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Part 10d-1 DATA TABLE 2 - Extended SUMMARY FOR 3d BLOCK METALS

Z and symbol

21 Sc

property\name

22 Ti

scandium titanium

melting pt./ C

23 V

24 Cr

25 Mn

26 Fe

27 Co

28 Ni

29 Cu

30 Zn

vanadium

chromium

manganese

iron

cobalt

nickel

copper

zinc

1541

1668

1910

1857

1246

1538

1495

1455

1083

420

boiling pt./ C

2836

3287

3380

2672

1962

2861

2870

2730

2567

907

-3

density/gcm

2.99

4.54

6.11

7.19

7.33

7.87

8.90

8.90

8.92

7.13

-1

631

658

650

653

717

759

760

737

745

906

-1

1235

1310

1414

1592

1509

1561

1646

1753

1958

1733

-1

2389

2652

2828

2987

3248

2957

3232

3393

3554

3832

4th IE/kJmol-1

7089

4175

4507

4740

4940

5290

4950

5300

5326

5730

-1

8844

9573

6294

6690

6990

7240

7670

7280

7709

7970

Z and symbol

21 Sc

22 Ti

23 V

24 Cr

25 Mn

26 Fe

27 Co

28 Ni

29 Cu

30 Zn

atomic radius/pm

161

145

132

125

124

124

125

125

128

133

na

90

88

84

80

76

74

72

69

74

Polarising power M
ion

na

2.2

2.3

2.4

2.5

2.6

2.7

2.8

2.9

2.7

M3+ ionic radius/pm

81

76

74

69

66

64

63

62

na

na

3.7

3.9

4.1

4.3

4.5

4.7

4.8

4.8

na

na

na

68

60

56

54

na

na

na

na

na

na

5.9

6.7

7.1

7.4

na

na

na

na

na

21 Sc

22 Ti

23 V

24 Cr

25 Mn

26 Fe

27 Co

28 Ni

29 Cu

30 Zn

+3 only +2,+3,+4 +2,+3,+4,+5 +2,+3,+6 +2,+3,+4,+6,+7 +2,+3

+2,+3

+2,+3

+1,+2

+2 only

1st IE/kJmol

2nd IE/kJmol
3rd IE/kJmol
5th IE/kJmol

2+

ionic radius/pm
2+

3+

Polarising power M
ion

M4+ ionic radius/pm

4+

Polarising power M
ion
Z and symbol

oxidation states, less

common/stable

electron configuration 2,8,9,2 2,8,10,2

2,8,11,2

2,8,13,1

2,8,13,2

outer electrons

3d14s2

3d24s2

3d34s2

3d54s1

3d54s2

3d64s2

Electrode pot'l
M(s)/M2+(aq)

na

-1.63V

-1.18V

-0.90V

-1.18V

-0.44V -0.28V -0.26V +0.34V -0.76V

-2.03V -1.21V

-0.85V

-0.74V

-0.28V

-0.04V

Electrode pot'l
M(s)/M3+(aq)

2,8,14,2 2,8,15,2 2,8,16,2 2,8,18,1 2,8,18,2

3d74s2

+0.40

3d84s2

na

3d104s1

na

3d104s2

na

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Electrode pot'l
M2+(aq)/M3+(aq)

na

-0.37V

-0.26V

-0.42V

+1.52V

Electronegativity

1.36

1.54

1.63

1.66

1.55

1.83

Z and symbol

21 Sc

22 Ti

23 V

24 Cr

25 Mn

26 Fe

+0.77V +1.87V

na

na

na

1.88

1.91

1.90

1.65

27 Co

28 Ni

29 Cu

30 Zn

3d block data notes:

1. Atomic and ionic radii are quoted in pm (1 picometre, 10-12 m), 1000 pm = 1 nm (1 nanometre = 10-9 m)
2. na means 'not applicable' or 'not available'.
3. The electronegativity values are from the Pauling scale.
4. Ionic radii relate to the 'isolated' theoretical ion, NOT hydrated aqueous ions.
5. Polarizing power is a measure of the ions charge density which has important chemical consequences e.g.
the bonding nature of metals with non-metals e.g. an ionic or a covalent MCln
and the acidity of the hydrated aqueous ion [M(H2O)6]n+(aq).
The ion charge divided by the ionic radius of the 'isolated ion' is a 'reasonable' number scale for easy
comparison of polarising power, and in the tables I've multiplied the charge/radius by 100 to make a
suitable scale.
Obviously, the larger the charge, or the smaller the volume or radius, the greater the charge density or
polarising power.
Note that as the oxidation state of the transition metal increases,
i.e. increase in charge if an ionic compound, the greater the polarising power of the cation,
which increases the covalent character of the compound, exemplified by comparing iron(II) and
iron(III) compounds or complex ions
e.g. FeCl2 is essentially an ionic compound and FeCl3 is covalent in character,
the greater the polarising power of the central metal ion, the greater the acidity of the
hexaaqua ion
e.g. [Fe(H2O)6]3+ is more acidic than [Fe(H2O)6]2+
Going from iron(II) to iron(III) involves an increases in cationic positive charge and
decrease in radius of the 'isolated' central metal ion. The decrease in radius is bound
to result from the same nuclear charge of 26+ 'pulling in' 24 and 23 electrons
respectively, i.e. less electron density in the same quantum level, less space occupied.
For more details see Transition Metals Appendix 1 Acidity of hexaaqua-ions
Relative polarising power of Groups 1-3 ions for comparison with the 3d block ions above:

Group of the Periodic

Table

Metal ion and ionic

charge

ionic radius/pm

relative polarizing
power = 100 x charge
/ radius

Na+

98

1.0

Mg2+

78

2.6

3+

60

5.0

133

0.75

106

1.9

1
2

Al

K+
2+

Ca

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Note the substantial increase in polarizing power of the cations across Period 3 from sodium to
aluminium as the ion charge increases and the ionic radius decreases. From the data from Groups and 1
and 2 you can see the polarising power of similarly charged cation decreases down a group as the ionic radius
increases.

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Part 10d-2 A summary of some 3d-block compounds, complexes and oxidation states
Most are mentioned in the detailed individual element notes, but some have been added to illustrate other
oxidation states you may not encounter on your course - but some good oxidation number practice!
Ox.
State

Sc

Ti

Cr

Mn

Fe

Co

Ni

+1,
(I)

+3,
(III)

Zn

CuI white(s)
[CuCl3]

[Ti(H2O)6]2+ [V(H2O)6]2+
violet(aq)
violet(aq)

Sc2O3
Sc(OH)3
white(s)

2+

[Mn(H2O)6]2+
very pale
pink(aq)

3+

[Sc(H2O)6]
colourless(aq)

[Fe(H2O)6]
pale
green(aq)

CoO (s)
[Co(H2O)6]
pink(aq)

2+

[Ni(H2O)6]2+
green(aq)

[Cu(H2O)6]
blue
green(aq)

[Ni(CN)4]2-

2+

ZnO, ZnCO3
white(s)
[Zn(H2O)4]2+
colourless(aq)

Fe2O3
brown(s)

Cr2O3 (s)
[Ti(H2O)6]3+ [V(H2O)6]3+
purple(aq)
green(aq) [Cr(H2O)6]3+
green(aq)

2-

NiCl2 (s)

MnO (s)
+2,
(II)

Cu

Mn2O3
brown(s)

[Fe(H2O)6]3+
yellowishbrown(aq)

[Co(NH3)6]3+(aq)

TiO2 white(s)
+4,
(IV)

[TiO]2+
colourless(aq)

[VO]2+
blue(aq)

MnO2
black(s)

V2O5
white(s)

TiCl4
colourless(l)
+5,
(V)

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VO43[VO2]+
yellow(aq)
CrO3 (s)
+6,
(VI)

Cr2O72orange(aq)

MnO42green(aq)

FeO42- (in s)

CrO42yellow(aq)

+7,
(VII)

KMnO4 dark
purple(s)
-

MnO4purple(aq)

Notes

1. See REDOX pages for the meaning of oxidation state and how to work it out in a compound.
2. Can you see in each case why the oxidation state is as quoted? i.e. can you work out the oxidation number
3.
4.
5.
6.
7.

of the 3d-block metal.

The text is small to fit the table on a minimum of a 1024 x 768 screen.
Nice pattern of maximum oxidation state from Sc to Mn i.e. equivalent to using/losing all the outer
electrons (3dx 4sy) beyond the [Ar] core.
All except scandium (Sc3+) form an M2+ ion.
All except zinc form compounds with a (III) oxidation sate compound.
Only copper has important compounds of oxidation state +1.

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Part 10d-3 Standard Electrode Potential Chart Diagram for the 3d-block elements

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Redox potential chart comments:

All data quoted is for standard conditions i.e. 298K, 1 atm. pressure and 1 mol dm-3 solutions of ions.
Other than the solid metals, MnO2 and FeO42-, hydrogen gas, you can assume all ions are in aqueous media.
Unless an oxyanion, oxocation or another ligand in a complex is indicated, you assume you are dealing with hexaaqua-metal
ions (H2O ligand only).
Further comments below draw out some general patterns and other points of interest.
o All except scandium (Sc3+), which is not that reactive to acids despite the relatively negative M/M3+ potential, form
a hydrated M2+ ion either by reaction of the metal with acid or reduction of a higher oxidation state complexcompound.
o The stable oxidation states in aqueous solution containing dissolved oxygen from air are for the hydrated ions ...
(only Sc3+), [TiO]2+, VO2+, Cr3+, Mn2+, Fe3+, Co2+ and Ni2+ (only Zn2+).
On the basis of the electrode potential chart above, the argument is simple. In neutral or acid solution the
oxidising potential of the oxygen-proton-water system is +1.23V. Therefore any e.g. M3+/M2+ potential less
positive than +1.23V will result in the oxidation of the lower oxidation state species to the higher oxidation
state species in the presence of dissolved oxygen which is reduced to water.
Oxidation states higher than the stable ones tend to oxidise water liberating oxygen and as

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o
o
o

mentioned above, lower oxidation states tend to be reducing and liberate hydrogen from water. So
the Mn3+/Mn2+ and Co3+/Co2+ potentials lie above +1.23V so Mn3+ and Co3+ will oxidise water and cannot
be stable in acid solution.
Note that the +4 oxidation states of Ti and V exist as hydrated oxo-cations because the high polarising
power of the highly charged central metal ion causes deprotonation (see Appendix 1. Acidity of hexa-aqua
ions).
The rest are [M(H2O)n]2+/3+ where n is usually 6, can be 4 for Cu and Zn.
Apart from iron, there is a tendency for the lower oxidation state to become increasingly more stable with
increasing atomic number.
Higher oxidation states which are normally oxidising in aqueous solution can be stabilised by complexing e.g. compare
the Co(II)/Co(III) potential when complexed with water (+1.82V) and with the ligand ammonia (+0.10V).
There are classic examples of disproportionation where an intermediate oxidation state species spontaneously
changes into a higher and lower' oxidation state species e.g. the disproportionation reactions
Cu(I) ==> Cu(0) + Cu(II) and Mn(VI) ==> Mn(II) + Mn(VII).
These are described in detail, complete with electrode potential arguments for thermodynamic feasibility,
under the respective metal.
How do you work out what will oxidise what? or what will reduce what?
How to work out the feasibility of reaction from electrode potential data is described in Appendix 5.
Using an electrode potential chart like the one above or a list of redox potentials the following rules apply.
To facilitate an oxidation, the half-cell potential of the oxidising agent must be less negative or
more positive than the redox potential of the 'system' you wish to oxidise.
So using at the redox potential chart for example:
Dissolved oxygen will oxidise Co2+ to Co3+ in presence of ammonia - forms the amine
complexes, but the hexaaqua complex of Co2+ is stable in the presence of oxygen if no
ammonia present.
Co3+/Co2+ (H2O ligand, E = +1.82V), O2/H2O (E = +1.23, less than +1.82 but more than
+0.10V), Co3+/Co2+ (NH3 ligand, E = +0.10V)
So [Co(H2O)6]2+ is stable in the presence of oxygen, but [Co(NH3)6]2+ will be oxidised
to [Co(NH3)6]3+.
You could then further predict that [Co(H2O)6]3+ will oxidise water to oxygen!
To facilitate a reduction, the half-cell potential of the reducing agent must be more negative or less
positive than the redox potential of the 'system' you wish to reduce.
So using the redox potential chart and the half-cell redox potential for I2/I- of +0.54V:
hexaaquairon(III) ions will be reduced by iodide ions because E for Fe3+/Fe2+ (H2O
ligand) is +0.77V i.e. the Fe3+ will oxidise the iodide ions rather than iodine oxidising
the Fe2+ ions. [Fe(H2O)6]3+ is reduced to [Fe(H2O)6]2+, iron(III) to iron(II).
However if the ligand is the cyanide ion, then iodide ions will not reduce the Fe3+
cyanide ion complex but iodine would oxidise [Fe(CN)6]4- to [Fe(CN)6]3-, iron(II) to
iron(III).
Fe3+/Fe2+ (H2O ligand, E = +0.77V), I2/I- (E = +0.54, less than +0.77 but more than
+0.36V), Fe3+/Fe2+ (CN- ligand, E = +0.36V)

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Part 10d-4 PICTURES of PRECIPITATES and COMPLEX FORMATION

Prior to, and with, excess reagent for selected 3d block aqueous ions.
They can be used as simple tests for identifying transition metal ions.
E:\INORGA NIC CHEMISTRY\C O ORDINA TIO N COMP\extratrans_files\transppt.gif

Text and formula summary of these reactions of 3d block ions is given below but there are more details in most cases in the
notes for each metal for ...

[M(H2O)6]n+ where M = metal, n = 2 or 3 and Al3+ for comparison (See Chemical Tests for more precipitates)
... and many are useful simple tests to identify metal ions (ppt. = precipitate, gel. = gelatinous)

Reagent\Ion Cr3+(aq)
and initial
colour
green

Mn2+(aq) very Fe2+(aq)

pale pink ~
colourless
pale green

Fe3+(aq)

Co2+(aq)

Ni2+(aq)

Cu2+(aq)

Zn2+(aq)

Al3+(aq)

yellow-

pink

green

blue

colourless

colourless

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initial
NaOH(aq)

green gel.
ppt. of

strong
base/alkali

Cr(OH)3

excess
NaOH(aq)

strong
base/alkali

ppt.
dissolves to
give clear
green
solution of
complex ion
[Cr(OH)6]3green gel.
ppt. of

initial
NH3(aq)

weak
base/alkali

excess
NH3(aq)

weak
base/alkali

Cr(OH)3

dissolves clear green

solution of
complex ion

white gel.
ppt. but
darkens with
oxidation

dark green
ppt. =>
brown on
oxidation

Mn(OH)2
==> Mn2O3
==> MnO2
no further
effect - just
as above with
more
oxidation

Fe(OH)2 ==>
Fe(OH)3
no further
effect - just
as above with
more
oxidation

white ppt.
darkens with
oxidation
from O2

dark green
ppt. turns
brown oxidation

Mn(OH)2
==> Mn2O3
==> MnO2
no further
effect

Fe(OH)2 ==>
Fe(OH)3
no further
effect

brown
brown gel.
ppt. of
Fe(OH)3

no further
no further
effect - just effect
as above with
more
oxidation

weak
base/alkali

brown gel.
ppt. of
Fe(OH)3

Zn(OH)2

Al(OH)3

no further effect

ppt.
dissolves clear
solution,
colourless
complex ion

ppt.
dissolves clear
solution,
colourless
complex ion

[Zn(OH)4]2white gel.
ppt. of

[Al(OH)6]3white gel.
ppt. of

gel. blue ppt. of

blue gel. ppt. green gel.

that turns
ppt. of
pink on
standing
Ni(OH)2

Zn(OH)2

Al(OH)3

ppt.
dissolves clear
colourless
solution of

no further
effect

Cu(OH)2

Co(OH)2

no further
effect

green gel.
ppt. +
bubbles

white ppt.
that darkens
with
oxidation

Cr(OH)3 +
CO2

Fe(OH)3 +
MnCO3 ==> Fe(OH)2 ==> CO2
Mn2O3 ==> Fe(OH)3
MnO2
Mn2+(aq) very Fe2+(aq)
Fe3+(aq)
pale pink ~
colourless
pale green yellowbrown

Reagent/Ion Cr3+(aq)
and initial
colour
green

white gel.
ppt. of

Cu(OH)2

no further
effect

ppt.
dissolves clear brown
solution of
complex ion
2+

dark green
ppt. turns
brown oxidation

white gel.
ppt. of

Co(OH)2

[Cr(NH3)6]3+

adding of
Na2CO3(aq)

gel. blue ppt. of

blue gel.
green gel.
ppt. that
ppt. of
turns pink on
standing
Ni(OH)2

brown gel.
ppt. +
bubbles

[Co(NH3)6]
blue gel. ppt.
that turns
pink on
standing

dissolves clear pale

blue solution
of complex
ion
[Ni(NH3)6]
green gel.
ppt of
Ni(OH)2 +
NiCO3

Co(OH)2 +
CoCO3

2+

ppt. dissolves to
give clear blue
solution of
complex ion
[Cu(NH3)4(H2O)2]2+

[Zn(NH3)4]2+
white gel.
gel. blue-turquoise white gel.
ppt of
ppt.
ppt. +
bubbles
Cu(OH)2 + CuCO3 Zn(OH)2 +
ZnCO3
Al(OH)3+
CO2

Co2+(aq)

Ni2+(aq)

Cu2+(aq)

Zn2+(aq)

Al3+(aq)

pink

green

blue

colourless

colourless

The comparison equations for the aluminium ion (NOT a 3d block metal)

The addition of limited amounts of the bases sodium hydroxide or ammonia solution to an aluminium salt solution.
o [Al(H2O)6]3+(aq) + 3OH-(aq) ==> [Al(H2O)3(OH)3](s) + 3H2O(aq)
o A white gelatinous precipitate of aluminium hydroxide is formed.

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Simplified equation: Al3+(aq) + 3OH-(aq) ==> Al(OH)3(s)

The further addition of excess sodium hydroxide or ammonia solution.
o With excess ammonia there is no effect, but with excess sodium hydroxide the aluminium hydroxide dissolves to
form a soluble aluminate complex anion - amphoteric behaviour.
o

[Al(H2O)3(OH)3](s) + 3OH-(aq) ==>

*[Al(OH)6]3-(aq)

+ 3H2O(aq)

*[Al(OH)6]3-(aq)

Simplified equation: Al(OH)3(s) + 3OH-(aq) ==>

*The products will be an equilibrium mixture including [Al(H2O)2(OH)4]-(aq) and [Al(H2O)(OH)5]2-(aq) too. You

could write the equation in terms of forming these species too and any of the three possibilities should get
you the marks.
o To complete the 'amphoteric' picture of aluminium hydroxide consider it dissolving in mineral acids to form
typical salts e.g. aluminium chloride, aluminium nitrate and aluminium sulphate.
Al(OH)3(s) + 3HCl(aq) ==> AlCl3(aq) + 3H2O(l)
Al(OH)3(s) + 3HNO3(aq) ==> Al(NO3)3(aq) + 3H2O(l)
2Al(OH)3(s) + 3H2SO4(aq) ==> Al2(SO4)3(aq) + 6H2O(l)
The addition of sodium carbonate solution to an aluminium salt solution.
o Bubbles of carbon dioxide and a white gelatinous precipitate of aluminium hydroxide are formed.
2[Al(H2O)6]3+(aq) + 3CO32-(aq) ==> 2[Al(H2O)3(OH)3](s) + 3CO2(g) + 3H2O(aq)
There several equation 'permutations' to represent this quite complicated reaction, so I've just composed
one that shows the formation of both observed products. Since sodium carbonate solution is alkaline you can
legitimately write a hydroxide ppt. equation as for sodium hydroxide above but it doesn't show the
formation of carbon dioxide.
You can write an equation to show the formation of carbon dioxide leaving a soluble cationic complex
of aluminium in solution and this equation fits in well with the acid-base nature of this reaction.
[Al(H2O)6]3+(aq) + CO32-(aq) ==> 2[Al(H2O)4(OH)2]+(aq) + CO2(g) + 3H2O(aq)
This equation shows the hexaaquaaluminium ion acting as a Bronsted-Lowry acid donating two
protons to the carbonate ion (B-L base) to form carbon dioxide and water.
This reaction shows why 'aluminium carbonate' 'Al2(CO3)3' cannot exist. The hydrated highly charged
central metal ion is too acidic to co-exist with a carbonate ion. The same situation applies to the
chromium(III) Cr3+ and iron(III) Fe3+ ions i.e. no chromium(III) carbonate or iron(III) carbonate exists.
However with a lesser charged, lesser acidic ion, carbonates can exist, so there is an iron(II) carbonate
FeCO3.
The addition of excess sodium carbonate solution has no further effect. Sodium carbonate is too weak a base to effect
the amphoteric nature of aluminium hydroxide.

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