A2 TM Revision Mar ‘17 0

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A2 (yr 13) TM Chemistry

Revision Workshop
21 March 2017

Preparing for your A-level Examinations

Participants Notes
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A2 TOPICS INDEX

1. Transition Elements p2

2. Redox p25

3. Electrochemistry p28
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1. TRANSITION ELEMENTS

Transition Series

Transition Series Elements

First Series Sc – Zn 3d
Second Series Y – Cd 4d
Third Series La – Hg 5d

1.1 General Characteristics of Transition Metals:

1. Form complex ions

2. Form coloured ions
3. Act as catalysts
4. Form compounds with the transition element in different oxidation states

These properties are linked to the presence of an incomplete d-sub-shell in an ion.

Consider:

Sc 1s2 2s2 2p6 3s2 3p6 3d1 4s2

Cu 1s2 2s2 2p6 3s2 3p6 3d10 4s1
Cu+ 1s2 2s2 2p6 3s2 3p6 3d10 4s0
Cu2+ 1s2 2s2 2p6 3s2 3p6 3d9 4s0

1.2 Complex Formation Definitions

Complex A central metal atom or ion surrounded by ions or

molecules called ligands

Ligand An ion or molecule which donates an electron pair to

form a co-ordinate bond, i.e. a Lewis Base or
nucleophile

Coordinate bond A covalent bond formed using two electrons from one
atom (the ligand)

Coordination The number of coordinate bonds formed to the central

number metal atom (NOT the number of ligands – see later)
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1.3 Co-ordination Numbers / Shapes of Complexes

If the coordination number is 6, the shape is octahedral:

co-ordinate bond

If the coordination number is 4, the shape is often tetrahedral:

If the coordination number is 2, the shape is linear:

1.4 Types of ligands

1.4.1 Unidentate ligands

These are “one-bite” ligands – one lone pair of electrons donated per ligand.
Examples include ligands with a period 2 donor atom: H2 O, NH3 , OH-, CN -
or ligands with a period 3 donor atom: Cl-, S2 O3 2-

Examples:

Metal Ligand Coordination Complex Shape Colour

Ion Number
3+
Cr3+ H2 O 6 [Cr(H2 O)6 ] octahedral green
3+
Co3+ NH3 6 [Co(NH3 )6 ] octahedral brown
2-
Cu2+ Cl- 4 [CuCl4 ] tetrahedral blue
3-
Ag+ S2 O3 2- 2 [Ag(S2 O3 )2 ] linear colourless
+
Ag+ NH3 2 [Ag(NH3 )2 ] linear colourless
-
Ag+ Cl- 2 [AgCl2 ] linear colourless
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1.4.2 Bidentate Ligands

These are “two bite” ligands - two lone pairs of electrons donated per ligand.

Examples:

Ethanediamine (en):

H2N CH2CH2 NH2

Ethanedioate anion:

O O
C C
O O

1.4.3 Multidentate ligands

Examples: a hexadentate ligand - six lone pairs of electrons donated per ligand.

Ethylenediaminetetraacetate ion, EDTA4-

O O
C C H2 H2 C C
O O
N CH2 CH2 N
O O
C C H2 H2 C C
O O

3-
Example 1 [Fe(C2 O4 )3 ]

Example 2 [Pt(NH3 )2 Cl2 ]

1.5 Formation of coloured ions

1.5.1 Colour depends upon:

1. The transition metal.

2. The oxidation state of the transition metal.
3. The number of ligands surrounding the transition metal ion.
4. The nature of the ligands surrounding the transition metal ion.
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1.5.2 Origin of colour:

 In presence of ligand, the 5 x 3d orbitals of a transition metal ion split to form

2 slightly different energy levels
 The electrons in the lower 3d sub-level absorb visible light
 Electrons move to a higher, more excited energy state (d → d transitions)
 Difference in energy between levels is:
E2 – E1 = E = hhc / 
(where h = Planck’s constant, is the frequency of light absorbed, c = speed of
light and  is the wavelength).
 We see the colours which are not absorbed, i.e. the complementary colour

Energy

E2 – E1
3d = E

1.5.3 An application
 Measurement of transition metal ion concentration using a colorimeter/
spectrophotometer
 Note that an intense colour is needed for accurate results and this can be
achieved by use of a suitable ligand, e.g.
Fe2+ (aq) absorption weak: add 2,2-bipyridyl (intense red complex)
Fe3+ (aq) absorption weak; add thiocyanate (intense red complex)

1.6 Catalytic activity

Area under curve

No. of
= total number of particles
particles with
given energy

Ea Ea
(catalyst)
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The transition metal as a catalyst has the following effect on the reaction:
 Provides an alternative route.
 Lowers the activation energy.
 Hence more molecules can react.
 Remember the catalyst remains unchanged in amount and chemical nature.

There are 2 types of catalysts: homogeneous (same state) and heterogenous (different
state):

1.6.1 Examples of Homogeneous catalysis include

NB These two examples are specifically mentioned in both the AQA & Edexcel
specifications! 

Example 1:
2- - 2-
Overall: S2 O8 (aq) + 2 I (aq) → 2 SO4 (aq) + I2 (aq);

This reaction is catalysed by Fe2+

(note this reaction has a high Ea due to a reaction between two like charged ions)

2- 2+ 2- 3+
Step 1: S2 O8 (aq) + Fe (aq) → 2 SO 4 (aq) + Fe (aq)
3+ 2+
Step 2: 2 I- (aq) + Fe (aq) → I2 (aq) + Fe (aq)

2+
NB Fe does not appear in the overall equation and is recovered unchanged at the end
of the reaction.

Example 2:
-
MnO 4 / C2 O 4 2- : catalysed by Mn2+ (NB this is an example of autocatalysis – the
catalyst is generated in the reaction and thus the reaction speeds up as it proceeds).
- 2- + 2+
2 MnO 4 (aq) + 5 C2 O4 (aq) + 16 H (aq) → 2 Mn (aq) + 5 CO 2 (g) + 8 H2 O (l)

Mechanism:
2+ - + 3+
Step 1: 4 Mn + MnO 4 + 8 H → 5 Mn + 4 H2 O
3+ 2- 2+
Step 2: 2 Mn + C2 O 4 → 2 Mn + 2 CO 2

2+
NB Mn does not appear in the overall equation and is recovered unchanged at the
end of the reaction.
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1.6.2 Examples of Heterogenous catalysis

These are reversible reactions

The 5 steps in heterogenous catalysis and a simple analogy:

1. Diffusion to surface Beach party to ice cream seller

2. Adsorption on surface Arriving at the counter
3. Reaction on surface Making friends
4. Desorption from surface Leaving the counter
5. Diffusion from surface Moving away

Example 1: Vanadium(V) oxide, V2 O5 , used in the Contact Process:

V2O5
2 SO2 (g) + O2 (g) 2 SO3 (g)

Step 1: SO 2 + V2 O5 → SO 3 + V2 O4
Step 2: 2 V2 O4 + O2 → 2 V2 O5

Example 2: Iron on silica support, used in the Haber process to manufacture

ammonia:
Fe
N2 (g) + 3 H2 (g) 2 NH3 (g)

Example 3: Nickel, very finely divided, used in the hydrogenation of vegetable oil:

Ni
HC CH + n H2 H 2C CH2

n n

Hydrogenation causes hardening of vegetable oil forming fat. It is an

important step in the manufacture of margarine. The extent of
hydrogenation is linked to hardness.
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1.7 Acidity reactions of metal aqua complexes (hydrolysis) (AQA ONLY)

Consider separate solutions containing the ions:

[M(H2 O)6 ]3+
[M(H2 O)6 ]2+
[M(H2 O)6 ]+

Example 1: for a solution containing approximately 1 mol dm-3 of [M(H2 O)6 ]3+

H H 3+
H O H
H O O H polarising power
M3+ 
H O O H 

H H O H
O
H
H H

Overall: [M(H2O)6]3+ + H2O [M(H2O)5(OH)]2+ + H3O+

Approximately 1000 n 1 1

Hence: [H+] ~10-3 and pH ~3

Example 2: for a solution containing approximately 1 mol dm-3 of [M(H2 O)6 ]2+

H H 2+
H O H
H O O H polarising power
M2+
H O O H 

H H O H
O
H
H H

Overall: [M(H2O)6]2+ + H2O [M(H2O)5(OH)]+ + H3O+

Approximately 100 000 n 1 1

Hence: [H+] ~10-5 and pH ~5

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1.8 Reactions of metal aqua complexes with other bases

Consider the relative base strengths of the following:

OH-; NH3 ; CO 3 2-

Example 1: The addition of a 2.0 mol dm-3 solution of NaOH to a solution

containing, e.g. Al3+ (aq)

H H 3+
H H O H-
O
H O O H
O H-
Al3+
H O O H
H H O H-
O
H H O H-

3+ -
Dropwise NaOH [Al(H2O)6] + 3 OH [Al(H2O)3(OH)3] + 3 H2O

colourless solution white precipitate

- -
Excess NaOH [Al(H2O)3(OH)3] + OH [Al(H2O)2(OH)4] + H2O

white precipitate colourless solution

acting as a ligand

NB The [Al(H2 O)2 (OH)4 ]- complex ion is often more simply written as [Al(OH)4 ]-

Summary:
 OH- acting as a base.
 Precipitation when no repulsion; species hydrogen bond together.
 Excess OH- (aq) forms negatively-charged species.
 Repulsion causes separation, precipitate re-dissolves.
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Example 2: Addition of concentrated NH3 (aq) to a solution containing Cr3+ (aq)

H H 3+
NH3
H O H
H O O H NH3
3+
Cr NH3
H O O H
H H NH3
O
H H NH3
NH3

acting as a base

3+
Dropwise NH3 [Cr(H2O)6] + 3 NH3 [Cr(H2O)3(OH)3] + 3 H2O

green/ blue solution grey/ green precipitate

3+ -
Excess NH3 [Cr(H2O)3(OH)3] + 6 NH3 [Cr(NH3)6] + 3 H 2O + 3 OH

grey/ green precipitate purple solution

acting as a ligand

Summary:
 NH3 is a weaker base than OH-.
 NH3 acts first as a base than as a ligand.
 Precipitation when no repulsion; species hydrogen bond together.
 Excess NH3 (aq) forms positively charged species.
 Repulsion casues separation, precipitate re-dissolves.
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Example 3: In concentrated NH3 (aq) the ratio H2 O: NH3 is 2:1

Substitution reactions are in equilibria and sometimes not all H2 O replaced

H H 2+
NH3
H O H
H O O H NH3
2+
Cu NH3
H O O H
H H NH3
O
H H

Example 4: Addition of solution containing CO 3 2- to solution containing M3+ (aq)

CO3 2- acts only as a base, e.g.

H H 3+
O
H O H
O C
H O O H
O
3+
Cr
H O O H O
H H O C
O
O
H H

3+ 2-
2 [Cr(H2O)6] + 3 CO3 2 [Cr(H2O)3(OH)3] + 3 H2O + 3 CO2
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The following INCORRECT stepwise equations aid understanding of this reaction:

3+ +
2 [Cr(H2O)6] 2 [Cr(H2O)3(OH)3] + 6 H

2- +
3 CO3 + 6 H 3 H2O + 3 CO2

NB Aqueous complex ions of metals in oxidation state (II) form simple carbonate
precipitates on the addition of aqueous Na2 CO 3 . NO CO2 is produced.

e.g. Fe2+ (aq) + CO 3 2- (aq) → FeCO 3 (s)

1.9 Redox reactions

Useful rules of thumb:

 High oxidation state to low oxidation state:

Reagents: acid (e.g. dilute H2 SO 4 ) + reducing agent (e.g. Zn or SO 2 )

 Low oxidation state to high oxidation state

Reagents: base (e.g. NaOH (aq) ) + oxidising agent (e.g. H2 O2 )

Explanations:
High oxidation states are commonly found in complexes containing oxygen
-
Consider the reduction: MnO 4 → [Mn(H2 O)6 ]2+
Oxidation States: VII II

Consider the oxidation: [Cr(H2 O)6 ]3+ → CrO 4 2-

Oxidation States: III VI

1.10 Oxidation states of vanadium (AQA & Edexcel only)

Summary table:

Oxidation state Formula of species Colour of aqueous solution

-
+5 VO 3 yellow
+5 VO 2 + orange
+4 VO 2+ blue
+3 V3+ green
+2 V2+ violet

There are two aqueous species which are both V(V) – converted in presence of acid:
-
VO3 + 2 H+ → VO2 + + H2 O
V V

Note that this is NOT a redox reaction as there are no electrons in the overall equation.
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V(V) can be reduced stepwise through the other oxidation states down to V(II) with an
appropriate reducing agent, i.e:
+
VO 2 + 2 H+ + e- → VO2+ + H2 O SO2 will reduce V(V) to V(IV)
V IV
+
VO 2 + 2 H+ + e- → V3+ + H2 O SO2 will reduce V(IV) to V(III)
IV III Sn will reduce V(IV) to V(III)
+
V3 + e- → V2+ Zn will reduce V(III) to V(II)
III II

Each of these reductions can be predicted using the appropriate half-equations and Eo
values listed below:
+
VO 2 + 2 H+ + e- → VO2+ + H2 O Eo = +1.00 V
+
VO 2 + 2 H+ + e- → V3+ + H2 O Eo = +0.34 V
-
SO 4 2 + 4 H+ + 2e- → H2 SO 3 + H2 O Eo = +0.17 V
+
Sn2 + 2e- → Sn Eo = - 0.14 V
+
V3 + e- → V2+ Eo = - 0.26 V
+
Zn2 + 2e- → Zn Eo = - 0.76 V
+
V2 + 2e- → V Eo = - 1.18 V

1.11 Substitution reactions

1.11.1 Substitution by chloride ligands

1. Chloride ions are larger than water and ammonia molecules (period 3 vs.
period 2).
2. Substitution of all water ligands by chloride ligands results in a change in
coordination number and shape.
3. The colour of the complex changes.
4. Since chloride ions are charged, the charge on the complex changes.
5. Substitutions are equilibria; conc. HCl (aq) gives chloro complexes (NaCl is
not very soluble and does not have a sufficiently high chloride ion
concentration).

e.g. [Co(H2 O)6 ]2+ + 4 Cl- → [CoCl4 ]2- + 6 H2 O

pink solution blue solution

[Cr(H2 O)6 ]3+ [Cr(H2 O)5 Cl]2+ [Cr(H2 O)4 Cl2 ]+

green/blue pale green dark green
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1.11.2 Substitution of monodentate ligands by bidentate ligands:

e.g. [Co(H2 O)6 ]2+ + 3 en → [Co(en)3 ]2+ + 6 H2 O

e.g. [Co(H2 O)6 ]2+ + 3 C2 O 4 2- → [Co(C2 O4 )3 ]4- + 6 H2 O

These complexes are octahedral.

NB: bidentate ligands can also bond two metal ions together acting as a bridge.

1.11.3 Substitution of monodentate ligands by the hexadentate ligand EDTA4-

1. EDTA4- is a hexadentate ligand and forms a 6 coordinate complex.

2. A colour change ususally occurs when water is replaced by EDTA4-.
3. The complexes formed are octahedral.
4. There is a large entropy change when a monodentate ligand is replaced by EDTA4-

e.g. [Co(H2 O)6 ]2+ + EDTA4- → [Co(EDTA)]2- + 6 H2 O

2 ions form 7 species

1.12 The stability of complexes

Complexes in which bidentate or multidentate ligands are bonded to one central metal
ion are known as chelates. Chelate stability depends on:

1. Size of ring formed by ligand with metal ion, i.e. strain.

2. Metal-ligand bond energy.
3. Number of bonds to be broken when ligand replaced, e.g. 6 for EDTA4-.
4. A reaction is feasible when Gibbs Free Energy, G, is negative.
G = H – TS.
If the change in entropy, S, is large and positive; and change in energy H is
small when bond energies are similar, then TS >>> H. Hence, Gibbs Free
Energy (G) is large and negative.

NB: The stability of EDTA4- complexes is so high that the reactions go to completion
so that, for example, no precipitate forms when NaOH (aq) is added. This is known as
the chelate effect.
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1.13 Summary Table of Aqueous Metal Ion Chemistry (AQA)

Formula &
colour of Al3+ Fe2+ Fe3+ Cu2+
species
3+ 2+ 3+ 2+
aqueous [Al(H 2O)6] [Fe(H 2O)6] [Fe(H 2O)6] [Cu(H 2O)6]
solution Colourless Pale green Brown solution Light blue solution
solution solution

dropwise [Al(H 2O)3(OH)3] [Fe(H 2O)4(OH)2] [Fe(H 2O)3(OH)3] [Cu(H 2O)4(OH)2]

NaOH White ppt Green ppt Brown ppt Blue ppt
turns to brown
ppt in air

excess [Al(H 2O)2(OH)4]- No change No change No change

NaOH Colourless
solution

dropwise Al(H 2O)3(OH)3] [Fe(H 2O)4(OH)2] [Fe(H 2O)3(OH)3] [Cu(H 2O)4(OH)2]

NH3 White ppt Green ppt Brown ppt Blue ppt
turns to brown
ppt in air

excess NH 3 No change No change No change [Cu(NH 3)4(H 2O)2]2+

Deep blue solution

excess [Al(H 2O)3(OH)3] FeCO3 [Fe(H 2O)3(OH)3] CuCO3

Na2CO3 White ppt & CO2 Green ppt Brown ppt & Green ppt
produced CO2 produced

2-
excess [CuCl 4]
conc. HCl X X X Green solution
Tetrahedral

pH of pH = 2 – 3 pH = 7 pH = 2 – 3 pH = 5 – 6
aqueous
solution acidic neutral acidic weakly acidic

NB. Shapes of ALL complexes are octahedral unless otherwise stated in the table.
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1.13a My Summary Rules for Learning Aqueous Metal Ion Chemistry (AQA)

1. With dropwise NaOH:

ALL give a ppt. of the metal hydroxide, [M(OH)n (H2 O)6-n ], where n = 2 or 3

2. With excess NaOH:

-
Al only dissolves and gives [Al(OH)4 (H2 O)2 ]
Others don’t (still metal hydroxide ppt. above)

3. With dropwise NH3 :

ALL give a ppt. of the metal hydroxide (same as with dropwise NaOH)

4. With excess NH3 :

2+ 3+
ALL dissolve except Fe and Fe (still metal hydroxide ppts.)
2+ 3+
Cu gives [Cu(NH3 )4 (H2 O)2 ] ; Al gives [Al(NH3 )6 ]

5. With Na2 CO 3 :
3+
M ALL give ppt. of metal hydroxide and effervescence of CO 2
2+
M ALL give ppt. of metal carbonate, MCO 3

6. With c. HCl:
2-
Cu only - gives tetrahedral [CuCl4 ] complex ion

7. Acidity:
3+
M ALL acidic
2+ 2+
M ALL neutral, except Cu which is only slightly acidic
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1.14 Summary Table of Aqueous Metal Ion Chemistry (OCR-A)

Formula &
colour of Cr 3+ Mn2+ Fe2+ Fe3+ Cu2+
species

aqueous [Cr(H 2O)6]3+ [Mn(H 2O)6]2+ [Fe(H 2O)6]2+ [Fe(H 2O)6]3+ [Cu(H 2O)6]2+
solution Purple solution Pale pink Pale green Brown solution Light blue solution
(colourless) solution
solution

dropwise [Cr(H 2O)3(OH)3] [Mn(H 2O)4(OH)2] [Fe(H 2O)4(OH)2] [Fe(H 2O)3(OH)3] [Cu(H 2O)4(OH)2]
NaOH Grey/green ppt Pale brown ppt Green ppt Brown ppt Blue ppt
turns darker turns to brown
brown ppt in air ppt in air

excess [Cr(OH)6]3- No change No change No change No change

NaOH Green solution

dropwise [Cr(H 2O)3(OH)3] [Mn(H 2O)4(OH)2] [Fe(H 2O)4(OH)2] [Fe(H 2O)3(OH)3] [Cu(H 2O)4(OH)2]
NH3 Grey/green ppt Pale brown ppt Green ppt Brown ppt Blue ppt
turns darker turns to brown
brown ppt in air ppt in air

excess NH 3 [Cr(NH 3)6]3+ No change No change No change [Cu(NH 3)4(H2O)2]2+

Purple solution Deep blue solution

excess conc. [CuCl 4]2-

HCl X X X X Green solution
Tetrahedral

NB. Shapes of ALL complexes are octahedral unless otherwise stated in the table.
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1.14a My Summary Rules for Learning Aqueous Metal Ion Chemistry (OCR-A)

1. With dropwise NaOH:

ALL give a ppt. of the metal hydroxide, [M(OH)n (H2 O) 6-n ] where n = 2 or 3

2. With excess NaOH:

3-
Cr only dissolves and gives [Cr(OH)6 ]
Others don’t (still metal hydroxide ppt. above)

3. With dropwise NH3 :

ALL give a ppt. of the metal hydroxide (same as with dropwise NaOH)

4. With excess NH3 :

3+ 2+
Cr & Cu only dissolve - Cr gives [Cr(NH3 )6 ] and Cu gives [Cu(NH3 )4 (H2 O)2 ]
Others don’t (still metal hydroxide ppt. as above)

5. With c. HCl:
2-
Cu only - gives tetrahedral [CuCl4 ] complex ion
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1.15 Summary Table of Aqueous Metal Ion Chemistry (OCR-Salters)

Formula &
colour of Fe2+ Fe3+ Cu2+
species

aqueous [Fe(H 2O)6]2+ [Fe(H 2O)6]3+ [Cu(H 2O)6]2+

solution Pale green Brown solution Light blue solution
solution

dropwise [Fe(H 2O)4(OH)2] [Fe(H 2O)3(OH)3] [Cu(H 2O)4(OH)2]

NaOH Green ppt Brown ppt Blue ppt
turns to brown
ppt in air

excess No change No change No change

NaOH

dropwise [Fe(H 2O)4(OH)2] [Fe(H 2O)3(OH)3] [Cu(H 2O)4(OH)2]

NH 3 Green ppt Brown ppt Blue ppt
turns to brown
ppt in air

excess NH 3 No change No change [Cu(NH 3)4(H 2O)2]2+

Deep blue solution

excess conc. [CuCl 4]2-

HCl X X Green solution
Tetrahedral

NB. Shapes of ALL complexes are octahedral unless otherwise stated in the table.
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1.15a My Summary Rules for Learning Aqueous Metal Ion Chemistry (OCR-Salters)

1. With dropwise NaOH:

ALL give a ppt. of the metal hydroxide, [M(OH)n (H2 O) 6-n ] where n = 2 or 3

2. With excess NaOH:

ALL ppts remain (still metal hydroxide ppt. above)

3. With dropwise NH3 :

ALL give a ppt. of the metal hydroxide (same as with dropwise NaOH)

4. With excess NH3 :

2+
Cu only dissolves and gives [Cu(NH3 )4 (H2 O)2 ]
Others don’t (still metal hydroxide ppt. as above)

5. With c. HCl:
2-
Cu only - gives tetrahedral [CuCl4 ] complex ion
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1.16 Summary Table of Aqueous Metal Ion Chemistry (Edexcel)

Formula &
colour of Cr 3+ Fe2+ Fe3+ Co2+ Cu2+
species
3+ 2+ 3+ 2+ 2+
aqueous [Cr(H 2O)6] [Fe(H 2O)6] [Fe(H 2O)6] [Co(H 2O)6] [Cu(H 2O)6]
solution Purple solution Pale green Brown solution Pink solution Light blue solution
solution

dropwise [Cr(H 2O)3(OH)3] [Fe(H 2O)4(OH)2] [Fe(H 2O)3(OH)3] [Co(H 2O)4(OH)2] [Cu(H 2O)4(OH)2]
NaOH Grey/green ppt Green ppt Brown ppt Blue ppt Blue ppt
turns to brown but leave in air
ppt in air forms beige ppt
[Co(H 2O)3(OH)3]

excess [Cr(OH)6]3- No change No change No change No change

NaOH Green solution

dropwise [Cr(H 2O)3(OH)3] [Fe(H 2O)4(OH)2] [Fe(H 2O)3(OH)3] [Co(H 2O)4(OH)2] [Cu(H 2O)4(OH)2]
NH3 Grey/green ppt Green ppt Brown ppt Blue ppt Blue ppt
turns to brown
ppt in air

excess [Cr(NH 3)6]3+ No change No change [Co(NH 3)6]2+ → [Cu(NH 3)4(H 2O)2]2+
3+
NH3 Purple solution [Co(NH 3)6] Deep blue solution
Straw/yellow
solution turns to
brown solution
in air

excess [CoCl 4]2- [CuCl 4]2-

conc. HCl X X X Blue solution Green solution
Tetrahedral Tetrahedral

NB. Shapes of ALL complexes are octahedral unless otherwise stated in the table.
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1.16a My Summary Rules for Learning Aqueous Metal Ion Chemistry (Edexcel)

1. With dropwise NaOH:

ALL give a ppt. of the metal hydroxide, [M(OH)n (H2 O) 6-n ], where n = 2 or 3

2. With excess NaOH:

3-
Cr only dissolves to give [Cr(OH)6 ]
Others don’t (still metal hydroxide ppt. above)

3. With dropwise NH3 :

ALL give a ppt. of the metal hydroxide (same as with dropwise NaOH)

4. With excess NH3 :

2+ 3+
ALL dissolve except Fe and Fe (still metal hydroxide ppts.)
n+ 2+
Cr & Co give [M(NH3 )6 ] ; Cu gives [Cu(NH3 )4 (H2 O)2 ]

5. With c. HCl:
2-
Co & Cu only - give tetrahedral [MCl4 ] complex ions
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1.17 Summary Table of Aqueous Metal Ion Chemistry (WJEC)

Formula &
colour of Cr3+ Fe2+ Fe3+ Cu2+ Co2+
species
3+ 2+ 3+ 2+ 2+
aqueous [Cr(H2O)6] [Fe(H2O)6] [Fe(H2O)6] [Cu(H2O)6] [Co(H2O)6]
solution Purple solution Pale green Brown solution Light blue Pink solution
solution solution

dropwise [Cr(H2O)3(OH)3] [Fe(H2O)4(OH)2] [Fe(H2O)3(OH)3] [Cu(H2O)4(OH)2] X

NaOH Grey/green ppt Green ppt Brown ppt Blue ppt
turns to brown
ppt in air

3-
excess [Cr(OH)6] No change No change No change X
NaOH Green solution

2- 2-
excess [CuCl4] [CoCl4]
conc. HCl X X X Green solution Blue solution
Tetrahedral Tetrahedral

NB. Shapes of ALL complexes are octahedral unless otherwise stated in the table.
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1.17a My Summary Rules for Learning Aqueous Metal Ion Chemistry (WJEC)

1. With dropwise NaOH:

ALL give a ppt. of the metal hydroxide, [M(OH)n (H2 O)6-n ], where n = 2 or 3

2. With excess NaOH:

3-
Cr only dissolves to give [Cr(OH)6 ]
Others don’t (still metal hydroxide ppt. above)

3. With c. HCl:
2-
Co & Cu only - give tetrahedral [MCl4 ] complex ion
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2. REDOX
2.1 Redox reactions

You should already know from AS Chemistry;

 That oxidation and reduction involve transfer of electrons

 Recall the acronym “OILRIG” to remember that:
Oxidation Is Loss and Reduction Is Gain (of electrons)
 To use OILRIG to deduce if a species has been oxidised or reduced in a reaction
 To know the difference between oxidised and an oxidising agent and reduced and
a reducing agent! 
 Be able to write balanced half-equations when reactant and product are specified
 Be able to add two balanced half-equations to produce the overall equation
(electrons cancel).

2.1.1 Writing balanced half-equations:

1. write down the reactant and product as supplied.
+
2. balance the equation for atoms – remember, you can use H and.or H2 O to balance
the loss or gain of H or O in an equation – do NOT write H2 or O 2 !!
3. finally, add the appropriate number of electrons to balance the charges.
2-
Example Deduce the half equation for the oxidation, in acid solution, of SO 2 to SO 4
2-
SO2 → SO 4 Two “oxygens” needed - add 2 H2 O to LHS
2- + +
2 H2 O + SO 2 → SO 4 + 4H Balance for atoms – add 4 H to RHS
2- + - -
2 H2 O + SO 2 → SO 4 + 4 H + 2e Balance for charges by adding 2e to RHS

2.1.2 Writing the balanced full equation from the half-equations:

1. firstly, multiply up each half-equation as necessary to get the same number of
electrons in each one.
2. add the two half equations together – the electrons will cancel out and you may
+
find that other species such as H or H2 O cancel down or out too.
3. finally, double check the final equation is balanced for the atoms of each element
on each side and the charges too.
2
Example Deduce the full equation for the oxidation of SO 2 to SO 4 - by MnO 4 - ?
2- + -
Half equations: 1. 2H2 O + SO 2 → SO 4 + 4H + 2e
2. MnO4 - + 8H+ + 5e- → Mn2+ + 4H2 O

Multiply 1. by 5 and 2. by 2 to get same no. of electrons in each one:

2- + -
1. 10H2 O + 5SO2 → 5SO4 + 20H + 10e
2. 2MnO4 - + 16H+ + 10e- → 2Mn2+ + 8H2 O
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2- +
Add together: 10H2 O + 5SO2 + 2MnO 4 - + 16H+ → 5SO 4 + 20H + 2Mn2+ + 8H2O
Cancel H+ and H2 O on each side to produce final equation:
2- +
2H2 O + 5SO2 + 2MnO 4 - → 5SO4 + 4H + 2Mn2+

2.2 Redox titration calculations

2.2.1 Basic method

A reminder that most moles calculations involve the same three steps:

Step 1 – calculate the no. of moles (n) of the known substance;

Step 2 – use the balanced equation or stoichiometry for the reaction (always supplied)
to deduce the no. moles of the unknown (the one you’re asked to find in the
question);

Step 3 – convert the unknown no. of moles into the required answer (mass, M r,
concentration, volume, % purity, etc)

We will use this method in all the calculations in this booklet.

2.2.2 Calculations

Again, these use the same basic three step method as for other moles calculations (see
previous section).

– this time step 1 to calculate the known usually (but not always) involves the titre
value.

e.g. 1 25.0 cm3 of an acidified solution of ethandioate, C 2 O4 2-, was found to react
with exactly 22.7 cm3 of a 0.020 M solution of potassium manganate(VII).
Calculate the concentration of the ethanedioate solution?

1. No. moles MnO 4 - (known) = C x V / 1000 = 0.020 x 22.7 / 1000 = 4.54 x 10-4 mol

2. Using equation:
2MnO4- (aq) + 5C2O42- (aq) + 16H+ (aq) 2Mn2+ (aq) + 10CO2 (aq) + 8H2O (l)

2 mol MnO 4 - reacts with 5 mol C 2 O4 2-

1 mol MnO 4 - reacts with 5 /2 mol C2 O4 2-
4.54 x 10-4 mol MnO4 - reacts with 4.54 x 10-4 x 5 /2 = 1.14 x 10-3 mol C2 O4 2-

3. Concentration (C) of C 2 O 4 2- = 1000 x n / V = 1000 x 1.14 x 10-3 / 25.0 = 0.0454 M

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e.g. 2 A 0.152g iron sample containing an insoluble impurity was found to react with
exactly 17.3 cm3 of a 0.0160 M solution of Cr2 O7 2-.
Calculate the % by mass of iron in the sample?

1. No. moles Cr2 O7 2- (known) = C x V / 1000 = 0.0160 x 17.3/1000 = 2.77 x 10-4 mol

2. Using equation:
Cr2O72- (aq) + 6Fe2+ (aq) + 14H+ (aq) 2Cr3+ (aq) + 6Fe3+ (aq) + 7H2O (l)

1 mol Cr2 O7 2- reacts with 6 mol Fe2+

2.77 x 10-4 mol Cr2 O 7 2- reacts with 2.77 x 10-4 x 6 mol Fe = 1.66 x 10-3 mol

3. Mass of Fe = n x Mr = 1.66 x 10-3 x 55.9 = 0.0928 g

4. % Fe = 0.0928 / 0.152 x 100 = 61.1 %

e.g. 3 Separate aqueous solutions of potassium manganate(VII) (KMnO 4 ) and

sodium manganate(VII) (NaMnO 4 ) each contained 1.00 g of the compound in
250 cm3 . A 25.0 cm3 sample of one of these solutions reacted with exactly
17.6 cm3 of a 0.100 M acidified solution of sodium ethanedioate, Na2 C2 O4.

1. No. moles C2 O4 2- (known) = C x V / 1000 = 0.100 x 17.6/1000 = 1.76 x 10 -3 mol

2. Using equation:
2MnO4- (aq) + 5C2O42- (aq) + 16H+ (aq) 2Mn2+ (aq) + 10CO2 (aq) + 8H2O (l)

5 mol C2 O4 2- reacts with 2 mol MnO 4 -

1 mol C2 O4 2- reacts with 2 /5 mol MnO 4 -
1.76 x 10-3 mol C2 O4 2- reacts with 1.76 x 10-3 x 2 /5 mol MnO4 - = 7.04 x 10-4 mol

3. Moles of MnO 4 – in 250 cm3 = 7.04 x 10-4 x 10 = 7.04 x 10-3 mol

4. Molar mass of MMnO 4 salt, Mr = m/n = 1.00/7.04 x 10-3 = 142 g mol-1

5. Mr (KMnO 4 ) = 158 g mol-1 & Mr (NaMnO 4 ) = 142 g mol-1 so solution is NaMnO4

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3. ELECTROCHEMISTRY
3.1 Electrode potentials

These are measured against a reference electrode, the HYDROGEN electrode, which is
arbitarily assigned a potential of 0.00 V.

All other half-cells have their potentials measured against this hydrogen electrode – if
this is done under the usual “standard conditions”, i.e. a pressure of 100 kPa, a
temperature of 298 K and a 1M solution, the electrode potential becomes the standard
o
electrode potential for that half-cell, given the symbol E .
o
We can use tables of E values to predict:
1. if two species are capable of reacting with each other in a redox reaction.
2. the likely reaction which will occur if two half-cell systems are brought together.

We will work through an example of each type of question.

o
A table of common E values is given below – you do NOT need to learn these – the
o
half-equations and E values you will need to answer an examination question will
always be supplied in the question paper! 

Table of some common electrode potentials

F2 (g) + 2e- 2F- (aq) Eo = + 2.56 V

MnO4- (aq) + 8H+ (aq) + 5e - Mn2+ + 4H2O (l) Eo = + 1.51 V
Cl (g) + 2e-
2 2Cl- (aq) Eo = + 1.36 V
Cr2O72- (aq) + 14H+ (aq) + 6e - 2Cr3+ + 7H2O (l) Eo = + 1.33 V
- -
Br2 (g) + 2e 2Br (aq) Eo = + 1.09 V
-
Ag+ (aq) + e Ag (s) Eo = + 0.80 V
-
Fe3+ (aq) + e Fe2+ (aq) Eo = + 0.77 V
- -
I2 (g) + 2e 2I (aq) Eo = + 0.54 V
-
Cu2+ (aq) + 2e Cu (s) Eo = + 0.34 V
-
2H+ (aq) + 2e H2 (g) Eo = + 0.00 V (defined)
-
Pb2+ (aq) + 2e Pb (s) Eo = - 0.13 V
-
Sn2+ (aq) + 2e Sn (s) Eo = - 0.14 V
-
V3+ (aq) + e V2+ (s) Eo = - 0.26 V
-
Fe2+ (aq) + 2e Fe (s) Eo = - 0.44 V
-
Zn2+ (aq) + 2e Zn (s) Eo = - 0.76 V
-
Mg2+ (aq) + 2e Mg (s) Eo = - 2.36 V
Ca2+ (aq) + 2e- Ca (s) Eo = - 2.87 V
Li+ (aq) + e- Li (s) Eo = - 3.05 V
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o
The more +ve E values are systems which are good oxidisers – they consume
electrons and would form the +ve right-hand electrode of a electrochemical cell. They
do the forward reduction reaction as written in the table above.
o
The more –ve E values are systems which are good reducers – they produce electrons
and would form the –ve left-hand electrode in an electrochemical cell. They do the
reverse oxidation reaction to that written in the table above.
o
Tables of E values are usually written in this format, with the most +ve best oxidisers
at the top (on the left hand side) and the most –ve best reducers at the bottom (on the
right-hand side).

It thus follows that any species on the left-hand side (a potential oxidiser) can react
with any species below it on the right-hand side (a potential reducer). It also follows
that species with the reverse relationship in the table can NEVER react together.

3.2 The Rules:

o
1. write down the half-equation with the most +ve E – this is the RH electrode
o
2. write down the half-equation with the more –ve E in reverse – this is the LH
electrode.
3. Multiply electrons and then add the two half-equations together to produce the
overall reaction.
o o o o
4. Calculate Ecell = ERight - ELeft (DO NOT multiply the E values – they are
independent of the number of electrons transferred).

2+
e.g 1: predict if V can react with I2 . Write an overall equation for the reaction and
o
calculate the overall Ecell .

- -
1. Most +ve E :
o I2 (g) + 2e 2I (aq) Eo = + 0.54 V

2. Reverse more –ve E :

o V2+ (aq) V3+ (s) + e- Eo = - 0.26 V

2V2+ (aq) + I2 (s) 2V3+ (s) + 2I-

3. Add half-eqns together:

4. Calculate Ecell = ER - EL = + 0.54 – (- 0.26) = + 0.80 V

o o
Since G = - nE F (you don’t need to remember this equation); when E is +ve,
G will be –ve and thus the reaction is feasible. Of course, if the forward reaction has
o o
a –ve E , then the reverse reaction will have a +ve E and be the feasible one in this
case.
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2+ 2+ 3+
e.g. 2: predict the cell reaction which will occur if the Pb /Pb and Fe /Fe cells are
connected together. Write the overall cell reaction and calculate the Ecell.

1. Most +ve E :
o Fe3+ (aq) + e- Fe2+ (aq) Eo = + 0.77 V

2. Reverse more –ve E :

o Pb (s) Pb2+ + 2e- Eo = - 0.13 V

3. Add half-eqns together: Pb (s) + 2Fe3+ (aq) Pb2+ + 2Fe2+

4. Calculate Ecell = ER - EL = + 0.77 – (- 0.13) = + 0.90 V

3.3 An alternative approach? 

e.g. Deduce the overall cell reaction between Cr2 O 7 2- and NO 3 - and calculate the Ecell?

Half-equations & electrode potentials:

Cr2O72- (aq) + 14H+ (aq) + 6e - 2Cr3+ + 7H2O (l) Eo = + 1.33 V

- -
NO3 (aq) + 3H+ (aq) + 2e HNO2 (aq) + H2O (l) Eo = + 0.94 V

Method:
1. Sketch a horizontal scale to represent the voltage.
2. Mark on the more +ve half-cell system – this is the RH electrode and thus the +ve.
3. Mark on the more –ve half-cell system – this is the LH electrode and thus the –ve.
4. Electrons flow from the –ve cathode to the +ve anode; thus oxidation takes place
at the cathode and reduction takes place at the anode as the electrons flow to there.
5. Reverse the half-equation for the cathode (LH electrode) as it produces electrons.
6. Add to produce the full equation and thus overall cell reaction.
7. Ecell = ER – EL.

This is a snapshot of the Powerpoint slide I went through in the workshop session:

5
3 2
1

6
12. POST-16 LEARNING RESOURCE
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