodate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`.. 126
`65. Hydrogen periodate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`.. 129
`
`III. Protonation values for other ligands ........................................... 131
`
`IV.
`
`Ligands considered but not included ........................................... 135
`
`v. Bibliography ............................................................. 137
`
`VI.
`
`Indexes
`Ligand formula index .................................................. 253
`A.
`B.
`Ligand name index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
`.. 255
`
`Mylan Ex 1056, Page 8
`
`

`

`INTRODUCTION
`
`Purpose
`
`This compilation of metal complex equilibrium (formation) constants and the corresponding enthalpy
`and entropy values represent the authors' selection of the most reliable values among those available
`in the literature. In many cases wide variations in published constants for the same metal complex
`equilibrium indicate the presence of one or more errors in ligand purity, in the experimental measure(cid:173)
`ments, or in calculations. Usually, the nature of these errors is not readily apparent in the publication,
`and the reader is frequently faced with uncertainties concerning the correct values. In the course of
`developing noncritical compilations of stability constants, the authors have long felt that these wide
`variations in published work constitute a serious impediment to the use of equilibrium data. Thus
`these critical tables were developed in order to satisfy what is believed to be an important need in the
`field of coordination chemistry.
`
`Scope
`
`These tables include all organic and inorganic ligands for which reliable values have been reported in
`the literature. The present volume is restricted to inorganic ligands.
`
`Values determined in nonaqueous solutions as well as values involving two or more different ligands
`(i.e., "mixed ligand" complexes) have not been included in this compilation but may be included in a
`subsequent volume. Mixed ligand complexes containing hydrogen or hydroxide ions are included since
`these ions are derived from the solvent and are therefore potentially always available. In general,
`data were compiled for only those systems that involve metal ion equilibria. Data on potentially im(cid:173)
`portant ligands for which only acid-base equilibria are presently available are given in a separate table.
`
`Selection Criteria
`
`When several workers are in close agreement on a particular value, the average of their results has
`been selected for that value. Values showing considerable scatter have been eliminated. I n cases
`where the agreement is poor and few results are available for comparison, more subtle methods were
`needed to select the best value. This selection was often guided by a comparison with values obtained
`for other metal ions with the same ligand and with values obtained for the same metal ion with similar
`ligands.
`
`While established trends among similar metal ions and among similar ligands were valuable in deciding
`between widely varying values, such guidelines were used cautiously, so as not to overlook occasion(cid:173)
`ally unexpected real examples of specificity or anomalous behavior.
`
`When there was poor agreement between published values and comparison with other metal ions and
`ligands did notsuggestthe best value, the results of more experienced research groups who had supplied
`reliable values for other ligands were selected. When such assurances were lacking, it was sometimes
`
`ix
`
`Mylan Ex 1056, Page 9
`
`

`

`x
`
`INTRODUCTION
`
`possible to give preference to values reported by an investigator who had published other demonstrably
`reliable values obtained by the same experimental method.
`
`In some cases the constants reported by several workers for a given group of metal ions would have
`similar relative values, but would differ considerably in the absolute magnitudes of the constants. Then
`a set of values from one worker near the median of all values reported were selected as the best con(cid:173)
`stants. By this method it is believed that internal consistency was preserved to a greater extent than
`would be obtained by averaging reported values for each individual metal ion. When an important con(cid:173)
`stant was missing from the selected set of values, but was available in another set of values not selected
`for this compilation, the missing constant was obtained by adjusting the nonselected values by a
`common factor, which was set so as to give the best agreement between the two groups of data.
`
`Values reported by only one investigator are included in these tables unless there was some reason
`to doubt their validity. It is recognized that some of these values may be in error, and that such errors
`will probably not be detected until the work is repeated by other investigators, or until more data
`become available for analogous ligands or other closely related metal ions. Some values involving
`unusual metal ions have been omitted because of serious questions about the form of their complexes.
`
`Papers deficient in specifying essential reaction conditions (e.g., temperature, ionic strength, nature
`of supporting electrolyte) were not employed in this compilation. Also used as a basis for disqualifica(cid:173)
`tion of published data is lack of information on the purity of the ligand. Frequent deficiencies are lack
`of calibration of potentiometric apparatus, and failure to define the equilibrium quotients reported in
`the paper. Papers in which both temperature and ionic strength are not controlled have been omitted
`from the bibliography.
`
`A bibliography for each ligand is included so that the reader may determine the completeness of the
`literature search employed in the determination of critical values. The reader may also employ these
`references to make his own evaluation if he has any questions or reservations concerning this compila(cid:173)
`tion.
`
`Arrangement
`
`The arrangement of the tables is based on the periodic table position of the central atom of the ligand
`except that the hydroxide ion is placed first because of its importance in considering equilibria involv(cid:173)
`ing other ligands. This is followed by transition metal ligands and then those of groups III through VII
`of the periodic table. Within each group of tables involving the same atom, the arrangement is from
`the lowest oxidation state to higher ones. Next there is a table of protonation constants for ligands for
`which no stability constants or only questionable metal stability constants are reported. Finally, there
`is a list of other ligands considered but not included in the tables for various reasons.
`
`Metal Ions
`
`The metal ions within each table are arranged in the following order: hydrogen, alkali metals, alkaline
`earth metals, lanthanides (including Sc and V), actinides, transition metals, and posttransition metals.
`Within each group the arrangement is by increasing oxidation state of the metal, and within each oxi(cid:173)
`dation state the arrangement follows the periodic table from top to bottom and from left to right. An
`exception is that Cu+, Ag+, PdH , and ptH are included with the posttransition metals.
`
`Equilibrium
`
`An abbreviated equilibrium quotient expression in the order products/ reactants is included for each
`constant, and periods are used to separate distinct entities. Charges have been omitted as these can
`be determined from the charge of the metal ion and the abbreviated ligand formulas (such as H L) given
`
`Mylan Ex 1056, Page 10
`
`

`

`INTRODUCTION
`
`xi
`
`after the name. Water has not been included in the equilibrium expressions since all of the values cited
`are for aqueous solutions. For example, M4 L4 /M 4 'L 4 for MgH and hydroxide ion would represent the
`equilibrium: 4MgH + 40H- ~ M94 (OH):+. The symbol M represents the metal ion given in the first
`column and may include more than one atom as in the case of Hg~+. The symbol H .• (H. 2 , etc.) is used
`for the ionization of a proton from the ligand alone at high pH.
`
`Equilibria involving protons are written as stability constants (protonation constants) rather than as
`ionization constants to be consistent with the metal complex formation constants. Consequently the
`t::,H andt::,S values have signs opposite to those describing ionization constants.
`
`Solids and gases are identified by (s) and (g) respectively and are included for identification purposes
`even though they are not involved in the equilibrium quotient.
`
`Log K Values
`
`The log K values are the logarithms of the equilibrium quotients given in the second column at the
`specified conditions of temperature and ionic strength. The selected values are those considered to
`be the most reliable of the ones available. In some cases the value is the median of several values and
`in other cases it is the average of two or more values. The range of other values considered reliable is
`indicated by + or - quantities describing the algebraic difference between the other values and the
`selected value. The symbol ±O.OO indicates that there are one or more values which agree exactly with
`the stated value to the number of significant figures given. Values considered to be of questionable
`validity are enclosed in parentheses. Such values are included when the evidence available is not strong
`enough to exclude them on the basis of the above criteria. Values concerning which there is con(cid:173)
`sierable doubt have been omitted.
`
`The log K values are given for the more commonly reported ionic strengths. The ionic strengths most
`used for inorganic ligands are 0.1, 0.5, 1.0, 2.0, 3.0, 4.0, and O. Zero ionic strength is perhaps more
`important from a theoretical point of view, but several assumptions are involved in extrapolating or
`calculating from the measured values. The Davies equation is often used to calculate constants to zero
`from low·ionic-strength measurements. It was established from results obtained with monovalent and
`divalent ions and its extension to trivalent ions is extremely questionable.
`
`The temperature of 25°C was given preference in the tables because of its widespread use in equi(cid:173)
`librium measurements and reporting other physical properties. When available, enthalphy changes
`(t::,H) were used to calculate log K at 25°C when only measurements at other temperatures were
`available.
`
`Other temperatures frequently employed are 20°C, 30°C, and 37°C. These are not included in the
`tables when there is a lack of column space and t::,H is available, since they may be calculated using the
`t::,H value. Values at other temperatures, especially those at 20°C and 30°C, were converted to 25°C to
`facilitate quantitative comparisons with the 25°C values listed.
`
`Equilibria involving protons have been expressed as concentration constants in order to be more con(cid:173)
`sistent with the metal ion stability constants which involve only concentration terms. Concentration
`constants may be determined by calibrating the electrodes with solutions of known hydrogen ion con(cid:173)
`centrations or by conversion of pH values using the appropriate hydrogen ion activity coefficient.
`When standard buffers are used, mixed constants (also known as Bronsted or practical constants) are
`obtained which include both activity and concentration terms. Literature values expressed as mixed
`constants have been converted to concentration constants by using the hydrogen ion activity coeffi(cid:173)
`cients determined in KCI solution before inclusion in the tables. In some cases, papers were omitted
`because no indication was given as to the use of concentration or mixed constants. Some papers were
`
`Mylan Ex 1056, Page 11
`
`

`

`xii
`
`INTRODUCTION
`
`retained despite this lack of information when it could be ascertained which constant was used by
`comparing to known values or by personal communication with the authors. For those desiring to con(cid:173)
`vert the listed protonation constants to mixed constants, the following values should be added to the
`listed values at the appropriate ionic strength (the tabulation applies only to single proton association
`constants) :
`
`Ionic strength
`
`Increase in log K
`
`0.05
`0.10
`0.15
`0.2
`0.5
`1.0
`2.0
`3.0
`
`0.09
`0.11
`0.12
`0.13
`0.15
`0.14
`0.11
`0.07
`
`The values in the tables have not been corrected for complexation with medium ions for the most part.
`There are insufficient data to make corrections for most of the ligands, and in order to make values
`between ligands more comparable, the correction has not been made in the few cases where it could
`be made. In general the listed formation constants at constant ionic strength include competition by
`ions from KN0 3 and NaCIO. and are somewhat smaller than they would be if measured in solutions of
`tetraalkylammonium salts.
`
`Limited comparisons were made between values at different ionic strengths using observed trends.
`With inorganic ligands the stability constants usually decrease with ionic strength until a minimum is
`reached and then increase with increasing ionic strength. The minimum is often at about 0.5 ionic
`strength when hydrogen or hydroxide ion is involved but may change with other ions. With basic
`ligands such as ammonia there is a continuing increase with ionic strength and no maximum or minimum
`is generally observed. With phosphorous compounds containing oxygen donors there is a continuing
`decrease with ionic strength because of the increased competition from sodium ions in the background
`electrolyte.
`
`The solubility products of precipitates frequently become more negative with longer digestive times.
`This is apparently due to conversion to less soluble forms of the precipitate with time. Since various
`digestive times have been used to ,measure solubility products, their comparison becomes rather
`tenuous, except for rough approximations. With lanthanide hydroxides, the solubility products have
`been measured as a function of time at constant temperature in some cases, and the values listed in the
`table have been corrected to the fresh or active precipitate by using the average change with time of
`the lanthanide hydroxides as a whole.
`
`The hydrolysis of highly charged metal ions, such as Th H , apparently leads to different polymerization
`products in different media. Consequently the species formed may be different with a change in
`the background electrolyte if the background electrolyte becomes part of the polymeric ions.
`
`Enthalpy Values
`
`The enthalpy of complexation values (!::.H) listed in the tables have the units kcal/mole because of the
`widespread use of these units by workers in the field. These may be converted to SI units of kj/mole
`by multiplying the listed values by 4.184.
`
`Calorimetrically determined values and temperature-variation-determined values from cells without
`liqu id ju nction were considered of equal validity for the tables. Other temperature-variation-determined
`values were rounded off to the nearest kcal/mole and were enclosed in parentheses because of their
`reduced accuracy. Other values considered to be reliable but differing from the listed value were
`
`Mylan Ex 1056, Page 12
`
`

`

`INTRODUCTION
`
`xiii
`
`indicated by + or - quantities describing the algebraic difference between the other value and the
`selected value.
`
`The magnitude of £::,.H may vary with temperature and ionic strength, but usually this is less than the
`variation between different workers and little attempt has been made to show £::,.H variation with
`changing conditions except for certain carefully measured equilibria such as the protonation of hy(cid:173)
`droxide ion and of ammonia. These £::,.H values may be used for estimating log K values at temperatures
`other than those listed, using the relationship
`
`f::>.H
`2.303RP
`
`=
`
`d log K
`dT
`
`log K. = log K. + f::>.H(T. - T. )(0.00246).
`
`This assumes that £::,.Cp = 0, which is not necessarily the case. The greater the temperature range em(cid:173)
`ployed, the greater the uncertainty of the calculated values.
`
`Entropy Values
`
`The entropy of complexation values (.cS) listed in the tables have the units cal/mole/degree and have
`been calculated from the listed log K and £::,.H values, using the expression
`
`.c:.S = 3.36 (1.363 log K + .c:.H).
`
`These entropy values have been rounded off to the nearest cal/mole/degree, except in cases where
`f::>.H values were quite accurate.
`
`Bibliography
`
`The references considered in preparing each table are given at the end of the table. The more reliable
`references are listed after the ions for which values are reported. In some tables groups of similar
`metal ions have been grouped together for the bibliography. The term "Other references" is used for
`those reporting questionable values, or values at conditions considerably different from those used in
`the tables, or values for metal ions not included in the tables because of questionable knowledge
`about the forms of their complexes. These additional references are cited to inform the reader of the
`extent of the literature search made in arriving at the selected values.
`
`The bibliographical symbols used represent the year of the reference and the first letter of the sur(cid:173)
`names of the first two listed authors. I n cases of duplication, letters a, b, c, etc., or the first letter of
`the third author's name are employed. The complete reference is given in the bibliography at the end
`of each volume.
`
`In a work of this magnitude, there will certainly be errors and a few pertinent publications will have
`been overlooked by the compilers. We should like to request those who believe they have detected
`errors in the selection process, know of publications that were omitted, or have any suggestions for
`improvement of the tables, write to:
`
`A. E. Martell, Head
`Department of Chemistry
`Texas A&M University
`College Station, Texas 77843, U.S.A.
`
`It is the intention of the authors to publish more complete and accurate revisions of these tables as
`demanded by the continually growing body of equilibrium data in the literature.
`
`Mylan Ex 1056, Page 13
`
`

`

`56
`
`II.
`
`INORGANIC LIGANDS
`
`o
`II
`HO-P-DH
`I
`OH
`
`Hydrogen phosphate
`
`(phosphoric acid)
`
`Metal
`ion
`H+
`
`Equilibrium
`HL/H.L
`H2L/HL.H
`
`Log K
`Log K
`Log K
`25°, 0
`25°, 1.0
`25°, 0.5
`11.74a±0.08 10.7ge±0.07 12.35 ±0.02
`6.46 ±0.02 7.199±0.002
`6.57 ±0.05
`6.36d
`5.72a±0.05
`6.79r ,s
`6.26e±0.02
`1.70 ±0.02 2.148+0.001
`1.86e±0.03
`
`1.72
`2.0a ±0.1
`
`flH
`25°, 0
`-3.5 ±0.9
`-0.8 ±0.2
`_1.2 a
`
`1.9 ±0.1
`
`(6)r,t
`
`(8)r,t
`
`(6)r,t
`
`45
`30
`
`16
`
`(23)r,s
`
`(30)r,s
`
`(22)r,s
`
`0.60r ,s
`
`0.49r ,s
`
`3.4u
`1.8u ±O.O
`1.42e
`0.7u
`0.16e
`
`MHL/M.HL
`
`MHL/M.HL
`
`MHL/M.HL
`
`ML/M.L
`MHL/M.HL
`
`2+
`Ca
`
`3 2 M .L /M3L2 (H20)8(s)
`M.HL/MHL(H20)3(s)
`ML/M.L
`MHL/M.HL
`
`MH2L/M.H2L
`M.HL/MHL(H20)2(s)
`
`(4.2)h
`1.2h
`1.52r ,s
`0.3h
`
`ML/M.L
`MHL/M.HL
`
`MH2L/M.H2L
`M.HL/MHL(s)
`
`M.HL/MHL(s)
`
`2.91
`
`3
`
`23
`
`(40)
`(23)
`
`(17)
`(-28)
`
`-25.20
`-5.82
`
`6.46
`2.74 -0.06
`
`1.4 -0.6
`-6.58 ±0.03
`
`2.65
`
`a 250, 0.1; d 25°, 2.0; e 25°, 3.0; h 20°, 0.1; 0 20°, 0; r (C3H7)4NC1 used as background
`electrolyte; s 25°, 0.2; t o-25 °, 0.2; u 37°, 0.15; v 25-37°, 0; w 18-37°, 0; x 20°, 0.2
`
`Mylan Ex 1056, Page 14
`
`

`

`E. GROUP V LIGANDS
`
`Hydrogen phosphate (continued)
`
`Metal
`ion
`La3+
`
`Pm3+
`
`Gd3+
`
`Ac3+
`
`Am3+
`
`Th4+
`
`UO 2+
`2
`
`2+
`Fe
`
`Co2+
`
`Equilibrium
`MH2L/M.H2L
`M.L/ML(s)
`
`ML/M.L
`MH2L/M.H2L
`
`MH2L/M.H2L
`
`M.L/ML(s)
`
`MH2L/M.H2L
`
`MH2L/M.H2L
`
`MH2L/M.H2L
`2
`M(H2L) /M. (H2L)
`3 2 M .L /M3L2 (s)
`M.HL/MHL(s)
`
`Log K
`25°, 0.5
`1. 61
`-22.43
`
`-22.26
`
`1.59
`
`1.69X
`
`3.96d
`7.5d
`
`-49.7 i
`-12.17 i
`
`MHL/M.HL
`MH2L/M.H2L
`3 2
`M .L /M3L2 (H20)S(s)
`MHL/M.HL
`
`2.1Sa
`
`MHL/M.HL
`
`MHL/M.HL
`MH2L/M.H2L
`
`MHL/M.HL
`MH2L/M.H2L
`M.L/ML(H20)2(s)
`3 2 M .L /M3