text:
Metal ions in aqueous solution
From Wikipedia, the free encyclopedia
Jump to: navigation, search
It has been suggested that this article be merged with Metal aquo complex. (Discuss) Proposed since June 2017.
A metal ion in aqueous solution (aqua ion) is a cation, dissolved in water, of chemical formula [M(H2O)n]z+. The solvation number, n, determined by a variety of experimental methods is 4 for Li+ and Be2+ and 6 for elements in periods 3 and 4 of the periodic table. Lanthanide and actinide aqua ions have solvation number of 8 and 9. The strength of the bonds between the metal ion and water molecules in the primary solvation shell increases with the electrical charge, z, on the metal ion and decreases as its radius, r, increases. Aqua ions are subject to hydrolysis. The logarithm of the first hydrolysis constant is proportional to z2/r for most aqua ions. The aqua ion is associated, through hydrogen bonding with other water molecules in a secondary solvation shell. Water molecules in the first hydration shell exchange with molecules in the second solvation shell and molecules in the bulk liquid. The residence time of a molecule in the first shell varies among the chemical elements from about 100 picoseconds to more than 200 years. Aqua ions are prominent in electrochemistry.
Contents
[hide]
1 Introduction to metal aqua ions
2 Occurrence in nature
3 Experimental methods
3.1 Nuclear magnetic resonance (NMR)
3.2 X-ray diffraction (XRD)
3.3 Neutron diffraction
3.4 Vibrational spectra
3.5 Dynamic methods
4 Solvation numbers and structures
4.1 Alkali metals
4.2 Alkaline earth metals
4.3 Aluminium and group 3 metals
4.4 Transition metals and group 12 metals
4.5 Group 13-15 metals
4.6 Lanthanides and actinides
4.7 Oxo-aqua-cations
5 Thermodynamics
6 Hydrolysis of aqua ions
6.1 First hydrolysis constant
6.2 Multiple hydrolysis reactions
6.3 Oxyanions
7 Exchange kinetics
7.1 Mechanisms
8 Formation of complexes
9 Electrochemistry
10 References
11 Bibliography
Introduction to metal aqua ions[edit]
The metallic elements (including superheavy elements predicted but not yet known to be metals)
Li Be
Na Mg Al
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn
Cs Ba La† Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po
Fr Ra Ac‡ Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts
(La)† Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
(Ac)‡ Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Most chemical elements are metallic and form simple aqua ions with the formula [M(H2O)n]z+ when the oxidation state is 1, 2 or 3. With the higher oxidation states the simple aqua ions dissociate losing hydrogen ions to yield complexes that contain both water molecules and hydroxide or oxide ions, such as the vanadium(IV) species [VO(H2O)5]2+. In the highest oxidation states only oxyanions, such as the permanganate(VII) ion, MnO−
4, are known.[1]
Schematic representation of the aqua ion [Na(H2O)6]+. The oxygen atoms are arranged at the vertices of a regular octahedron centered on the sodium ion
First and second solvation shells of an octahedral aqua ion. Up to 12 water molecules may be present in the second shell (only two are shown in this diagram) linked by hydrogen bonds to the molecules in the first shell.
In aqueous solution the water molecules directly attached to the metal ion are said to belong to the first coordination sphere, also known as the first, or primary, solvation shell. The bond between a water molecule and the metal ion is a dative covalent bond, with the oxygen atom donating both electrons to the bond. Each coordinated water molecule may be attached by hydrogen bonds to other water molecules. The latter are said to reside in the second coordination sphere. The second coordination sphere is not a well defined entity for ions with charge 1 or 2. In dilute solutions it merges into the water structure in which there is an irregular network of hydrogen bonds between water molecules.[2] With tripositive ions the high charge on the cation polarizes the water molecules in the first solvation shell to such an extent that they form strong enough hydrogen bonds with molecules in the second shell to form a more stable entity.[3]
The strength of the metal-oxygen bond can be estimated in various ways. The hydration enthalpy, though based indirectly on experimental measurements, is the most reliable measure. The scale of values is based on an arbitrarily chosen zero, but this does not affect differences between the values for two metals. Other measures include the M–O vibration frequency and the M–O bond length. The strength of the M-O bond tends to increase with the charge and decrease as the size of the metal ion increases. In fact there is a very good linear correlation between hydration enthalpy and the ratio of charge squared to ionic radius, z2/r.[4] For ions in solution Shannon's "effective ionic radius" is the measure most often used.[5]
Water molecules in the first and second solvation shells can exchange places. The rate of exchange varies enormously, depending on the metal and its oxidation state. Metal aqua ions are always accompanied in solution by solvated anions, but much less is known about anion solvation than about cation solvation.[6]
Understanding of the nature of aqua ions is helped by having information on the nature of solvated cations in mixed solvents[7] and non-aqueous solvents, such as liquid ammonia, methanol, dimethyl formamide and dimethyl sulfoxide to mention a few.[8]
Occurrence in nature[edit]
Aqua ions are present in most natural waters.[9] Na+, K+, Mg2+ and Ca2+ are major constituents of seawater.
Aqua ions in seawater (Salinity = 35)
Ion
Concentration
/mol·kg−1
Na+
0.469
K+
0.0102
Mg2+
0.0528
Ca2+
0.0103
Many other aqua ions are present in seawater in concentrations ranging from ppm to ppt.[9] The concentrations of sodium, potassium, magnesium and calcium in blood are similar to those of seawater. Blood also has lower concentrations of essential elements such as iron and zinc. Sports drink is designed to be isotonic and also contains the minerals which are lost in perspiration.
Magnesium and calcium ions are common constituents of domestic water and are responsible for permanent and temporary hardness, respectively. They are often found in mineral water.
Experimental methods[edit]
Information obtained on the nature of ions in solution varies with the nature of the experimental method used. Some methods reveal properties of the cation directly, others reveal properties that depend on both cation and anion. Some methods supply information of a static nature, a kind of snapshot of average properties, others give information about the dynamics of the solution.
Nuclear magnetic resonance (NMR)[edit]
Ions for which the water-exchange rate is slow on the NMR time-scale give separate peaks for molecules in the first solvation shell and for other water molecules. The solvation number is obtained as a ratio of peak areas. Here it refers to the number of water molecules in the first solvation shell. Molecules in the second solvation shell exchange rapidly with solvent molecules, giving rise to a small change in the chemical shift value of un-coordinated water molecules from that of water itself. The main disadvantage of this method is that it requires fairly concentrated solutions, with the associated risk of ion-pair formation with the anion.
Solvation numbers determined by NMR[10]
ion
number
nucleus
Be2+ 4 1H 17O
Mg2+ 6 1H
Zn2+ 6 1H
Al3+ 6 1H 17O
Ga3+ 6 1H 17O
In3+ 6 1H
Fe2+ 6 17O
Co2+ 6 1H
Ni2+ 6 1H 17O
Th4+ 9 1H
X-ray diffraction (XRD)[edit]
A solution containing an aqua ion does not have the long-range order that would be present in a crystal containing the same ion, but there is short-range order. X-ray diffraction on solutions yields a radial distribution function from which the coordination number of the metal ion and metal-oxygen distance may be derived. With aqua ions of high charge some information is obtained about the second solvation shell.[11][12]
This technique requires the use of relatively concentrated solutions. X-rays are scatted by electrons, so scattering power increases with atomic number. This makes hydrogen atoms all but invisible to X-ray scattering.
Large angle X-ray scattering has been used to characterize the second solvation shell with trivalent ions such as Cr3+ and Rh3+. The second hydration shell of Cr3+ was found to have 7001130000000000000♠13±1 molecules at an average distance of 6990402000000000000♠402±20 pm. This implies that every molecule in the first hydration shell is hydrogen bonded to two molecules in the second shell.[13]
Neutron diffraction[edit]
Diffraction by neutrons also give a radial distribution function. In contrast to X-ray diffraction, neutrons are scatted by nuclei and there is no relationship with atomic number.[14] Indeed, use can be made of the fact that different isotopes of the same element can have widely different scattering powers. In a classic experiment, measurements were made on four nickel chloride solutions using the combinations of 58Ni, 60Ni, 35Cl and 37Cl isotopes to yield a very detailed picture of cation and anion solvation.[15] Data for a number of metal salts show some dependence on the salt concentration.
Cation hydration determined by neutron diffraction[16]
Cation
Anion
Molality
/mol kg−1 (a)
Hydration
number
θ /deg (b)
Li+ Cl− 27.77 2.3 (2)(c) 75 (5)
9.95 3.0 (5) 52 (5)
3.57 5.5 (3) 40 (5)
Ca2+ Cl− 4.49 6.4 (3) 34 (9)
2.80 7.2 (2) 34 (9)
1.0 10.0 (6) 38 (9)
Ni2+ Cl− 3.05 5.8 (2) 42 (8)
0.85 6.6 (5) 27 (10)
0.46 6.8 (8) 17 (10)
0.086 6.8 (8) 0 (20)
Ni2+ ClO−
4 3.80 5.8 (2) 42 (8)
Cu2+ ClO−
4 2.00 4.9 (3) 38 (6)
Fe3+ NO−
3 2.0 5.0 (2) 22 (4)
Nd3+ Cl− 2.85 8.5 (2) 24 (4)
Dy3+ Cl− 2.38 7.4 (5) 17 (3)
(a) moles solute per kg of solvent. (b) angle between M-O and the H-m lines, m= mid point between H or D atoms. (c) Figures in brackets are standard deviations on the last significant figure of the value.
Most of these data refer to concentrated solutions in which there are very few water molecules that are not in the primary hydration spheres of the cation or anion, which may account for some of the variation of solvation number with concentration even if there is no contact ion pairing. The angle θ gives the angle of tilt of the water molecules relative to a plane in the aqua ion. This angle is affected by the hydrogen bonds formed between water molecules in the primary and secondary solvation shells.
The measured solvation number is a time-averaged value for the solution as a whole. When a measured primary solvation number is fractional there are two or more species with integral solvation numbers present in equilibrium with each other. This also applies to solvation numbers that are integral numbers, within experimental error. For example, the solvation number of 5.5 for a lithium chloride solution could be interpreted as being due to presence of two different aqua ions with equal concentrations.
[Li(H2O)6]+ ⇌ [Li(H2O)5]+ + H2O
Another possibility is that there is interaction between a solvated cation and an anion, forming an ion pair. This is particularly relevant when measurements are made on concentrated salt solutions. For example, a solvation number of 3 for a lithium chloride solution could be interpreted as being due to the equilibrium
[Li(H2O)4]+ + Cl− ⇌ [Li(H2O)3Cl] + H2O
lying wholly in favour of the ion pair.
Vibrational spectra[edit]
Infrared spectra and Raman spectra can be used to measure the M-O stretching frequency in metal aqua ions. Raman spectroscopy is particularly useful because the Raman spectrum of water is weak whereas the infrared spectrum of water is intense. Interpretation of the vibration frequencies is somewhat complicated by the presence, in octahedral and tetrahedral ions, of two vibrations, a symmetric one measured in the Raman spectrum and an anti-symmetric one, measured in the infrared spectrum.
Symmetric M-O stretching vibrations of some aqua ions in solution[17]
metal ion
wavenumber /cm−1
Be2+ 530-543
Mg2+ 360-365
Mn2+ 395
Fe2+ 389
Ni2+ 405
Cu2+ 440
Zn2+ 385-400
Hg2+ 380[18]
Al3+ 520-526
Ga3+ 475
In3+ 400
Although the relationship between vibration frequency and force constant is not simple, the general conclusion that can be taken from these data is that the strength of the M-O bond increases with increasing ionic charge and decreasing ionic size. The M-O stretching frequency of an aqua ion in solution may be compared with its counterpart in a crystal of known structure. If the frequencies are very similar it can be concluded that the coordination number of the metal ion is the same in solution as it is in a compound in the solid state.
Dynamic methods[edit]
Data such as conductivity, mobility and diffusion relate to the movement of ions through a solution. When an ion moves through a solution it tends to take both first and second solvation shells with it. Hence solvation numbers measured from dynamic properties tend to be much higher that those obtained from static properties.
Hydration numbers measured by dynamic methods[19]
Li+
Na+
Cs+
Mg2+
Ca2+
Ba2+
Zn2+
Cr3+
Al3+
Transport number 13-22 7-13 4 12-14 8-12 3-5 10-13
Ion mobility 3-21 2-10 10-13 7-11 5-9 10-13
Diffusion 5 3 1 9 9 8 11 17 13
Solvation numbers and structures[edit]
Alkali metals[edit]
Solvation numbers of 3 - 6 have been found for lithium aqua ions. Solvation numbers less than 4 may be the result of the formation of contact ion pairs. The higher solvation numbers may be interpreted in terms of water molecules that approach [Li(H2O)4]+ through a face of the tetrahedron, though molecular dynamic simulations may indicate the existence of an octahedral aqua ion.[20] There are most probably six water molecules in the primary solvation sphere of the sodium ion. For potassium, rubidium and caesium even the primary solvation shell is not well defined.[21]
Alkaline earth metals[edit]
Molecular hydration data for group 2 metal ions[22]
M2+(aq)
M-O distance /pm
− Δ H ⊖ / k J m o l − 1 {\displaystyle -\Delta H^{\ominus }\mathrm {/kJ\ mol^{-1}} }
− Δ V ⊖ / c m 3 m o l − 1 {\displaystyle -\Delta V^{\ominus }\mathrm {/cm^{3}\ mol^{-1}} }
Be 167 2494 -12.0
Mg 209 1921 -21.2
Ca 242 1577 -17.9
Sr 263 1443 -18.2
Ba 281 1305 -12.5
[Be(H2O)4]2+ has a very well-defined primary solvation shell; The BeO4 part has tetrahedral symmetry, Td.[23] [Mg(H2O)6]2+ is also a well-characterized species, with an octahedral core. The situation for calcium is more complicated. Neutron diffraction data gave a solvation number for calcium chloride, CaCl2, which is strongly dependent on concentration: 7001100000000000000♠10.0±0.6 at 1 mol·dm−3, decreasing to 7000640000000000000♠6.4±0.3 at 2.8 mol·dm−3. The Shannon radius of the six-coordinate calcium ion is 100 pm compared to 72 pm for magnesium, a 28% increase in size. This allows for higher aquation numbers and the lower charge density (z2/r) results in weaker M-O bonds, which makes ion pairing easier. Various solid hydrates are known with 8-coordination in square antiprism and dodecahedral geometry.[24]
Aluminium and group 3 metals[edit]
By convention aluminium is placed in group 13, with gallium, indium and thallium. Nevertheless, a comparison of aluminium and scandium aqua ions illustrates a trend between the congeners Na+/K+, Mg2+/Ca2+ and Al3+/Sc3+ which depends on the increase in size on going from rows 3 to 4 in the periodic table. Shannon radii for 6-coordinate Al3+ and Sc3+ are 54 and 74.5 pm. Ga3+ has a Shannon radius of 62 pm, only about 13% larger than that of Al3+. This is due to the presence of the ten elements between scandium and gallium, which make an additional contribution to the general decrease in size across all rows of the periodic table. The aluminium aqua ion, [Al(H2O)6]3+ is very well characterized in solution and the solid state. The AlO6 core has octahedral symmetry, point group Oh.
There is now a substantial body of indirect evidence that seven molecules of water are present in the aqua ion of scandium, Sc3+.[25] Yttrium(III) has approximately the same Shannon radius as holmium(III) so Y3+ has very similar properties to those of Ho3+, so its aqua ion is probably 8-coordinate. The lanthanum aqua ion is probably 9-coordinate, as are those of the lighter lanthanides.
Transition metals and group 12 metals[edit]
See also: Metal aquo complex
Jahn-Teller distorted octahedral structure of [Cu(H2O)6]2+ found in the solid state and possibly also in solution[26]
Proposed square pyramidal structure of [Cu(H2O)5]2+ in aqueous solution[27]
The ions of these metals in the +2 and +3 oxidation states have a solvation number of 6. All have a regular octahedral structure except the aqua ions of chromium(II) and copper(II) which are subject to Jahn-Teller distortion. In the copper case the two axial Cu−O distances are 238 pm, whereas the four equatorial Cu−O distances are 195 pm in the solid state.[28] However, it is unclear whether Cu2+ has a solvation number of 5 or 6 in aqueous solution, with conflicting experimental reports.[26] Silver(I) is probably 4-coordinate, [Ag(H2O)4]+.[29]
A solvation number of 6 with an octahedral structure is well established for zinc(II) and cadmium(II) in dilute solutions. In concentrated solutions the Zn2+ ion may adopt a 4-coordinate, tetrahedral, structure, but the evidence is not conclusive because of the possibility of ion pairing and/or hydrolysis.[30] The solvation number of mercury(II) is most likely to be 6.[31]
The bis aqua structure of the mercury(I) ion,[(H2O)-Hg-Hg-(OH2]+, found in solid compounds, is also found in solution.[32] Another aqua species in which there is a metal-metal bond is the molybdenum(II) species formulated as [(H4O)-Mo-Mo-(OH4]4+ on the basis of theoretical considerations of the nature of the Mo-Mo bond. Each molybdenum is surrounded by four water molecules in a square-planar arrangement, in a structure similar to that of the known structure of the chloro complex [Mo2Cl8]4−. The presence of a fifth water molecule in the axial position is not ruled out, however.[33]
There are a few divalent and trivalent aqua ions of transition metals in the second and third transition series. With oxidation state 4, however, only hydrolyzed species exist.
Group 13-15 metals[edit]
The aqua ions of gallium(III) and indium(III) and thallium(III) have a solvation number of 6. The aqua ion of thallium(I) is often assumed to be 6-coordinate, but this assumption is not based on strong experimental evidence.[34] The Shannon radius of Tl+, at 150 pm, is not very different from that of K+, at 138 pm, so some similarity between Tl+ and K+ chemistry is both expected and observed.[35]
The solvation number of the tin(II) aqua ion, [Sn(H2O)n]2+ is not known with any certainty due to the presence of hydrolysis in the concentrated solutions needed for X-ray scattering measurements.[36] The same is true for the lead(II) aqua ion. With bismuth(III) there is indirect evidence for a solvation number of 9. A nonahydrate is been characterized in the solid state, with a face-capped trigonal prism structure. The Shannon radius for 9-coordinate bismuth (115 pm) is comparable to that of neodymium (116.3 pm) for which a solvation number of 9 is well-established.[37]
Lanthanides and actinides[edit]
face-capped trigonal prism structure
The trivalent lanthanide ions decrease steadily in size from lanthanum to lutetium, an effect known as the lanthanide contraction. Nevertheless, there is strong evidence that the hydration number changes from 9 to 8 at around gadolinium.[38] Structures of aqua ions in the solid state include the 9-coordinate tricapped trigonal prism structure with the lighter lanthanide ions and the 8-coordinate square antiprism structure with the heavier lanthanide ions.There are no experimental data for the solvation state of cerium(IV) or europium(II).[39]
Solvation numbers of 9 or more are believed to apply to the actinide ions in the +3 and +4 oxidation states, but an experimental value is available only for thorium(IV).
Oxo-aqua-cations[edit]
Some elements in oxidation states higher than 3 form stable, aquated, oxo ions. Well known examples are the vanadyl(IV) and uranyl(VI) ions. They can be viewed as particularly stable hydrolysis products in a hypothetical reaction such as
[V(H2O)6]4+ → [VO(H2O)5]2+ + 2H+
The vanadium has a distorted octahedral environment (point group C4v) of one oxide ion and 5 water molecules.[40] Vanadium(V) is believed to exist as the dioxo-ion [VO2(H2O)4]+ at pH less than 2, but the evidence for this ion depends on the formation of complexes, such as oxalate complexes which have been shown to have the VO+
2 unit, with cis-VO bonds, in the solid state.[41] The chromium(IV) ion [CrO(H2O)5]2+, similar to the vanadium ion has been proposed on the basis of indirect evidence.[42]
The uranyl ion, UO2+
2, has a trans structure. The aqua ion UO2+
2(aq) has been assumed, on the basis of indirect evidence, to have five water molecules in the plane perpendicular to the O-U-O axis in a pentagonal bipyramid structure, point group D5h. However it is also possible that there are 6 water molecules in the equatorial plane, hexagonal bipyramid, point group D6h, as many complexes with this structure are known.[43] The solvation state of the plutonyl ion, PuO2+
2, is not known.
Thermodynamics[edit]
The main goal of thermodynamics in this context is to derive estimates of single-ion thermodynamic quantities such as hydration enthalpy and hydration entropy. These quantities relate to the reaction
Mz+ (gas) + solvent → Mz+ (in solution)
The enthalpy for this reaction is not directly measurable, because all measurements use salt solutions that contain both cation and anion. Most experimental measurements relate to the heat evolved when a salt dissolves in water, which gives the sum of cation and anion solvation enthalpies. Then, by considering the data for different anions with the same cation and different cations with the same anion, single ion values relative to an arbitrary zero, are derived.
Minus hydration enthalpy for (octahedral) divalent transition metal M2+ ions[44]
Hydration enthalpies of trivalent lanthanide Ln3+ ions[44]
Single ion standard hydration enthalpy /kJ mol−1[44]
Li+
-514.6 Be2+
-2487.0
Na+
-404.6 Mg2+
-1922.1 Al3+
-4659.7
K+
-320.9 Ca2+
-1592.4 Sc3+
-3960.2 ... Ga3+
-4684.8
Rb+
-296.2 Sr2+
-1444.7 Y3+
-3620.0 ... In3+
-4108.7 Sn2+
-1554.4
Cs+
-263.2 Ba2+
-1303.7 La3+
-3282.8 ... Tl3+
-4184.0 Pb2+
-1479.9
Other values include Zn2+ -2044.3, Cd2+ -1805.8 and Ag+ -475.3 kJ mol−1.
There is an excellent linear correlation between hydration enthalpy and the ratio of charge squared, z2, to M-O distance, reff.[45]
Δ H ⊖ = − 69500 z 2 / r e f f {\displaystyle \Delta H^{\ominus }=-69500\ \mathrm {z^{2}/r_{eff}} }
Values for transition metals are affected by crystal field stabilization. The general trend is shown by the magenta line which passes through Ca2+, Mn2+ and Zn2+, for which there is no stabilization in an octahedral crystal field. Hydration energy increases as size decreases. Crystal field splitting confers extra stability on the aqua ion. The maximum crystal field stabilization energy occurs at Ni2+. The agreement of the hydration enthalpies with predictions provided one basis for the general acceptance of crystal field theory.[46]
The hydration enthalpies of the trivalent lanthanide ions show an increasingly negative values at atomic number increases, in line with the decrease in ionic radius known as the lanthanide contraction.
Single ion hydration entropy can be derived. Values are shown in the following table. The more negative the value, the more there is ordering in forming the aqua ion. It is notable that the heavy alkali metals have rather small entropy values which suggests that both the first and second solvation shells are somewhat indistinct.
Single ion standard hydration entropy at 25 °C /J deg−1 mol−1[47]
Li+
-118.8
Na+
-87.4 Mg2+
-267.8 Al3+
-464.4
K+
-51.9 Ca2+
-209.2 ... Ga3+
-510.4
Rb+
-40.2 Sr2+
-205.0 ... In3+
-426.8
Cs+
-36.8 Ba2+
-159.0 La3+
-368.2 ...
Hydrolysis of aqua ions[edit]
See also: Hydrolysis
There are two ways of looking at an equilibrium involving hydrolysis of an aqua ion. Considering the dissociation equilibrium
[M(H2O)n]z+ - H+⇌ [M(H2O)n-1(OH)](z-1)+
the activity of the hydrolysis product, omitting the water molecules, is given by
{ [ M ( OH ) ] ( z − 1 ) + } = K 1 , − 1 { M z + } { H + } − 1 {\displaystyle \{[{\ce {M(OH)}}]^{(z-1)+}\}=K_{1,-1}\{{\ce {M}}^{z+}\}\{{\ce {H}}^{+}\}^{-1}}
The alternative is to write the equilibrium as a complexation or substitution reaction
[M(H2O)n]z+ +OH− ⇌ :[M(H2O)n-1(OH)](z-1)+ + H2O
In which case
{ [ M ( OH ) ] ( z − 1 ) + } = K 1 , 1 { M z + } { OH − } {\displaystyle \{[{\ce {M(OH)}}]^{(z-1)+}\}=K_{1,1}\{{\ce {M}}^{z+}\}\{{\ce {OH}}^{-}\}}
The concentration of hydrogen and hydroxide ions are related by the self-ionization of water, Kw = {H+} {OH−} so the two equilibrium constants are related as
K 1 , − 1 = K 1 , 1 × K w {\displaystyle K_{1,-1}=K_{1,1}\times K_{w}}
In practice the first definition is more useful because equilibrium constants are determined from measurements of hydrogen ion concentrations. In general,
[ M x ( OH ) y ] = β x , − y ∗ [ M ] x [ H ] − y {\displaystyle [{\ce {M}}_{x}({\ce {OH}})_{y}]=\beta _{x,-y}*[{\ce {M}}]^{x}[{\ce {H}}]^{-y}}
charges are omitted for the sake of generality and activities have been replaced by concentrations. β ∗ {\displaystyle \beta *} are cumulative hydrolysis constants.
Modeling the hydrolysis reactions that occur in solution is usually based on the determination of equilibrium constants from potentiometric (pH) titration data. The process is far from straightforward for a variety of reasons.[48] Sometimes the species in solution can be precipitated as salts and their structure confirmed by X-ray crystallography. In other cases, precipitated salts bear no relation to what is postulated to be in solution, because a particular crystalline substances may have both low solubility and very low concentration in the solutions.
First hydrolysis constant[edit]
The logarithm of hydrolysis constant, K1,-1, for the removal of one proton from an aqua ion
[M(H2O)n]z+ - H+ ⇌ [M(H2O)n-1(OH)](z-1)+
[ [M(OH)]{(z-1)+ ] = K1,-1 [Mz+] [H+] −1
shows a linear relationship with the ratio of charge to M-O distance, z/d. Ions fall into four groups. The slope of the straight line is the same for all groups, but the intercept, A, is different.[49]
log K1,-1 = A + 11.0 z/d
cation
A
Mg2+, Ca2+, Sr2+, Ba2+
Al3+, Y3+, La3+ 2998780000000000000♠−22.0±0.5
Li+, Na+, K+
Be2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+
Sc3+, Ti3+, V3+, Cr3+, Fe3+, Rh3+, Ga3+, In3+
Ce4+, Th4+, Pa4+, U4+, Np4+, Pu4+, 2998802000000000000♠−19.8±1
Ag+, Tl+
Pb2+
Ti3+, Bi3+, 2998841000000000000♠−15.9±1
Sn2+, Hg2+, Sn2+, Pd2+ ca. 12
The cations most resistant to hydrolysis for their size and charge are hard pre-transition metal ions or lanthanide ions. The slightly less resistant group includes the transition metal ions. The third group contains mostly soft ions ion of post-transition metals. The ions which show the strongest tendency to hydrolyze for their charge and size are Pd2+, Sn2+ and Hg2+.[49]
The standard enthalpy change for the first hydrolysis step is generally not very different from that of the dissociation of pure water. Consequently, the standard enthalpy change for the substitution reaction
[M(H2O)n]z+ +OH− ⇌ :[M(H2O)n-1(OH)](z-1)+ + H2O
is close to zero. This is typical of reactions between a hard cation and a hard anion, such as the hydroxide ion.[50] It means that the standard entropy charge is the major contributor to the standard free energy change and hence the equilibrium constant.
Δ G ⊖ = − R T ln  K = Δ H ⊖ − T Δ S ⊖ {\displaystyle \Delta G^{\ominus }=-RT\ln K=\Delta H^{\ominus }-T\Delta S^{\ominus }}
The change in ionic charge is responsible for the effect as the aqua ion has a greater ordering effect on the solution than the less highly charged hydroxo complex.
Multiple hydrolysis reactions[edit]
Beryllium hydrolysis as a function of pH. Water molecules attached to Be are omitted
trimeric hydrolysis product of beryllium
The molybdenum(IV) oxo-aqua ion [Mo3O4(H2O)9]4+
The hydrolysis of beryllium shows many of the characteristics typical of multiple hydrolysis reactions. The concentrations of various species, including polynuclear species with bridging hydroxide ions, change as a function of pH up to the precipitation of an insoluble hydroxide. Beryllium hydrolysis is unusual in that the concentration of [Be(H2O)3(OH)]+ is too low to be measured. Instead a trimer ([Be3(H2O)6(OH3))3+ is formed, whose structure has been confirmed in solid salts. The formation of polynuclear species is driven by the reduction in charge density within the molecule as a whole. The local environment of the beryllium ions approximates to [Be(H2O)2(OH)2]+. The reduction in effective charge releases free energy in the form of a decrease of the entropy of ordering at the charge centers.[51]
Some polynuclear hydrolysis products[52]
Species formula
cations
structure
M2(OH)+ Be2+, Mn2+, Co2+, Ni2+
Zn2+, Cd2+, Hg2+, Pb2+ single hydroxide bridge between two cations
M2(OH)(2z-2)+
2 Cu2+, Sn2+
Al3+, Sc3+, Ln3+, Ti3+, Cr3+
Th4+
VO2+, UO2+
2, NpO2+
2, PuO2+
2 double hydroxide bridge between two cations
M
3(OH)3+
3 Be2+, Hg2+ six-membered ring with alternate Mn+ and OH− groups
M
3(OH)(3z-4)+
4 Sn2+, Pb2+
Al3+, Cr3+, Fe3+, In3+ Cube with alternate vertices of Mn+ and OH− groups, one vertex missing
M
4(OH)4+
4 Mg2+, Co2+, Ni2+, Cd2+, Pb2+ Cube with alternate vertices of Mn+ and OH− groups
M
4(OH)8+
8 Zr4+, Th4+ Square of Mn+ ions with double hydroxide bridges on each side of the square
The hydrolysis product of aluminium formulated as [Al13O4(OH)24(H2O)12]7+ is very well characterized and may be present in nature in water at pH ca. 5.4.[53]
The overall reaction for the loss of two protons from an aqua ion can be written as
[M(H2O)n]z+ - 2 H+⇌ [M(H2O)n-2(OH)2](z-2)+
However, the equilibrium constant for the loss of two protons applies equally well to the equilibrium
[M(H2O)n]z+ - 2 H+⇌ [MO(H2O)n-2](z-2)+ + H2O
because the concentration of water is assumed to be constant. This applies in general: any equilibrium constant is equally valid for a product with an oxide ion as for the product with two hydroxyl ions. The two possibilities can only be distinguished by determining the structure of a salt in the solid state. Oxo bridges tend to occur when the metal oxidation state is high.[54] An example is provided by the molybdenum(IV) complex [Mo3O4(H2O)9]4+ in which there is a triangle of molybdenum atoms joined by σ- bonds with an oxide bridge on each edge of the triangle and a fourth oxide which bridges to all three Mo atoms.[55]
Oxyanions[edit]
Main article: oxyanion
There are very few oxo-aqua ions of metals in the oxidation state +5 or higher. Rather, the species found in aqueous solution are monomeric and polymeric oxyanions. Oxyanions can be viewed as the end products of hydrolysis, in which there are no water molecules attached to the metal, only oxide ions.
Exchange kinetics[edit]
A water molecule in the first solvation shell of an aqua ion may exchange places with a water molecule in the bulk solvent. It is usually assumed that the rate-determining step is a dissociation reaction.
[M(H2O)n]z+ → [M(H2O)n-1]z+* + H2O
The * symbol signifies that this is the transition state in a chemical reaction. The rate of this reaction is proportional to the concentration of the aqua ion, [A].
r a t e = − ( d [ A ] d t ) T = k [ A ] {\displaystyle \mathrm {rate} =-\left({\frac {d[A]}{dt}}\right)_{T}=k[A]} .
The proportionality constant, k, is called a first-order rate constant at temperature T. The unit of the rate constant for water exchange is usually taken as mol dm−3s−1. The half-life for this reaction is equal to loge2 / k. This measure is useful because it is independent of concentration. It has the dimension of time. The quantity 1/k, equal to the half life divided by 0.6932, is known as the residence time or time constant.[56]
The residence time for water exchange varies from about 10−10 s for Cs+ to about 10+10 s (more than 200 y) for Ir3+. It depends on factors such as the size and charge on the ion and, in the case of transition metal ions, crystal field effects. Very fast and very slow reactions are difficult to study. The most information on the kinetics a water exchange comes from systems with a residence time between about 1 μs and 1 s. The enthalpy and entropy of activation, ΔH‡ and ΔS‡ can be obtained by observing the variation of rate constant with temperature.
Selected kinetic parameters for water exchange at 25 °C[57]
ion
residence
time /μs
ΔH‡
/kJ mol−1
ΔS‡
/J deg−1mol−1
Be2+ 7003100000000000000♠1.0×103
Mg2+ 2.0 43 8
V2+ 7004130000000000000♠1.3×104 69 21
Cr2+ 0.0032 13 -13
Mn2+ 0.0316 34 12
Fe2+ 0.32 32 -13
Co2+ 0.79 33 -17
Ni2+ 40 43 -22
Cu2+ 6996500000000000000♠5.0×10−4 23 25
Zn2+ 0.032
Al3+ 7006630000000000000♠6.3×106 11 117
Ti3+ 16 26 -63
Cr3+ 7012200000000000000♠2.0×1012 109 0
Fe3+ 316 37 -54
Ga3+ 501 26 -92
Rh3+ 7013320000000000000♠3.2×1013 134 59
In3+ 50 17
La3+ 0.050
U2+
2 1.3
The kinetic parameters for aqua ions of the transition metals are affected by crystal field stabilization energy (CFSE) on both the aqua ion and its dissociation product which has one less water molecule in the primary solvation shell. This explains the inertness (long residence time) of Cr3+, which has an octahedral structure and a d3 electronic configuration and Rh3+ and Ir3+ which are also octahedral and have a low-spin d6 configuration. Trivalent ions have longer residence time than divalent ions, except for the very large lanthanide ions. The values in the table show that this is due to both activation enthalpy and entropy factors.[58]
Mechanisms[edit]
The assignment of mechanisms to the water exchange reaction has not yet been made unambiguously. The simple dissociation mechanism needs to be modified to take into account the presence of a second solvation shell. In all cases exchange between molecules in the second shell and bulk water is fast compared to the rate-determining step. Three possible mechanism arise.[59]
Id (dissociative interchange) mechanism. A water molecule leaves the first solvation shell and enters the second shell.
Ia (associative interchange) mechanism. The same exchange reaction takes place, but there is a significant interaction, in the transition state, between the incoming water molecule and the metal ion.
A mechanism. This is an associative mechanism involving a molecule from the bulk solvent.
This classification represents extreme cases; the actual mechanism may have something of an intermediate nature. The most useful parameter for distinguishing between possible mechanism is the activation volume change, ΔV‡, which is obtained from the pressure variation of the rate constant.[60]
( ∂ l n k ∂ P ) T = Δ V ‡ R T {\displaystyle \left({\frac {\partial lnk}{\partial P}}\right)_{T}={\frac {\Delta V^{\ddagger }}{RT}}}
The activation volume increases for dissociative mechanisms and decreases for associative mechanisms.
Formation of complexes[edit]
Main articles: Coordination complex and Stability constants of complexes
Metal aqua ions are often involved in the formation of complexes. The reaction may be written as
pMx+(aq) + qLy− → [MpLq](px-qy)+
In reality this is a substitution reaction in which one or more water molecules from the first hydration shell of the metal ion are replaced by ligands, L. The complex is described as an inner-sphere complex. A complex such as [ML](p-q)+ may be described as a contact ion pair.
When the water molecule(s) of the second hydration shell are replaced by ligands, the complex is said to be an outer-sphere complex, or solvent-shared ion pair. The formation of solvent-shared or contact ion pairs is particularly relevant to the determination of solvation numbers of aqua ions by methods that require the use of concentrated solutions of salts, as ion pairing is concentration-dependent. Consider, for example, the formation of the complex [MgCl]+ in solutions of MgCl2. The formation constant K of the complex is about 1 but varies with ionic strength.[61] The concentration of the rather weak complex increases from about 0.1% for a 10mM solution to about 70% for a 1M solution (1M = 1 mol dm−3).
Electrochemistry[edit]
The standard electrode potential for the half-cell equilibrium Mz+ + z e− ⇌ M(s) has been measured for all metals except for the heaviest trans-uranium elements.
Standard electrode potentials /V for couples Mz+/M(s)[62]
Li+
−3.040 Be2+
−1.85
Na+
−2.71 Mg2+
−2.372 Al3+
−1.66
K+
−2.931 Ca2+
−2.868 Sc3+
−2.90 ... Zn2+
−0.751 Ga3+
−0.53
Rb+
−2.98 Sr2+
−2.899 Y3+
−2.37 ... Cd2+
−0.403 In3+
−0.342 Sn2+
−0.136
Cs+
−3.026 Ba2+
−2.912 ... Hg2+
−0.854 Tl3+
+0.73 Pb2+
−0.126 Bi3+
+0.16
La3+
−2.52 Ce3+
−2.32 Pr3+
−2.34 Nd3+
−2.32 Pm3+
−2.30 Sm3+
−2.28 Eu3+
−1.98 Gd3+
−2.27 Tb3+
−2.27 Dy3+
−2.32 Ho3+
−2.37 Er3+
−2.33 Tm3+
−2.30 Yb3+
−2.23 Lu3+
−2.25
Ac3+
−2.18 Th4+
−1.83 Pa4+
−1.46 U4+
−1.51 Np4+
−1.33 Pu4+
−1.80 Am3+
−2.06 Cm3+
−2.07 Bk3+
−2.03 Cf3+
−2.01 Es3+
−1.99 Fm3+
−1.97 Md3+
−1.65 No3+
−1.20 Lr3+
−1.96
Standard electrode potentials /V for 1st. row transition metal ions[62]
Couple
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
M2+ / M −1.63 −1.18 −0.91 −1.18 −0.473 −0.28 −0.228 +0.345
M3+ / M −1.37 −0.87 −0.74 −0.28 −0.06 +0.41
Miscellaneous standard electrode potentials /V[62]
Ag+ / Ag
Pd2+ / Pd
Zr4+ / Zr
Hf4+ / Hf
Au3+ / Au
Ce4+ / Ce
+0.799 +0.915 −1.53 −1.70 +1.50 −1.32
As the standard electrode potential is more negative the aqua ion is more difficult to reduce. For example, comparing the potentials for zinc (-0.75 V) with those of iron (Fe(II) -0.47 V, Fe(III) -0.06 V) it is seen that iron ions are more easily reduced than zinc ions. This is the basis for using zinc to provide anodic protection for large structures made of iron or to protect small structures by galvanization.
References[edit]
Jump up ^ Burgess, Section 1.2.
Jump up ^ Burgess, p. 20.
Jump up ^ Richens, p. 25.
Jump up ^ Burgess, p. 181.
Jump up ^ Shannon, R.D. (1976). "Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides". Acta Crystallogr. A. 32 (5): 751–767. Bibcode:1976AcCrA..32..751S. doi:10.1107/S0567739476001551. . Richens, Appendix 2.
Jump up ^ Burgess, chapter 11.
Jump up ^ Burgess, Chapter 6.
Jump up ^ Chipperfield, John (1999). Non-Aqueous Solvents. Oxford: OUP. ISBN 0-19-850259-1.
^ Jump up to: a b Stumm&Morgan
Jump up ^ Burgess, p. 53.
Jump up ^ Sykes, A.G. (Editor); Johansson, Georg (1992). Structures of Compexes in Solution Derived from X-ray Diffraction Measurements. Advances in Inorganic Chemistry. 39. San Diego: Academic Press. pp. 161–232. ISBN 0-12-023639-7. CS1 maint: Extra text: authors list (link)
Jump up ^ Ohtaki, H.; Radnai, T. (1993). "Structure and dynamics of hydrated ions". Chem. Rev. 93 (3): 1157–1204. doi:10.1021/cr00019a014.
Jump up ^ Magini, M.; Licheri, G.; Paschina, G.; Piccaluga,G.; Pinna, G. (1988). X-ray diffraction of ions in aqueous solutions : hydration and complex formation. Boca Raton, Fla: CRC Press. ISBN 0-8493-6945-2.
Jump up ^ Sykes, A.G. (Editor); Enderby, J.E.; Nielson, G.W. (1989). The Coordination of Metal Ions. Advances in Inorganic Chemistry. 34. San Diego: Academic Press. pp. 195–218. ISBN 0-12-023634-6. CS1 maint: Extra text: authors list (link)
Jump up ^ Nieson, G.W.; Enderby, J.E. (1983). "The Structure of an Aqueous Solution of Nickel Chloride". Proceedings of the Royal Society A. 390: 353–371. Bibcode:1983RSPSA.390..353N. doi:10.1098/rspa.1983.0136.
Jump up ^ Enderby, J.E. (1987). "Diffraction Studies of Aqueous Ionic Solutions". In Bellisent-Funel, M-C.; Neilson, G.W. The Physics and Chemistry of Aqueous Solutions. NATO ASI Series. Reidel. pp. 129–145. ISBN 90-277-2534-9. p. 138.
Jump up ^ Burgess, p. 85.
Jump up ^ Adams, D.M. (1967). Metal-Ligand and Related Vibrations. London: Edward Arnold. p.254.
Jump up ^ Richens, p. 40.
Jump up ^ Richens, p. 126.
Jump up ^ Richens, p. 127.
Jump up ^ Richens, p. 140. Data from Persson, I.; Sandstrom, M.; Yokohama, H.; Chaudhry, M. (1995). "?". Z. Naturforsch. A. 50: 21.
Jump up ^ Richens, p. 129.
Jump up ^ Richens, section 2.3.
Jump up ^ Richens, p. 176.
^ Jump up to: a b Persson, Ingmar (2010). "Hydrated metal ions in aqueous solution: How regular are their structures?". Pure Appl. Chem. 82: 1901–1917. doi:10.1351/PAC-CON-09-10-22.
Jump up ^ Frank, Patrick; Benfatto, Maurizio; Szilagyi, Robert K.; D'Angelo, Paola; Della Longa, Stefano; Hodgson, Keith O. (2005). "The Solution Structure of [Cu(aq)]2+ and Its Implications for Rack-Induced Bonding in Blue Copper Protein Active Sites". Inorganic Chemistry. 44: 1922–1933. doi:10.1021/ic0400639.
Jump up ^ Richens, chapters 4-12
Jump up ^ Richens, p. 521
Jump up ^ Richens, p. 544.
Jump up ^ Richens, p. 555.
Jump up ^ Richens, p 551.
Jump up ^ Richens, p. 282.
Jump up ^ Richens, section 2.4.
Jump up ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 241. ISBN 0-08-037941-9. .
Jump up ^ Richens, pp152-153.
Jump up ^ Richens, p. 157.
Jump up ^ Richens, p. 185.
Jump up ^ Richens, p. 198.
Jump up ^ Richens, p. 236
Jump up ^ Richens, p. 240
Jump up ^ Richens, p. 278.
Jump up ^ Richens, p.202.
^ Jump up to: a b c Data from Burgess, p. 182.
Jump up ^ Richens, Figure 1.2.
Jump up ^ Orgel, Lesie E. (1966). An introduction to transition-metal chemistry. Ligand field theory (2nd. ed.). London: Methuen. p. 76.
Jump up ^ Burgess, p. 187.
Jump up ^ Baes&Mesmer, chapter 3.
^ Jump up to: a b Baes&Mesmer, p407
Jump up ^ Baes&Mesmer, p 409.
Jump up ^ Baes&Mesmer, section 18.2.
Jump up ^ Baes&Mesmer, Table 18.3.
Jump up ^ Richens, p. 145.
Jump up ^ Baes&Mesmer, p. 420.
Jump up ^ Richens, Figure 6.26, p. 295
Jump up ^ * Atkins, P.W.; de Paula, J. (2006). Physical Chemistry (8th. ed.). Oxford University Press. ISBN 0-19-870072-5. Chapter 22.
Jump up ^ Adapted from Burgess, Tables 11.4 and 11.5
Jump up ^ Burgess, p. 326.
Jump up ^ Burgess, p. 319.
Jump up ^ Richens, p. 74. Burgess, p. 323.
Jump up ^ IUPAC SC-Database A comprehensive database of published data on equilibrium constants of metal complexes and ligands
^ Jump up to: a b c Burgess, Table 8.1
Bibliography[edit]
Baes, C.F.; Mesmer, R.E. (1986) [1976]. The Hydrolysis of Cations. Malabar, FL: Robert E. Krieger. ISBN 0-89874-892-5.
Burgess, John (1978). Metal Ions in Solution. Chichester: Ellis Horwood. ISBN 0-85312-027-7.
Richens, David. T. (1997). The Chemistry of Aqua Ions. Wiley. ISBN 0-471-97058-1.
Stumm, Werner; Morgan, James J. (1995). Aquatic Chemistry - Chemical Equilibria and Rates in Natural Waters (3rd. ed.). Wiley-Blackwell. ISBN 0-471-51185-4.
Schweitzer, George K.; Pesterfield, Lester L. (2010). The Aqueous Chemistry of the Elements. Oxford: OUP. ISBN 0-19-539335-X.
Retrieved from "https://en.wikipedia.org/w/index.php?title=Metal_ions_in_aqueous_solution&oldid=797447094"
Categories:
Solutions
Hidden categories:
CS1 maint: Extra text: authors list
Articles to be merged from June 2017
All articles to be merged
Navigation menu
Personal tools
Not logged in
Talk
Contributions
Create account
Log in
Namespaces
Article
Talk
Variants
Views
Read
Edit
View history
More
Search
Navigation
Main page
Contents
Featured content
Current events
Random article
Donate to Wikipedia
Wikipedia store
Interaction
Help
About Wikipedia
Community portal
Recent changes
Contact page
Tools
What links here
Related changes
Upload file
Special pages
Permanent link
Page information
Wikidata item
Cite this page
Print/export
Create a book
Download as PDF
Printable version
Languages
Add links
This page was last edited on 27 August 2017, at 03:12.
Text is available under the Creative Commons Attribution-ShareAlike License; additional terms may apply. By using this site, you agree to the Terms of Use and Privacy Policy. Wikipedia® is a registered trademark of the Wikimedia Foundation, Inc., a non-profit organization.
Privacy policy
About Wikipedia
Disclaimers
Contact Wikipedia
Developers
Cookie statement
Mobile view
Enable previews

key: html

type: local

value: div

attrs: id class

values: mw-page-base noprint

values: mw-head-base noprint

attrs: id class style

value: a

attrs: id class lang

values: firstHeading firstHeading en

values: siteSub noprint

values: jump-to-nav mw-jump

value: img

attrs: alt src width height srcset data-file-width data-file-height

value: td

attrs: href title

value: i

value: small

value: span

value: tr

value: tbody

value: table

attrs: class role

values:
plainlinks metadata ambox ambox-move
presentation

value: b

attrs: href class title

values: Edit section: Introduction to metal aqua ions

attrs: alt src width height class srcset data-file-width data-file-height

values:
/wiki/First_coordination_sphere
mw-redirect
First coordination sphere

values:
/wiki/Dative_covalent_bond
mw-redirect
Dative covalent bond

values:
/wiki/Liquid_ammonia
mw-redirect
Liquid ammonia

values:
/wiki/Dimethyl_formamide
mw-redirect
Dimethyl formamide

values:
/wiki/Parts_per_million
mw-redirect
Parts per million

values:
/wiki/Parts_per_trillion
mw-redirect
Parts per trillion

values:
/wiki/Dietary_mineral
mw-redirect
Dietary mineral

values:
/wiki/Domestic_water
mw-redirect
Domestic water

values: Edit section: Nuclear magnetic resonance (NMR)

values:
/wiki/Nickel_chloride
mw-redirect
Nickel chloride

values: Edit section: Solvation numbers and structures

values: vertical-align: -0.838ex; width:17.718ex; height:3.176ex;

values: vertical-align: -0.838ex; width:19.139ex; height:3.176ex;

values:
/wiki/Molecular_point_group
mw-redirect
Molecular point group

values: Edit section: Aluminium and group 3 metals

values: Edit section: Transition metals and group 12 metals

attrs: alt src width height class data-file-width data-file-height

values: vertical-align: -0.838ex; width:23.359ex; height:3.176ex;

values:
/wiki/Crystal_field
mw-redirect
Crystal field

values: vertical-align: -1.005ex; width:40.39ex; height:3.509ex;

values: vertical-align: -1.005ex; width:38.575ex; height:3.509ex;

values: vertical-align: -1.005ex; width:19.324ex; height:2.843ex;

values: vertical-align: -1.005ex; width:31.537ex; height:3.009ex;

values: vertical-align: -0.671ex; width:3.031ex; height:2.509ex;

values:
/wiki/Hsab_theory
mw-redirect
Hsab theory

values: vertical-align: -0.338ex; width:36.643ex; height:2.509ex;

values: Edit section: Multiple hydrolysis reactions

values: vertical-align: -2.505ex; width:26.348ex; height:6.343ex;

values: {\mathrm  {rate}}=-\left({\frac  {d[A]}{dt}}\right)_{T}=k[A]

values:
/wiki/Rate_constant
mw-redirect
Rate constant

values:
/wiki/Kilojoule_per_mole
mw-redirect
Kilojoule per mole

values: vertical-align: -2.505ex; width:19.122ex; height:6.343ex;

values:
/wiki/Reduction_(chemistry)
mw-redirect
Reduction (chemistry)

values: Category:CS1 maint: Extra text: authors list

values:
nofollow
external text
//doi.org/10.1021%2Fcr00019a014

values:
nofollow
external text
//doi.org/10.1098%2Frspa.1983.0136

values:
nofollow
external text
//doi.org/10.1351%2FPAC-CON-09-10-22

values:
nofollow
external text
//doi.org/10.1021%2Fic0400639

values: -moz-column-width: 25em; -webkit-column-width: 25em; column-width: 25em; list-style-type: decimal;

values: Category:Articles to be merged from June 2017

values: Discussion about edits from this IP address [ctrl-alt-n]

values: A list of edits made from this IP address [ctrl-alt-y]

values: You are encouraged to create an account and log in; however, it is not mandatory

values: You're encouraged to log in; however, it's not mandatory. [ctrl-alt-o]

values:
/wiki/Metal_ions_in_aqueous_solution
View the content page [ctrl-alt-c]
c

values: Discussion about the content page [ctrl-alt-t]

values: p-namespaces navigation vectorTabs p-namespaces-label

values:
p-variants
navigation
vectorMenu emptyPortlet
p-variants-label

values: Past revisions of this page [ctrl-alt-h]

values: p-views navigation vectorTabs p-views-label

values:
p-cactions
navigation
vectorMenu emptyPortlet
p-cactions-label

values:
mw-wiki-logo
/wiki/Main_Page
Visit the main page

values:
/wiki/Main_Page
Visit the main page [ctrl-alt-z]
z

values: Featured content – the best of Wikipedia

values: Find background information on current events

values:
/wiki/Special:Random
Load a random article [ctrl-alt-x]
x

values: portal navigation p-navigation p-navigation-label

values: Guidance on how to use and edit Wikipedia

values: About the project, what you can do, where to find things

values:
uls-settings-trigger
Language settings
0
button
true

values: mediawiki ltr sitedir-ltr mw-hide-empty-elt ns-0 ns-subject page-Metal_ions_in_aqueous_solution rootpage-Metal_ions_in_aqueous_solution skin-vector action-view


text:
Splish Splash (song)
From Wikipedia, the free encyclopedia
Jump to navigation Jump to search
"Splish Splash"
Single by Bobby Darin
B-side
"Judy Don't Be Moody"
Released
May 19, 1958
Format
LP
Recorded
April 10, 1958
Atlantic Studios
(New York, New York)
Genre
Rock and roll, novelty song
Length
2:12
Label
Atco 6117
Songwriter(s)
Bobby Darin, Murray Kaufman
Bobby Darin singles chronology
"Just in Case You Change Your Mind"
(1958) "Splish Splash"
(1958) "Early in the Morning"
(1958)
"Just in Case You Change Your Mind"
(1958) "Splish Splash"
(1958) "Early in the Morning"
(1958)
"Splish Splash" is a 1958 song performed and co-written by Bobby Darin. It was written with DJ Murray the K (Murray Kaufman), who bet that Darin could not write a song that began with the words, "Splish Splash, I was takin' a bath", as suggested by Murray's mother, Jean Kaufman. The song was credited to Darin and "Jean Murray" (a combination of their names) to avoid any hint of payola. It was Darin's first hit and the song helped to give him a major boost in his career, reaching No. 3 on the U.S. pop singles chart and No. 2 on the R&B Best Sellers chart.[1] "Splish Splash" was Darin's only entry on the C&W Best Sellers in Stores chart, where it peaked at No. 14.[2] In a 1967 interview,[3] Darin claimed that he was so happy about having his first hit that his skin condition cleared up.[4]
Contents
1 Production
2 Other versions
3 References
4 External links
Production[edit]
Splish Splash was recorded in a session at New York's Atlantic Studios on the evening of April 10, 1958.[5] The personnel on the original recording included Jesse Powell on tenor sax,[6] Al Caiola, Billy Mure on guitar, Wendell Marshall on bass, and Panama Francis on drums.
Original copies of "Splish Splash" (Atco 6117) feature echo in the song. For the reissue (Atlantic Oldies Series 13055), the echo is filtered out.[citation needed]
The lyrics mention several characters from other songs of the period, including "Lollipop", "Peggy Sue", and "Good Golly Miss Molly".[4]
However, in an interview, former classmate Jerrold Atlas claimed that "Miss Molly" referred to Molly Epstein, Darin's former English teacher at the Bronx High School of Science. "She taught him to use the language in staccato notes: short fast, words...She was very fond of Bobby. Bobby told me she sharpened his respect for language".[7]
Other versions[edit]
British comedian Charlie Drake scored a top ten hit with a comedy version of the song in 1958, produced by future Beatles producer George Martin on the Parlophone label. The song was remade in 1979 by Barbra Streisand for her album Wet. It features new lyrics by Streisand and backing vocals from Toto lead singer Bobby Kimball and Chicago keyboardist Bill Champlin.
The song was featured in the trailer for the Patrick Dempsey film Loverboy. The song appears in the soundtrack for the 1998 movie, You've Got Mail, and also in an episode of Happy Days where Richie Cunningham becomes a DJ, 'Richie The C' (possibly a play on Murray the K). It was also featured as a DTV music video on The Disney Channel, set mostly to clips of Disney characters bathing, particularly from the 1948 cartoon Mickey and the Seal (illustrating the singer's bath in the first verse), but also Mickey's Birthday Party (to illustrate the party he walks in on). Kevin Spacey performs the song in the Bobby Darin biopic Beyond the Sea. The song was also featured on an insert on Sesame Street where the Zoo keepers at the Bronx Zoo are washing the elephants.
The song can also be heard in the films Because of Winn-Dixie and Air Bud. The song is also partially sung in 2012 film The Dictator, when the main character, General Aladeen (Sacha Baron Cohen) plays a practical joke on his new friend (Jason Mantzoukas) by singing the song with a severed head as a hand puppet, while his friend is taking a shower.
In 1976, Barry Williams, Maureen McCormick, Donny Osmond and Marie Osmond performed the song on The Brady Bunch Variety Hour.
In both the English and German versions of Animals United, Billy the Meerkat sings this song while taking a shower, but it's cut off by Toto the Chimpanzee.
Sky diver Andre Tayir performs this song on the Kidsongs Kids’ 1990 video: Ride the Roller Coaster.
References[edit]
Jump up ^ Whitburn, Joel (2004). Top R&B/Hip-Hop Singles: 1942-2004. Record Research. p. 145.
Jump up ^ Whitburn, Joel (2004). The Billboard Book Of Top 40 Country Hits: 1944-2006, Second edition. Record Research. p. 97.
Jump up ^ Gilliland, John (1969). "A-D interview index" (audio). Pop Chronicles. University of North Texas Libraries.
^ Jump up to: a b Bobby Darin interviewed on the Pop Chronicles (1969)
Jump up ^ "The Splish Splash Session - Session Notes by Dik de Heer, BobbyDarin.net/BobbyDarin.com". Bobbydarin.net. 1958-04-10. Retrieved 2011-08-19.
Jump up ^ Biography of Jesse Powell. Allmusic.
Jump up ^ David Evanier. "Chapter 3: The Nerve of a Burglar" Roman Candle: The Life of Bobby Darin (Holtzbrinck Publishers, 2004) pages 18-19.
External links[edit]
Official Bobby Darin Website, Bobby Darin: Splish Splash
Splish Splash page from the song's publisher Carlin America
Lyrics of this song at MetroLyrics
hide
v
t
e
Bobby Darin
Discography
Studio albums
Bobby Darin (1958)
That's All (1959)
This is Darin (1960)
For Teenagers Only (1960)
The 25th Day of December (1960)
Two of a Kind (1961)
Love Swings (1961)
Twist with Bobby Darin (1961)
Bobby Darin Sings Ray Charles (1962)
Things and Other Things (1962)
Oh! Look at Me Now (1962)
You're the Reason I'm Living (1963)
It's You or No One (1963)
18 Yellow Roses (1963)
Earthy! (1963)
Golden Folk Hits (1963)
Winners (1964)
From Hello Dolly to Goodbye Charlie (1964)
Venice Blue (1965)
Bobby Darin Sings The Shadow of Your Smile (1966)
In a Broadway Bag (Mame) (1966)
If I Were a Carpenter (1966)
Inside Out (1967)
Bobby Darin Sings Doctor Dolittle (1967)
Bobby Darin Born Walden Robert Cassotto (1968)
Commitment (1969)
Live albums
Darin at the Copa (1960)
Live at the Desert Inn (1987)
Compilation albums
The Bobby Darin Story (1961)
Aces Back to Back (2004)
Singles
"Splish Splash"
"Early in the Morning"
"Queen of the Hop"
"Dream Lover"
"Mack the Knife"
"Beyond the Sea"
"You Must Have Been a Beautiful Baby"
"Things"
"You're the Reason I'm Living"
"If I Were a Carpenter"
"Darlin' Be Home Soon"
Related articles
Beyond the Sea (film)
Dream Lover: The Bobby Darin Musical
Book:Bobby Darin
Retrieved from "https://en.wikipedia.org/w/index.php?title=Splish_Splash_(song)&oldid=843200285"
Categories:
1958 singles
Bobby Darin songs
Songs written by Bobby Darin
1958 songs
Atco Records singles
Hidden categories:
Articles with hAudio microformats
All articles with unsourced statements
Articles with unsourced statements from September 2010
Navigation menu
Personal tools
Not logged in
Talk
Contributions
Create account
Log in
Namespaces
Article
Talk
Variants
Views
Read
Edit
View history
More
Search
Navigation
Main page
Contents
Featured content
Current events
Random article
Donate to Wikipedia
Wikipedia store
Interaction
Help
About Wikipedia
Community portal
Recent changes
Contact page
Tools
What links here
Related changes
Upload file
Special pages
Permanent link
Page information
Wikidata item
Cite this page
Print/export
Create a book
Download as PDF
Printable version
Languages
Français
Norsk
Русский
Suomi
Edit links
This page was last edited on 27 May 2018, at 15:42 (UTC).
Text is available under the Creative Commons Attribution-ShareAlike License; additional terms may apply. By using this site, you agree to the Terms of Use and Privacy Policy. Wikipedia® is a registered trademark of the Wikimedia Foundation, Inc., a non-profit organization.
Privacy policy
About Wikipedia
Disclaimers
Contact Wikipedia
Developers
Cookie statement
Mobile view
Enable previews

values: mw-page-base noprint

values: mw-head-base noprint

values: firstHeading firstHeading en

values: siteSub noprint

attrs: class href

values: mw-jump-link #mw-head

values: mw-jump-link #p-search

value: th

attrs: colspan class style

values:
/wiki/New_York,_New_York
mw-redirect
New York, New York

values: width: 33%; text-align: center; vertical-align: top; padding: .2em .1em .2em 0;

values: width: 33%; text-align: center; vertical-align: top; padding:.2em .1em;

values: width: 33%; text-align: center; vertical-align: top; padding: .2em 0 .2em .1em;

values: background: transparent; width: 100%; min-width: 100%; border-collapse: collapse;

values: width:33%; padding:.2em .1em .2em 0; text-align: center;

values: width:33%; padding:.2em .1em; text-align: center;

values: width:33%; padding:.2em 0 .2em .1em; text-align: center;

values: checkbox button toctogglecheckbox toctogglecheckbox display:none

values: This claim needs references to reliable sources. (September 2010)

values:
noprint Inline-Template Template-Fact
white-space:nowrap;

values:
/wiki/Lollipop_(1950s_pop_song)
mw-redirect
Lollipop (1950s pop song)

values:
/wiki/Peggy_Sue_(song)
mw-redirect
Peggy Sue (song)

values:
/wiki/Good_Golly_Miss_Molly
mw-redirect
Good Golly Miss Molly

values:
/wiki/The_Disney_Channel
mw-redirect
The Disney Channel

values:
nofollow
external text
http://www.bobbydarin.net/splash.html

values:
Bobby_Darin
fn
font-size:114%;margin:0 4em

values:
navbox-abovebelow
2
background: #EEEEEE;

values:
row
navbox-group
width:1%;background: #EEEEEE;

values: Two of a Kind (Bobby Darin and Johnny Mercer album)

values: If I Were a Carpenter (Bobby Darin album)

attrs: alt src title width height srcset data-file-width data-file-height

values: nowraplinks vcard collapsible autocollapse navbox-inner mw-collapsible mw-made-collapsible

values: Category:Articles with hAudio microformats

values: Category:All articles with unsourced statements

values: Category:Articles with unsourced statements from September 2010

values: Discussion about edits from this IP address [ctrl-alt-n]

values: A list of edits made from this IP address [ctrl-alt-y]

values: You are encouraged to create an account and log in; however, it is not mandatory

values: You're encouraged to log in; however, it's not mandatory. [ctrl-alt-o]

values:
/wiki/Splish_Splash_(song)
View the content page [ctrl-alt-c]
c

values: A list of recent changes in the wiki [ctrl-alt-r]

values: portal navigation p-interaction p-interaction-label

values: List of all English Wikipedia pages containing links to this page [ctrl-alt-j]

values: Recent changes in pages linked from this page [ctrl-alt-k]

values:
/wiki/Wikipedia:File_Upload_Wizard
Upload files [ctrl-alt-u]
u

values: A list of all special pages [ctrl-alt-q]

values: Permanent link to this revision of the page

values: Link to connected data repository item [ctrl-alt-g]

values: Printable version of this page [ctrl-alt-p]

values: /static/images/wikimedia-button-1.5x.png 1.5x, /static/images/wikimedia-button-2x.png 2x

values: /static/images/poweredby_mediawiki_132x47.png 1.5x, /static/images/poweredby_mediawiki_176x62.png 2x

values:
suggestions
display: none; font-size: 13px;

values: mediawiki ltr sitedir-ltr mw-hide-empty-elt ns-0 ns-subject page-Splish_Splash_song rootpage-Splish_Splash_song skin-vector action-view


text:
God's Own Country
From Wikipedia, the free encyclopedia
Jump to navigation Jump to search
For the British film, see God's Own Country (2017 film). For the Indian film, see God's Own Country (2014 film).
God’s Own Country, is a phrase meaning an area, region or country supposedly favoured by God, that was first used to describe the Wicklow Mountains in Ireland,[1] and has subsequently been used to refer to various places, including Australia, Canada, England (Cornwall, Surrey, Yorkshire, Northumberland), United States, New Zealand, Indian state of Kerala, Scotland, Wales, and Northern Ireland.
Contents
1 Term uses
1.1 Ireland
1.2 England
1.3 United States
1.4 New Zealand
1.5 Australia
1.6 Kerala
1.7 Zimbabwe
2 References
Term uses[edit]
Ireland[edit]
Wicklow Mountains
The expression was first used to describe the Wicklow Mountains of Ireland by Edward du Bois, writing under the pseudonym "A Knight Errant" in 1807,[2]
England[edit]
When used in reference to England, "God's own country" refers to the legend that as a boy Jesus of Nazareth visited England with his great uncle, Joseph of Arimathea.[3] The event itself inspiring the musical prelude to William Blake's "Milton", the piece And did those feet in ancient time also known as 'Jerusalem' which has become an unofficial anthem of England.[4] The poem asks did Jesus visit England in ancient times, and in so doing created the New Jerusalem, or heaven in England.[5]
Another first usage of the term by Edward du Bois was in a poem describing the English county of Surrey in 1839.[6] The phrase was also used in its more literal meaning to refer to Heaven, in a poem by Elizabeth Harcourt Rolls Mitchell in 1857.[7]
The phrase is also used to describe Yorkshire, England's largest county.[8][9][10] This is used interchangeably with God's Own County.[11][12][13][14]
United States[edit]
The phrase later found sporadic use to describe several American regions. Most known is the Upper Peninsula of Michigan. It was also used by the Confederate army to describe parts of Tennessee in the 1860s.[15] The phrase was also used to describe California in the 1860s,[16] and by Clement Laird Vallandigham to describe the land of the Mississippi plains.[17] None of these remain widely used to describe a region, though it is still occasionally used to describe the United States overall.[18][19]
During World War II, German Nazi propaganda minister Joseph Goebbels sarcastically mocked the USA as "Aus Gottes eigenem Land" (From God's Own Country) in an essay that appeared in the German newspaper Das Reich on August 9, 1942.[20] Goebbels ridiculed America as a young land that lacked culture, education and history in contrast with Germany. In 1943, the Nazis published an anti-American, anti-semitic propaganda book written by Erwin Berghaus called "USA - nackt!: Bilddokumente aus Gottes eigenem Land" (USA naked! Photo documents from God's own country) which also mockingly characterized the USA with the phrase.[21][22] Several modern German newspapers such as Die Welt, Der Tagesspiegel and Die Zeit have also used the phrase "Gottes eigenes Land" (God's own country) to criticize American culture and society.[23][24][25]
New Zealand[edit]
The earliest recorded use of the phrase as applied to New Zealand was as the title of a poem about New Zealand written by Thomas Bracken.[26] It was published in a book of his poems in 1890, and again in 1893 in a book entitled Lays and Lyrics: God's Own Country and Other Poems.[27] God's Own Country as a phrase was often used and popularised by New Zealand's longest serving prime minister, Richard John Seddon. He last quoted it on 10 June 1906 when he sent a telegram to the Victorian premier, Thomas Bent, the day before leaving Sydney to return home to New Zealand. "Just leaving for God's own country," he wrote. He never made it, dying the next day on the ship Oswestry Grange.[28] Bracken's God's Own Country is less well known internationally than God Defend New Zealand which he published in 1876. The latter poem, set to music by John Joseph Woods, was declared the country's national hymn in 1940, and made the second national anthem of New Zealand along with God Save the Queen in 1977.
Australia[edit]
In Australia, the phrase "God's own country" was often used to describe the country in the early 1900s, but it appears to have gradually fallen out of favour.[29] The phrase "God's Country" is often used to describe Queensland[30][31][32] and the Sutherland Shire in southern Sydney[33]
Kerala[edit]
Kerala tourism logo.
Kerala is a state in south India; the phrase was adopted by the tourism department of the state's government in the 1980s. Kerala is famous for its Ayurvedic treatments, high mountains, gorges and deep-cut valleys, lush and evergreen rain forests, coconut palms, backwaters, and food items. According to Hindu mythology, Kerala was created by Lord Parashurama, an incarnation of Lord Vishnu by throwing his axe across the sea to create new land for his devotees to live peacefully, hence the expression.[34][35]
Zimbabwe[edit]
The phrase "God's own country" was heard during the 1970s in Rhodesia (formerly: Southern Rhodesia, now: Zimbabwe), where most people perceived the land as beautiful despite the ongoing Bush War of the time. Evidence of the phrase being used earlier in reference to Rhodesia is found in Chartered Millions: Rhodesia and the Challenge to the British Commonwealth by John Hobbis Harris, published 1920 by Swarthmore Press (refer to page 27). The phrase "Godzone" is distinctly different and was not used in Rhodesia.
References[edit]
Jump up ^ "God's Own Country, Godzone and Good Old New Zealand". Godzone.com. 2 November 2015.
Jump up ^ Du Bois, E. (1805) My pocket book: or, Hints for "A ryghte merrie and conceitede" tour by "A Knight Errant", p. 23. Google Books.
Jump up ^ "The strange myth about Jesus coming to England". 23 April 2018 – via www.bbc.co.uk.
Jump up ^ "English national anthem: Is Jerusalem the hymn we've been looking for?". 9 March 2016.
Jump up ^ "Analysis of Jerusalem by William Blake". 29 December 2015.
Jump up ^ Hone, W. (ed) (1839) The year book, of daily recreation & information, p. 469. Google Books.
Jump up ^ Mitchell, E.H.R. "To The memory of J.C.S." in First Fruits: Poems, p. 79. Google books.
Jump up ^ Ward, David (24 October 2007). "An ark park for God's own country". London: Guardian Unlimited. Retrieved 2010-05-03.
Jump up ^ Duncan, Hannah (10 August 2012). "Yorkshire back up to 12th in Olympic medal table after Nicola Adams's gold". Metro. Retrieved 2012-11-18.
Jump up ^ "Yorkshire 10th in Olympic medal table". Yahoo Eurosport. 6 August 2012. Archived from the original on 11 August 2012. Retrieved 18 November 2012.
Jump up ^ "God's own county". London: Guardian Unlimited. 2 June 2006. Retrieved 2010-05-03.
Jump up ^ "What's so special about Yorkshire?". BBC News. 1 August 2006.
Jump up ^ "Ee bah gum! If Yorkshire was a country, it would be higher in the Olympic medal table than South Africa, Japan and Australia". Daily Mail. 5 August 2012. Retrieved 2012-11-18.
Jump up ^ Rushby, Kevin (3 September 2013). "Yorkshire - God's own country is the best place in Europe". the Guardian. Retrieved 2 April 2018.
Jump up ^ Loring, F.W., and Atkinson, C.F. (1869) Cotton culture and the South considered with reference to emigration, p. 71. Google Books.
Jump up ^ Annual report of the State Board of Agriculture, Volume 4, Missouri State Board of Agriculture 1869, p. 468. Google Books.
Jump up ^ Speeches, arguments, addresses, and letters of Clement L. Vallandigham 1864, p. 211. Google Books.
Jump up ^ For example, in the title of Stephen Bates' book God's Own Country: Power and Religion in the USA: Religion and Politics in the USA.
Jump up ^ Christopher Hitchens (30 September 1998). "Rushdie: Free at last". salon.com. Retrieved 14 January 2014.
Jump up ^ Bytwerk, Randall. "Goebbels on the USA (1942)". research.calvin.edu. Retrieved 2 April 2018.
Jump up ^ Berghaus, Erwin (2 April 2018). "USA - nackt! Bilddokumente aus Gottes eigenem Land". Bischoff. Retrieved 2 April 2018 – via Open WorldCat.
Jump up ^ "very rare 1943 anti-Semitic / anti-American Third Reich photo book". www.od43.com. Retrieved 2 April 2018.
Jump up ^ Stein, Hannes (15 July 2013). "Martin-Prozess: Die Rassismus-Frage in Obamas Amerika". Retrieved 2 April 2018 – via www.welt.de.
Jump up ^ "Gottes eigenes Land". 3 September 2008. Retrieved 2 April 2018 – via Tagesspiegel.
Jump up ^ Groß, Th (15 May 2003). "Musik: Wie gut, dass es das Böse gibt". Retrieved 2 April 2018 – via Die Zeit.
Jump up ^ "Dictionary of Australian Biography Br-By". gutenberg.net.au. Retrieved 2 April 2018.
Jump up ^ "Dictionary Of New Zealand Biography". dnzb.govt.nz. Retrieved 2 April 2018.
Jump up ^ "Wayback Machine" (PDF). archive.org. 16 January 2007. Retrieved 2 April 2018.
Jump up ^ "God's Own Country", A Word Picture of Australia
Jump up ^ ""TRULY GOD'S OWN COUNTRY"". 27 June 1938. p. 5 – via Trove.
Jump up ^ "Great driving holidays - Brisbane to Townsville (Qld) - DriveNow Blog". 27 March 2010.
Jump up ^ Birchley, Delia (23 April 1986). "God's own country : the Johnstone Shire story". Bowen Hills, Qld. : Boolarong Publications – via Trove.
Jump up ^ ".: The Australian Route Register :". www.climb.org.au. Retrieved 2 April 2018.
Jump up ^ "How Kerala became God's Own Country". The Hindu. 2008-11-20. ISSN 0971-751X. Retrieved 2018-10-04.
Jump up ^ "God's Own Country Kerala - Best Tourist Places in Kerala". keralaaffairs.com. 3 August 2015. Retrieved 2 April 2018.
hide
v
t
e
Exceptionalism
National
American exceptionalism (USA)
Nihonjinron (Japan)
Cultural Exception (France)
Sonderweg (Germany)
Sinocentrism (China)
Third Rome (Europe & Russia)
European exceptionalism
Pinoy pride (Philippines)
Thai Exceptionalism
Hangul supremacy (Korea)
Nicaraguan exceptionalism
Religious
Jews as the chosen people
Unification Church (Korea)
Exclusivism
Terms
Chosen people
God's Own Country
Middle Kingdom
Sui generis
Other
Anthropocentrism
HIV exceptionalism
Particle chauvinism
Sentiocentrism
Retrieved from "https://en.wikipedia.org/w/index.php?title=God%27s_Own_Country&oldid=863485196"
Categories:
Exceptionalism
Alternative place names
Tourism in Kerala
Tourism campaigns
Hidden categories:
Articles containing Japanese-language text
Articles containing German-language text
Articles containing Latin-language text
Use dmy dates from July 2014
Navigation menu
Personal tools
Not logged in
Talk
Contributions
Create account
Log in
Namespaces
Article
Talk
Variants
Views
Read
Edit
View history
More
Search
Navigation
Main page
Contents
Featured content
Current events
Random article
Donate to Wikipedia
Wikipedia store
Interaction
Help
About Wikipedia
Community portal
Recent changes
Contact page
Tools
What links here
Related changes
Upload file
Special pages
Permanent link
Page information
Wikidata item
Cite this page
Print/export
Create a book
Download as PDF
Printable version
Languages
Add links
This page was last edited on 11 October 2018, at 02:26 (UTC).
Text is available under the Creative Commons Attribution-ShareAlike License; additional terms may apply. By using this site, you agree to the Terms of Use and Privacy Policy. Wikipedia® is a registered trademark of the Wikimedia Foundation, Inc., a non-profit organization.
Privacy policy
About Wikipedia
Disclaimers
Contact Wikipedia
Developers
Cookie statement
Mobile view
Enable previews

values: mw-page-base noprint

values: mw-head-base noprint

values: firstHeading firstHeading en

values: siteSub noprint

values: mw-jump-link #mw-head

values: mw-jump-link #p-search

attrs: role class

values:
note
hatnote navigation-not-searchable

value: sup

values: checkbox button toctogglecheckbox toctogglecheckbox display:none

values:
/wiki/Jesus_of_Nazareth
mw-redirect
Jesus of Nazareth

values:
/wiki/Clement_Laird_Vallandigham
mw-redirect
Clement Laird Vallandigham

values:
/wiki/Richard_John_Seddon
mw-redirect
Richard John Seddon

values:
/wiki/Guardian_Unlimited
mw-redirect
Guardian Unlimited

values:
nofollow
external text
http://www.zeit.de/2003/21/M__Manson

values:
nofollow
external text
//www.worldcat.org/issn/0971-751X

values:
/wiki/Thai_Exceptionalism
mw-redirect
Thai Exceptionalism

values:
/wiki/Unification_Church
mw-redirect
Unification Church

values: nowraplinks collapsible autocollapse navbox-inner mw-collapsible mw-made-collapsible

values: navigation navbox Exceptionalism padding:3px

values: Category:Articles containing Japanese-language text

values: Category:Articles containing German-language text

values: Category:Articles containing Latin-language text

values: Discussion about edits from this IP address [ctrl-alt-n]

values: A list of edits made from this IP address [ctrl-alt-y]

values:
/wiki/God%27s_Own_Country
View the content page [ctrl-alt-c]
c

values: Discussion about the content page [ctrl-alt-t]

values: p-namespaces navigation vectorTabs p-namespaces-label

values:
p-variants
navigation
vectorMenu emptyPortlet
p-variants-label

values: Past revisions of this page [ctrl-alt-h]

values: p-views navigation vectorTabs p-views-label

values:
p-cactions
navigation
vectorMenu emptyPortlet
p-cactions-label

values:
mw-wiki-logo
/wiki/Main_Page
Visit the main page

values:
/wiki/Main_Page
Visit the main page [ctrl-alt-z]
z

values: Featured content – the best of Wikipedia

values: Find background information on current events

values:
/wiki/Special:Random
Load a random article [ctrl-alt-x]
x

values: portal navigation p-navigation p-navigation-label

values: Guidance on how to use and edit Wikipedia

values: About the project, what you can do, where to find things

values: mediawiki ltr sitedir-ltr mw-hide-empty-elt ns-0 ns-subject page-God_s_Own_Country rootpage-God_s_Own_Country skin-vector action-view