21.3: Physical Properties - An Overview
- Page ID
- 34418
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Now given in more detail in individual pages covering each Transition Metal
Ti | V | Cr | Mn | Fe | Co | Ni | Cu |
Halides
Titanium
Formula | Color | MP | BP | Structure |
---|---|---|---|---|
TiF4 | white | - | 284 | fluoride bridged |
TiCl4 | Colorless | -24 | 136.5 | - |
TiBr4 | yellow | 38 | 233.5 | hcp I- but essentially monomeric cf. SnI4 |
TiI4 | violet-black | 155 | 377 | hcp I- but essentially monomeric cf. SnI4 |
Preparations:
They can all be prepared by direct reaction of Ti with halogen gas (X2). All are readily hydrolysed.
They are all expected to be diamagnetic.
Formula | Color | MP | BP | μ (BM) | Structure |
---|---|---|---|---|---|
TiF3 | blue | 950d | - | 1.75 | - |
TiCl3 | violet | 450d | - | - | BiI3 |
TiBr3 | violet | - | - | - | BiI3 |
TiI3 | violet-black | - | - | - | - |
Preparations:
They can be prepared by reduction of TiX4 with H2.
Vanadium
Formula | Color | MP | BP | μ (BM) | Structure |
---|---|---|---|---|---|
VF5 | white | 19.5 | 48.3 | 0 | trigonal bipyramid in gas phase |
Preparations:
Prepared by reaction of V with F2 in N2 or with BrF3 at 300C.
In the solid state it is an infinite chain polymer with cis-fluoride bridging.
Formula | Color | MP | BP | μ (BM) | Structure |
---|---|---|---|---|---|
VF4 | lime-green | 100 (a) | - | 1.68 | - |
VCl4 | red-brown | -25.7 | 148 | 1.61 | tetrahedral (monomeric) |
VBr4 | purple | -23d | - | - | - |
(a) sublimes with decomposition at 100 C.
Preparations:
VCl4 is prepared by reaction of V with chlorinating agents such as Cl2, SOCl2, COCl2 etc.
Reaction of VCl4 with HF in CCl3F at -78C gives VF4.
Chromium
Formula | Color | MP | M-X (pm) | μ (BM) (b) | Structure |
---|---|---|---|---|---|
CrF3 | green | 1404 | 190 | - | - |
CrCl3 | red-violet | 1152 | 238 | - | CrCl3 |
CrBr3 | green-black | 1130 | 257 | - | BiI3 |
CrI3 | black | >500d | - | - | - |
(b) all 3.7-4.1 BM.
Preparations:
CrX3 are prepared from Cr with X2, dehydration of CrCl3.6H2O requires SOCl2 at 650C.
Formula | Color | MP | μ (BM) | Structure |
---|---|---|---|---|
CrF2 | green | 894 | 4.3 | distorted rutile |
CrCl2 | white | 820-824 | 5.13 | distorted rutile |
CrBr2 | white | 844 | - | - |
CrI2 | red-brown | 868 | - | - |
Preparations:
Reduction of CrX3 with H2/HX gives CrX2.
Manganese
Formula | Color | MP | BP | μ (BM) | Structure |
---|---|---|---|---|---|
MnF2 | pale-pink | 920 | - | - | rutile |
MnCl2 | pink | 652 | 1190 | 5.73 | CdCl2 |
MnBr2 | rose | 695 | - | 5.82 | - |
MnI2 | pink | 613 | - | 5.88 | CdI2 |
Preparations:
Prepared from MnCO3 + HX -> MnX2 + CO2 + H2O
Iron
Formula | Color | MP | Structure |
---|---|---|---|
FeF3 | green | 1000 sublimes | - |
FeCl3 | black | 306 sublimes | BiI3 |
FeBr3 | dark-red-brown | - | BiI3 |
Preparations:
Prepared by reaction of Fe + X2 -> FeX3.
Note that FeBr3.aq when boiled gives FeBr2.
Formula | Color | MP | BP | Structure |
---|---|---|---|---|
FeF2 | white | 1000 | 1100 | rutile |
FeCl2 | pale yellow-grey | 670-674 | - | CdCl2 |
FeBr2 | yellow-green | 684 | - | CdI2 |
FeI2 | grey | red heat | - | CdI2 |
Preparations:
Fe +HX at red heat -> FeX2 for X=F,Cl and Br
Fe + I2 -> FeI2
Cobalt
Formula | Color | MP | μ (BM) | Structure |
---|---|---|---|---|
CoF2 | pink | 1200 | - | rutile |
CoCl2 | blue | 724 | 5.47 | CdCl2 |
CoBr2 | green | 678 | - | CdI2 |
CoI2 | blue-black | 515 | - | CdI2 |
Preparations:
Co or CoCO3 + HX -> CoX2.aq -> CoX2
Nickel
Formula | Color | MP | μ (BM) | Structure |
---|---|---|---|---|
NiF2 | yellow | 1450 | 2.85 | tetragonal rutile |
NiCl2 | yellow | 1001 | 3.32 | CdCl2 |
NiBr2 | yellow | 965 | 3.0 | CdCl2 |
NiI2 | Black | 780 | 3.25 | CdCl2 |
Preparations:
Ni + F2 55 C /slow -> NiF2
Ni + Cl2 EtOH/ 20 C -> NiCl2
Ni + Br2 red heat -> NiBr2
NiCl2 + 2NaI -> NiI2 + 2NaCl
Copper
Formula | Color | MP | BP | μ (BM) | Structure |
---|---|---|---|---|---|
CuF2 | white | 950d | - | 1.5 | |
CuCl2 | brown | 632 | 993d | 1.75 | CdCl2 |
CuBr2 | black | 498 | - | 1.3 |
Preparations:
Copper(II) halides are moderate oxidising agents due to the Cu(I)/ Cu(II) couple. In water, where the potential is largely that of the aquo-complexes, there is not a great deal of difference between them, but in non-aqueous media, the oxidising (halogenating) power increases in the sequence: CuF2 << CuCl2 << CuBr2.
Cu + F2 -> CuF2
Cu + Cl2 450 C -> CuCl2
Cu + Br2 -> CuBr2
or from CuX2.aq by heating -> CuX2
Formula | Color | MP | BP | Structure |
---|---|---|---|---|
CuCl | white | 430 | 1359 | - |
CuBr | white | 483 | 1345 | - |
CuI | white | 588 | 1293 | Zinc Blende |
Preparations:
Reduction of CuX2 -> CuX except for F which has not been obtained pure.
Note that Cu(II)I2 can not be isolated due reduction to CuI.
Oxides and Aquo Species
Titanium
Formula | Color | MP | μ (BM) | Structure |
---|---|---|---|---|
TiO2 | white | 1892 | diam. | rutile - Refractive Index 2.61-2.90 cf. Diamond 2.42 |
Preparations:
obtained from hydrolysis of TiX4 or Ti(III) salts.
TiO2 reacts with acids and bases.
In Acid:
TiOSO4 formed in H2SO4 (Titanyl sulfate)
In Base:
MTiO3 metatitanates (eg Perovskite, CaTiO3 and ilmenite, FeTiO3)
M2TiO4 orthotitanates.
Peroxides are highly Colored and can be used for Colorimetric analysis.
pH <1 [TiO2(OH)(H2O)x]+
pH 1-2 [(O2)Ti-O-Ti(O2)](OH) x2-x; x=1-6
[Ti(H2O)6]3+ -> [Ti(OH)(H2O)5]2+ + [H+] pK=1.4
TiO2+ + 2H+ + e- -> Ti3+ + H2O E=0.1V
Vanadium
Formula | Color | Common name | Oxidation State | MP | V-O distance (pm) |
---|---|---|---|---|---|
V2O5 | brick-red | pentoxide | V5+ | 658 | 158.5-202 |
V2O4 | blue | dioxide | V4+ | 1637 | 176-205 |
V2O3 | grey-black | sesquioxide | V3+ | 1967 | 196-206 |
Preparations:
V2O5 is the final product of the oxidation of V metal, lower oxides etc.
Aqueous Chemistry very complex:
In alkaline solution,
VO43- + H+ -> HVO42-
2HVO42- -> V2O74- + H2O
HVO42- + H+ -> H2VO4-
3H2VO4- -> V3O93- + 3H2O
4H2VO4- -> V3O124- + 4H2O
In acidic solution,
10V3O93- + 15H+ -> 3HV10O285- + 6H2O
H2VO4- + H+ -> H2VO4
HV10O285- + H+ -> H2V10O284-
H3VO4 + H+ -> VO2+ + 2H2O
H2V10O284- + 14H+ -> 10VO2+ + 8H2O
VO(H2O)4SO4
The crystal structure of this salt was first determined in 1965. The V=O bond length was 159.4 pm, the aquo group trans to this had the longest V-O bond length (228.4pm) and the equatorial bond lengths were in the range 200.5-205.6 pm. Note that SO42- was coordinated in an equatorial position.
The IR stretching frequency for the V=O in vanadyl complexes generally occurs at 985 +/- 50 cm-1.
Redox properties of oxovanadium ions:
VO2+ + 2H+ + e- -> VO2+ + H2O E=1.0v
VO2+ + 2H+ + e- -> V3+ + H2O E=0.34V
Chromium
Formula | Color | Oxidation State | MP |
---|---|---|---|
CrO3 | deep red | Cr6+ | 197d |
Cr3O8 | - | intermediate | - |
Cr2O5 | - | - | - |
Cr5O12 etc | - | - | - |
CrO2 | brown-black | Cr4+ | 300d |
Cr2O3 | green | Cr3+ | 2437 |
Dichromate and chromate equilibria is pH dependent:
HCrO4- -> CrO42- + H+ K=10-5.9
H2CrO4 -> HCrO4- + H+ K=10+0.26
Cr2O72- + H2O -> 2HCrO4- K=10-2.2
HCr2O7- -> Cr2O72- + H+ K=10+0.85
CrO3
pH > 8 CrO42- yellow
2-6 HCrO4- & Cr2O72- orange-red
< 1 H2Cr2O7
[Cr(H2O)6]3+ -> [Cr(H2O)5(OH)]2+ -> [(H2O)4Cr Cr(H2O)4]4+ pK=4 etc.
Manganese
Formula | Color | Oxidation State | MP |
---|---|---|---|
Mn2O7 | green oil | Mn7+ | 5.9 |
MnO2 | black | Mn4+ | 535d |
Mn2O3 | black | Mn3+ | 1080d |
Mn3O4 - Haussmanite | black | Mn2/3+ | 1705 |
MnO | grey-green | Mn2+ | 1650 |
Preparations:
Mn3O4 is prepared from the other oxides by heating in air. MnO is prepared from the other oxides by heating with H2 at temperatures below 1200 C
Redox properties of KMnO4.
strong base MnO4- + e- → MnO42- E=0.56V (RAPID) MnO42- + 2H2O + e- → MnO2 + 4OH- E=0.60V (SLOW) moderate base MnO4- + 2H2O + 3e- → MnO2 + 4OH- E=0.59V dil. H2SO4 MnO4- + 8H2O + 5e- → Mn2+ + 4H2O E=1.51V
Iron
Formula | Color | Oxidation State | MP | Structure / comments |
---|---|---|---|---|
Fe2O3 | red brown | Fe3+ | 1560d | α-form Haematite, β-form used in cassettes |
Fe3O4 | black | Fe2+/3+ | 1538d | magnetite/lodestone |
FeO | black | Fe2+ | 1380 | pyrophoric |
Preparations:
α-Fe2O3 is obtained by heating alkaline solutions of Fe(III) and dehydrating the solid formed.
FeO,Fe3O4, γ-Fe2O3 ccp α-Fe2O3 hcp
The Fe(III) ion is strongly acidic:
[Fe(H2O)6]3+ + H2O -> [Fe(H2O)5(OH)]2+ + H3O+ K=10-3.05 [Fe(OH)(H2O)5]2+ + H2O -> [Fe(OH)2(H2O)4]+ + H3O+ K=10-3.26
olation
2Fe(H2O)63+ + 2H2O -> [Fe2(OH)2(H2O)8]4++ 2H3O+ K=10-2.91
The Fe2+ ion is barely acidic:
Fe(H2O)62+ + H2O -> [Fe(OH)(H2O)5]+ + H3O+ K=10-9.5
The Redox chemistry of Iron is pH dependent:
Fe(H2O)63+ + e- -> Fe(H2O)62+ E=0.771V E=E-RT/nF Ln[Fe2+]/[Fe3+] at precipitation [Fe2+].[OH-]2 ~ 10-14 [Fe3+].[OH-]3 ~ 10-36 or for OH- =1M then [Fe2+]/[Fe3+] = 1022 E =0.771 -0.05916 log10(1022) =0.771 -1.301 =-0.530v
thus in base the value of E is reversed and the susceptibility of Fe2+ to oxidation increased. In base it is a good reducing agent and will reduce Cu(II) to Cu(0) etc. Note the implications for rust treatment.
Cobalt
Formula | Color | Oxidation State | MP | Structure / comments |
---|---|---|---|---|
Co2O3 | Co3+ | |||
Co3O4 | black | Co2+/3+ | 900-950d | normal spinel |
CoO | olive green | Co2+ | 1795 | NaCl -antiferromag. < 289 K |
Preparations:
Co2O3 is formed from oxidation of Co(OH)2.
CoO when heated at 600-700 converts to Co3O4
Co3O4 when heated at 900-950 reconverts back to CoO.
no stable [Co(H2O)6]3+ or [Co(OH)3 exist.
[Co(H2O)6]2+ not acidic
Nickel
Formula | Color | Oxidation State | MP | Structure / comments |
---|---|---|---|---|
NiO | green powder | Ni2+ | 1955 | NaCl |
thermal decomposition of Ni(OH)2, NiCO3, or NiNO3 gives NiO.
[Ni(H2O)6]2+ not acidic
Copper
Formula | Color | Oxidation State | MP |
---|---|---|---|
CuO | black | Cu2+ | 1026d |
Cu2O | red | Cu+ | 1230 |
[Cu(H2O)6]2+ not acidic
Preparations:
Cu2O is prepared from thermal decomposition of CuCO3, Cu(NO3)2 or Cu(OH)2. The Fehling's test for reducing sugars also gives rise to red Cu2O. It is claimed that 1 mg of dextrose produces sufficient red Color for a positive test.
The Redox chemistry of Copper:
Cu2+ + e- → Cu+ E=0.15V Cu+ + e- → Cu E=0.52V Cu2+ + 2e- → Cu E=0.34V
By consideration of this data, it will be seen that any oxidant strong enough to covert Cu to Cu+ is more than strong enough to convert Cu+ to Cu2+ (0.52 cf 0.14V). It is not expected therefore that any stable Cu+ salts will exist in aqueous solution.
Disproportionation can also occur:
2Cu+ → Cu2+ + Cu E=0.37V or K=106
Representative Coordination Complexes
Titanium
TiCl4 is a good Lewis acid and forms adducts on reaction with Lewis bases such as;
2PEt3 → TiCl4(PEt3)2 2MeCN → TiCl4(MeCN)2 bipy → TiCl4(bipy)
Solvolysis can occur if ionisable protons are present in the ligand;
2NH3 → TiCl2(NH2)2 + 2HCl 4H2O → TiO2.aq + 4HCl 2EtOH → TiCl2(OEt)2 + 2HCl
TiCl3 has less Lewis acid strength but can form adducts also;
3pyr → TiCl3pyr3
Vanadium
The Vanadyl ion (eg. from VO(H2O)4SO4 retains the V=O bond when forming complexes.
VO2+ + 2acac → VO(acac)2
Vanadyl complexes are often 5 coordinate square pyramidal and are therefore coordinately unsaturated. They can take up another ligand to become octahedral, eg;
VO(acac)2 + pyr → VO(acac)2pyr
The V=O stretching frequency in the IR can be monitored to see the changes occurring during these reactions. It generally is found at 985 cm-1 but will shift to lower wavenumbers when 6-coordinate, since the bond becomes weaker.
Chromium
The Chromium(III) ion forms many stable complexes which being inert are capable of exhibiting various types of isomerism. "CrCl3.6H2O" exists as hydrate isomers, including:
trans-[Cr(H2O)4Cl2]Cl.2H2O etc
CrCl3 anhydrous reacts with pyridine only in the presence of Zinc powder. This allows a small amount of Cr(II) to be formed, which is very labile.
CrCl3 + pyr/Zn → CrCl3pyr3
[Cr2(OAc)4].2H2O is an example of a Cr(II) complex which is reasonably stable in air once isolated. Each Cr(II) ion has 4 d electrons but the complex is found to be diamagnetic which is explained by the formation of a quadruple bond between the two metal ions. The Cr-Cr bond distance in a range of these quadruply bonded species has been found to vary between 195-255 pm.
Manganese
Octahedral complexes of Mn(III) are expected to show Jahn-Teller distortions. It was of interest therefore to compare the structures of Cr(acac)3 with Mn(acac)3 since the Cr(III) ion is expected to give a regular octahedral shape. In fact the Mn-O bond distances were all found to be equivalent.
An unusual Mn complex is obtained by the reaction of Mn(OAc)2 with KMnO4 in HOAc. This gives [MnO(OAc)6 3H2O] OAc. It is used as an industrial oxidant for the conversion of toluene to phenol.
Iron
An important Fe complex which is used in Actinometry since it is photosensitive is K3[Fe(C2 O4)3.3H2O.
It can be prepared from:
Fe(C2O4) in K2C2O4 by reacting with H2O2 in H2C2O4 to give green crystals. It is high spin m =5.9 BM at 300K and has been resolved into its two optical isomers, although they racemise in less than 1 hour.
In light the reaction is:
K3Fe(C2O4)3.3H2O → 2Fe(C2O4) + 2CO2 + 3K2C2O4
Another important complex is used as a redox indicator since the Fe(II) and Fe(III) complexes are both quite stable and have different Colors:
Fe(phen)33+ + e- → Fe(phen)32+ E=1.12V blue red
The ligand is 1,10 phenanthroline and the indicator is called ferroin.
Cobalt
The Cobalt(III) ion forms many stable complexes, which being inert, are capable of exhibiting various types of isomerism. The preparation and characterisation of many of these complexes dates back to the pioneering work of Werner and his students.
Coordination theory was developed on the basis of studies of complexes of the type:
[Co(NH3)6]Cl3 | yellow |
[CoCl(NH3)5]Cl2 | red |
trans-[CoCl2(NH3)4]Cl | green |
cis-[CoCl2(NH3)4]Cl | purple |
Another important complex in the history of coordination chemistry is HEXOL. This was the first complex that could be resolved into its optical isomers that did not contain Carbon atoms. Since then, only three or four others have been found.
An interesting complex which takes up O2 from the air reversibly is Cosalen. This has been used as an emergency oxygen carrier in jet aircraft.
Nickel
The Nickel(II) ion forms many stable complexes. Whilst there are no other important oxidation states to consider, the Ni(II) ion can exist in a wide variety of CN's which complicates its coordination chemistry.
For example, for CN=4 both tetrahedral and square planar complexes can be found,
for CN=5 both square pyramid and trigonal bipyramid complexes are formed.
The phrase "anomalous nickel" has been used to describe this behaviour and the fact that equilibria often exist between these forms.
Some examples include:
(a) addition of ligands to square planar complexes to give 5 or 6 coordinate species
(b) monomer/polymer equilibria
(c) square-planar/ tetrahedron equilibria
(d) trigonal-bipyramid/ square pyramid equilibria.
- (a) substituted acacs react with Ni2+ to give green dihydrates (6 Coord) by heating the waters are removed to give tetrahedral species. The unsubstituted acac complex, Ni(acac)2 normally exists as a trimer.
Lifschitz salts containing substituted ethylenediamines can be isolated as either 4 or 6 coordinate species depending on the presence of coordinated solvent. - (b) Ni(acac)2 is only found to be monomeric at temperatures around 200 C in non-coordinating solvents such as n-decane. 6-coordinate monomeric species are formed at room temperature in solvents such as pyridine but in the solid state Ni(acac)2 is a trimer, where each Ni atom is 6-coordinate. Note that Co(acac)2 actually exists as a tetramer.
- (c) Complexes of the type NiL2X2 where L are phosphines can give rise to either tetrahedral or square planar complexes. It has been found that:
L=P(aryl)3 are tetrahedral L=P(alkyl)3 are square planar
L= mixed aryl and alkyl phosphines, both stereochemistries can occur in the same crystalline substance. The energy of activation for conversion of one form to the other has been found to be around 50 kJ mol-1. Similar changes have been observed with variation of the X group:
Ni(PPh3)2Cl2 green tetrahedral μ = 2.83 BM Ni(PPh3)2(SCN)2 red sq. planar μ = 0.
Ni2+ reacts with CN- to give Ni(CN)2.nH2O (blue-green) which on heating at 180-200 is dehydrated to yield Ni(CN)2. Reaction with excess KCN gives K2Ni(CN)4.H2O (orange crystals) which can be dehydrated at 100C. Addition of strong concentrations of KCN produces red solutions of [Ni(CN)5]3-.
The crystal structure of the double salt prepared by addition of [Cr(en)3]3+ to [Ni(CN)5]3- showed that two types of Ni stereochemistry were present in the crystals in approximately equal proportions;
50% as square pyramid and 50% as trigonal bipyramid .
Copper
The Copper(II) ion forms many stable complexes which are invariably described as either 4 coordinate or distorted 6 coordinate species.
Cu(OH)2 reacts with NH3 to give a solution which will dissolve cellulose. This is exploited in the industrial preparation of Rayon. The solutions contain tetrammines and pentammines. With pyridine, only tetramines are formed eg Cu(py)4 SO4.
A useful reagent for the analytical determination of Cu2+ is the sodium salt of N,N-diethyldithiocarbamate. In dilute alcohol solutions, the presence of trace levels of Cu2+ is indicated by a yellow Color which can be measured by a spectrometer and the concentration determined from a Beer's Law plot. The complex is Cu(Et2dtc)2 which can be isolated as a brown solid.
Contributors and Attributions
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Transition Metal Oxides
The high oxidation state oxides are good oxidising agents with V2O5< CrO3< Mn2O7 becoming progressively more acidic as well.
Mixed oxidation state species M(II)M(III) 2O4 are formed by a number of elements, many of which adopt the spinel structure. The Normal Spinel structure, named after a mineral form of MgAl2O4 and of generic formula AB2O4 may be approximated as a cubic close packed lattice of oxide ions with one-eighth of the tetrahedral holes occupied by the A(II) ions and one-half of the octahedral holes occupied by the B(III) ions. Closely related is the Inverse Spinel structure where there is a site change between the A(II) ions and half of the B(III) ions. Given the fact that this occurs, it is evident that the energy factors directing the two different ions to the different sites are not overwhelmingly large, and it is not surprising that such structures are highly susceptible to defects in actual crystals. One factor that may influence this site selectivity is the crystal field stabilisation energy of transition metal ions.
Another ternary oxide structural type that is found is perovskite (CaTiO3). Again, the oxygens can be considered as cubic close packed.
All the elements from Ti to Fe give stable M2O3 oxides with corundum-type structures. These oxides are all ionic and predominantly basic. In air the M2O3 is the most stable oxide for Cr, Mn and Fe.
Dioxides-The elements Ti,V,Cr and Mn give MO2 oxides with rutile or distorted rutile structures. Note that CrO2 is ferromagnetic and used in the production of magnetic tapes.
All of the 3d elements from Ti to Cu form a monoxide, either by direct combination of the elements or by reduction of a higher oxide by the metal. Most of these have the NaCl structure and are basic. With the exception of TiO, they all dissolve in mineral acids to give stable salts or complexes of M2+ ions. The Ti 2+ ion liberates hydrogen from aqueous acid and so dissolution of TiO gives Ti3+ and hydrogen.
The monoxides show a variety of physical properties. Thus Ti and V are quasi-metallic, CrO is marginal but Mn to Cu are typical ionic insulators (or more precisely, semiconductors).
Fraction of holes occupied by cations | Sequence of close packed anionic layers | Formula | CN of M and X | |
---|---|---|---|---|
hcp (ABAB..) | ccp (ABCABC..) | |||
all octahedral | NiAs | NaCl | MX | 6:6 |
1/2 octahedral - all in alternate layers | CdI2 | CdCl2 | MX2 | 6:3 |
1/3 octahedral - 2/3 in alternate layers | BiI3 | CrCl3 | MX3 | 6:2 |
1/2 tetrahedral | ZnS - wurtzite | ZnS - zinc blende | MX | 4:4 |
all tetrahedral | - | CaF2- fluorite | MX2 | 8:4 |
For further details on the structures of some of these salts see The Virtual Museum of Minerals and Molecules.
Contributors and Attributions
Prof. Robert J. Lancashire (The Department of Chemistry, University of the West Indies)