Chemistry 2810 Lecture Notes

Dr. M. Gerken

Page51

4.3.4 Hydrolysis of cations and acidity of aqua complexes of metal cations

It will be very obvious to you by now that the majority of the elements are metals, and that these tend to form cations. It is therefore important to consider the Brnsted acidity of aqua complexes of metal cations. This is a point that is often ignored in General Chemistry, and it comes as a surprise to many students that aqueous solutions of metal ions are often acidic, since the metal oxides are closely associated with the hydroxide bases. Now the two phenomena are closely related, insofar as both can be though of as being due to the reaction of the bare cation with water, a type of reaction which is commonly called hydrolysis. It turns out that different metal ions, and different oxidation states of metal ions, have very different reactivity with water. Consider the reaction of the following anhydrous chlorides with an excess of water (effectively a source of the naked metal cation, since the chloride anion is non-basic and is a spectator ion in water). Reagent LiCl MgCl AlCl3 TiCl4 Cation radius, 0.90 0.86 0.67 0.74 Charge 1+ 2+ 3+ 4+ Electronegativity 0.98 1.31 1.61 1.54 resulting pH Z2/r 1.11 4.65 13.4 21.6

Note the large difference in solution pH. That means that differing amounts of H3O+ have been created from the original water. We can break the overall reactions of the metal ions with water into several plausible steps. 1. The metal ion is solvated by water molecules (we can also call this hydration); typically metal ions are surrounded by about six water molecules in what is known as the primary hydration sphere. Most of the heat liberated in the above reaction is due to the enthalpy of hydration. These hydrated cations are also called aqua complexes (or aqua acids). 2. The hydrated ion can now undergo step-wise hyrolysis in which it delivers one or more H+ to the bulk solvent. This is illustrated in the graphic below for the aluminum ion, though the same scheme applies for any element, differing only by degree. The first step in this diagram shows how a strong attraction of the cation for an oxygen of one of the directlyattached water molecules results in the splitting-off of one H+: [Al(H2O)5OH]2+ + H3O+ [Al(H2O)6]3+ + H2O 3. Each step in the hydrolysis reduced the charge as hydroxycations are formed. Eventually a neutral species, a hydrated metal hydroxide, forms. For most metal ions of 2+ or higher charge, such neutral species will be insoluble, and a precipitate will form. 4. In principle, if the effective electronegativity of the element is high enough, this process can continue to produce hydroxyanions and even oxoanions. This is what happens for the transition metal ions in their highest oxidation states, which have extremely high effective electronegativity, such as for example Mn(VII) which forms the familiar MnO4 ion in aqueous solution. 5. Re-acidifying the metal oxoanion does not necessarily return the hydroxide, but often leads to polymerization of the oxoanions to form polyoxoanions, through an acid-catalyzed condensation, that is, by loss of water between two such anions. 6. The dehydration of neutral species results in the formation of the anhydrous metal oxide; in principle complete condensation polymerization of the oxoanions will also lead to the same metal oxide.

Chemistry 2810 Lecture Notes

Dr. M. Gerken

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Since these are Brnsted equilibria, we can write a standard hydrolysis constant for any step in this reaction:

pKa = pH log10

[M ] [M ]
( n 1)+ n+

For purposes of comparison we can quite usefully focus only on the first step, the pKa1, for each element. It is found, for example, that metal hydroxide usually starts to precipitate when the pH of the solution is approximately equal to the pKa of the metal ion. Another way to represent the consequences of the hydrolysis reactions described above is to consider the solubility of the different species involved. This has been done for aluminum in the diagram shown at the right. The soluble forms at low pH are metal aqua ions, while at high pH are hydroxoanions. The central region of insolubility is dominated by the neutral hydroxide.

a)

Quantifying hydrolysis of cations

From the small experiment described above, it is clear that a major factor is the charge on the ion. More specifically, if the hydrolysis of cations is controlled by ionic forces, it should correlated to the ratio of the square of the charge to the radius of the ion, which is called the electrostatic parameter, , where = Z2/r. (Strictly speaking, the radius is often an effective radius which includes the distance to the surrounding negative charges, but often simply using ionic radii is sufficient). The plots below show the correlation of the pKa to the electrostatic parameter, which results in a good correlation for elements with an electronegativity of 1.5.
pKa Correlation to Z2/r
16 14 12 10 8 6 pKa 4 2 0 0 -2 -4 Z2/r 5 10 15 20 25 -2 -4 Z2/r+9.6(Chi-1.5) 16 14 12 10 8 6 pKa 4 2 0 0 5 10 15 20 25

pKa Correlation Corrected to Chi

A least-squares fit of the data provides a reasonable correlation so long as only data with 1.5 are used! The indicated line is drawn on the graph. From the slope of the line, the following empirical equation can be obtained:

Z2 pK a = 1514 08816 . . r
But for the more electronegative metals ( > 1.5 on Pauling scale), the points deviate far from this line. It has been shown that these wildly scattered points can be brought into good correlation to the same line as the electropositive cations using an empirical fudge factor, as shown in the right hand graph. The empirical equation that contains the fudge factor is:

Z2 pKa = 1514 0.8816 + 9.60 Pauling 150 . . r

The correction term is thus a contribution that increases with increasing electronegativity. This is a most suggestive result, because it means that with increasing covalency of the metal-oxygen bond, the acidity of the element increases. We would describe this in the language of Pauling as being the sum of a covalent and an ionic contribution to the EO bond strength in the metal hydroxide bond. Thus the borderline and soft Pearson acids are the very ones for which the Brnsted acidity is found to be unexpectedly strong - we have simply discovered two measurements in terms of chemical behavior of the same underlying element properties, and these properties can be related back to the electronic structure of the atoms and ions involved in terms of their electron configuration and shell structure.

Chemistry 2810 Lecture Notes

Dr. M. Gerken

Page53

ION +1 Ions K Na Li +2 Ions Ba Sr Ca

Hydrolysis Constants (pKa's) for Metal Cations Electronegativity < 1.5 Electronegativity > 1.5 pKa ION RADIUS Z2/r Z2/r RADIUS Z2/r + 9.6(p 1.50) 1.52 1.16 0.90 1.49 1.32 1.14 0.658 0.862 1.11 2.68 3.03 3.51 14.5 14.2 13.6 13.5 13.3 12.8 Tl Ag 1.64 1.29 0.610 0.775 1.57 4.90

pKa

13.2 12.0

Mg +3 Ions Pu La Lu Y Sc

0.86

4.65

11.4

Pb Sn Hg Cd Cr Mn Fe Co Ni Zn Be

1.33 1.41 1.16 1.09 0.94 0.97 0.92 0.88 0.83 0.88 0.59

3.01 2.84 3.45 3.67 4.25 4.12 4.35 4.55 4.82 4.55 6.78

6.56 5.72 8.25 5.49 5.79 4.60 7.52 8.19 8.76 5.99 7.45

7.7 3.4 3.4 10.1 10.0 10.6 9.5 9.6 9.9 9.0 6.2

1.14 1.17 1.00 1.04 0.88

7.89 7.69 9.00 8.65 10.2

7.0 8.5 7.6 7.7 4.3

Bi Tl Au In Ti Ga Fe Cr Al

1.17 1.02 0.99 0.94 0.81 0.76 0.78 0.75 0.67

7.69 8.82 9.09 9.57 11.1 11.8 11.5 12.0 13.4

12.7 14.0 19.1 12.3 11.5 14.8 14.7 13.5 14.5

1.1 0.6 1.5 4.0 2.2 2.6 2.2 4.0 5.0

+4 Ions Th 1.08 14.8 3.2 Pa 1.04 15.4 0.8 U 1.03 15.5 0.6 Np 1.01 15.8 1.5 Pu 1.00 16.0 0.5 Ce 1.01 15.8 1.1 Hf 0.85 18.8 0.2 Sn 0.83 19.3 22.2 Zr 0.86 18.6 0.3 Ti 0.74 21.6 22.00 Sources: Values of hydrolysis constants (pKa) taken from C, F, Baes and R.E. Mesmer, The Hydrolysis of Cations, Wiley-Interscience, New York, 1976; and when not available there from J. Burgess, Metal Ions in Solution, Ellis Horwood, Chichester, England, 1978, pp. 264-267.

0.6 4.0

b)

Base strength

Consider the bases corresponding to four cations in widely different acidity classes: LiOH Zn(OH)2 Al(OH)3 "Ti(OH)4" Which is the strongest base? LiOH. The hydroxides of the least acidic cations are the strongest alkalies. In terms of BrnstedLowry theory, this is because the conjugate acids of these bases show the least tendency to hydrolyse.

c)

Oxo cations

Several elements form stable oxo-cations from partial hydrolysis and dehydration. For example, vanadium(IV) readily forms VO2+, while uranium(VI) forms the uranyl, UO22+. Such ions exist in solution in the hydrated form, e.g. [VO(OH2)5]2+.

d)

Resistance to hydrolysis

Several factors go into the observation of hydrolysis at reasonable rates. For example, although TiCl4 and SiCl4 are both vigorously hydrolysed by water, CCl4 is not. This must be seen as being due to differences in kinetic stability. Indeed, at

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Dr. M. Gerken

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elevated temperatures CCl4 does react with water. At room temperature, the C atom is just so well shielded that the water can't get in to attack it. Thermodynamically hydrolysis is in fact favored for carbon tetrachloride at all temperatures.

e)

Brnsted acidity and the environmental distribution of the elements

Consideration of the many sophisticated ideas involved in Brnsted acidity can sometimes overwhelm us, and it is important to recognize that there are some very important consequences for the behavior of the elements under conditions that are commonly observed on this planet. A full discussion of this topic requires an understanding of the redox stability of the elements. Nevertheless, it is possible to simply list the most common forms of the elements in an aqueous environment. This is most commonly done in terms of pH distribution diagrams. For any polyprotic acid (or conjugate of a base) it is possible to write out a distribution diagram based on all the operative hydrolysis constants. This is sometimes called an alpha diagram, because the fraction of each species at a given pH is usually indicated by the Greek letter . At the right is shown a distribution diagram for phosphoric acid, a species which has several important forms at environmental pH values. To simplify this discussion, it is possible to draw vertical lines at the pH where any two -curves intercept. If the pH range of phosphoric acid is now broken into the four zones produced by these borders, we produce a simpler diagram which has been called a predominance diagram. We will use such diagrams extensively in this course, but it is worthwhile to remember their origin in distribution diagrams, insofar as in any region near the borders of a predominance diagram, species from both sides of the boundary will be present in appreciable concentration. The boundaries simply depict the major species within each zone. With this caution in mind, predominance diagrams can be effective tools for the qualitative comparison of acid/base behavior for a range of elements. The diagram below compares the Brnsted predominance for eight environmentally important elements. It was constructed for approximately 103 M solutions for the dominant oxidation state of each element. Ionic species in this table will be soluble in water, at least to a certain extent, while most neutral species will precipitate and thus in natural waters will become immobilized in the sludge at the bottom of the natural waterways. We see that sodium will remain soluble, and thus available, throughout the normal pH range. Calcium will precipitate under basic conditions, but aluminum will only dissolve under appreciably acidic conditions. Titanium will not dissolve under any pH conditions, and thus will remain fixed in the soil and in minerals. Phosphates are highly available at all pH values, which is important as it is a primary nutrient for plant life. These properties are important to the environmental behavior of the elements. For example, it is now believed that the reason that fish die in acidic lake waters, whose acidity is induced by acid-rain runoff, is the aluminum in the lake waters. An acidified lake (pH 2-4) will contain much more dissolved "Al3+" than natural fresh water does. As the fish draw this solution through their gills, maintained at physiological pH of about 7.5, the aluminum precipitates as the gelatinous hydrated hydroxide. This material forms a paste over the gills of the fish, destroying their ability to extract oxygen from the water. The fish end up dying from asphyxiation induced by the dissolved aluminum ions in solution.

If we now consider the fact that the pH range observed for moderately aerated water lies between 5.5 and 7.0 for almost all fresh-water sources, we can pick from a predominance diagram the form(s) that have high concentration within this pH range. If we do this for the most common oxidation states of the elements, the resulting compounds are a combination of aqueous

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Dr. M. Gerken

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ions, gases, liquids, insoluble hydroxides and insoluble oxides. The resulting list for the more common elements is presented in the periodic table below. Shading has been used to emphasize the soluble and insoluble species. Most of the elements are included, except the synthetic and highly-radioactive (short lived) elements, for which little reliable information is available. Those cells which have more than one entry represent species which have more than one predominant form within the 5.5 to 7.0 pH range. This table will be useful for anyone wishing to know how elements present in or released to the environment are likely to behave. This table should be compared carefully to the list of high-abundant and trace elements for biological systems provided back on page 4 of these notes. Be especially careful to note that many environmental scientists as well as nutritionists and medical scientists indiscriminately refer to any form of an element by the parent name of that element. They will thus talk about calcium levels in the blood, and actually mean all forms of calcium, though some may be present as the aqua ion, some in suspension as fine particles of solid, and some complexed to a wide variety of acceptor sites on biological ligands. Use this chart to recognize the most likely chemical form the element is going to be in natural waters.
1
H2O

Main Forms of the Elements in Moderately Aerated Water at pH 5.5 to 7.0

2 13 El Shading indicates the form indicated is insoluble 6
Cr(OH)3 MoO4 WO3 WO4 B(OH)3 Al(OH)3

14
CO2 HCO3 SiO2 GeO2 SnO2 Pb2+

15
NO3
H2PO4 HPO42 H2AsO4 HAsO42

16
H2O SO42 SeO42 HTeO3 ?

17
F Cl Br IO3 ?

Li+ Na+ K+ Rb+ Cs+ Fr+

Be(OH)2 Mg2+

3
Ca2+ Sr2+ Ba2+ Ra2+ Sc(OH)3 Y3+ Y(OH)3 La-Lu Ac-Lr

4
TiO2 ZrO2 HfO2

5
H3V2O7 H2VO4 Nb2O5 Ta2O5

7
Mn2 MnO2 TcO4 Re

8
Fe(OH)3 Ru(OH)3 OsO2

9
Co2+ Rh2O3 IrO2

10
Ni2+ Pd(OH)2 PtO2

11
Cu2+ Ag+ Au metal

12
Zn2+ Cd2+ HgO Ga(OH)3 In(OH)3 Tl+

Sb2O3 Bi2O3

Lanthanides Actinides

La3+ Ac3+

Ce3+ ThO2

Pr3+ Pa2O5

Nd3+ UO22+

Pm3+ NpO2+

Sm3+ PuO2

Eu3+ Am3+ Am(OH)4

Gd3+

Tb3+

Dy3+

Ho3+

Er3+

Tm3+

Yb3+

Lu3+