Chemistry Unit 5 Part 2
Chemistry Unit 5 Part 2
Chemistry Unit 5 Part 2
○ When the formula of a complex ion is given, the metal ion always comes first followed by the ligands.
○ The charge on the complex ion is the sum of the charge on the metal ion and the charges on the ligands
○ Over here, Mn has a charge of +2 and H2O has a charge of 0 hence the overall charge of the complex is +2
● The number of lone pairs attached to the metal ion is called the coordination number
and it determines the number of ligands which may be attached to the metal ion
Ligands (Continued…)
● Types of ligands:
○ Monodentate ligands each form one coordinate bond. Examples: H2O, Cl-, NH3
○ Bidentate ligands each form two coordinate bonds. Example: NH2CH2CH2NH2
○ Hexdentate ligands each form six coordinate bonds with the central metal ion. Example:
EDTA+
○ ’Polydentate’ and ‘multidentate‘ ligands are general terms for any ligands that form
more than one coordinate bond
7. Know that aqueous solutions of transition metal ions
are usually coloured
8. Understand that the colour of aqueous ions, and other
complex ions, is a consequence of the splitting of the
energy levels of the d-orbitals by ligands
9. Understand why there is a lack of colour in some
aqueous ions and other complex ions
Forming of coloured ions in solution
● Most of the transition metals form compounds which dissolve in water to
form coloured solutions.
○ Changes in the colour of the solution may indicate a change in the oxidation number
● Where the ion has a 3d0 or 3d10 arrangement, the solution of the ion is
colourless
Forming of coloured ions in solution (Continued…)
● Why do they display colour?
○ When water ligands are attached to the metal ion, the energy level splits into two levels
with slightly different energies.
○ If one of the electrons in the lower energy level absorbs energy from the visible spectrum,
it can move to the higher energy level.
■ Movement from a lower to a higher energy level is called promotion or excitation
○ When the electron moves, the amount of energy absorbed depends on the difference
of the energy level (high and low), this determines the colour of the solution.
○ For example:
■ Cu2+ ion has a small difference in energy level —> low frequency and high
wavelength visible light is absorbed —> red light is absorbed —> blue light is the
only one that remains hence giving a blue solution.
Forming of coloured ions in solution (Continued…)
● Why do some of the metal ion complex not have colour?
○ Colour arises when some wavelengths of light are absorbed while others are reflected,
which involves the excitation of electrons.
○ Ions and complexes where there are no available electrons to excite and move around
cannot absorb light and are therefore colourless.
○ For example:
■ Zinc is in the d-block of the periodic table and has completely filled d-orbitals.
Therefore, there are no unfilled or partially filled d orbitals into which an electron
can be promoted —> zinc is colourless
13. Understand why complexes with six-fold coordination have an octahedral shape,
such as those formed by metal ions with H2O, OH- and NH3 as ligands
14. Know that transition metal ions may form tetrahedral complexes with relatively
large ions such as Cl-
15. Know that square planar complexes are also formed by transition metal ions and
that cis-platin is an example of such a complex which is used in cancer treatment
where it is supplied as a single isomer and not in a mixture with the trans form
17. Know that haemoglobin is an iron(II) complex containing a polydentate ligand
and that ligand exchange occurs when an oxygen molecule bound to haemoglobin is
replaced by a carbon monoxide molecule The structure of the haem group will not be
assessed.
25. Understand, in terms of the positive increase in ΔSsystem, that the substitution of a
monodentate ligand by a bidentate or hexadentate ligand leads to a more stable
complex ion
Shapes of Complex Ions
● Octahedral complexes
○ Transition metal complexes with H2O and NH3 ligands commonly form octahedral
complexes with a bond of 90o.
○ Octahedral complexes are formed when there is six-fold coordination with monodentate
ligands
Shapes of Complex Ions (Continued…)
● Tetrahedral Complexes
○ When complexes form with larger ligands, such as Cl-, they form tetrahedral complexes
with a bond angle of 109.5o. Tetrahedral complexes can display optical isomerism.
Shapes of Complex Ions (Continued…)
● Linear Complexes
○ Formation of complex ions using 2 ligands
Shapes of Complex Ions (Continued…)
● Square Planar Complexes
○ Platinum and nickel complexes form a square planar shape. This consists of four
coordinate bonds with a bond angle of 90o.
+5 VO2+ Yellow
+4 VO2+ Blue
+3 V3+ Green
+2 V2+ Violet
Ecell value and its relation to vanadium reduction
● Vanadium can be reduced from an oxidation state of +5 all the way +2 via reduction
with zinc in acidic conditions. The Ecell values are given below for the reduction steps:
● Colour changes from yellow —> blue —> green —>
violet
● VO3- (yellow) is reduced to VO2+ (green) because
○ the E value of half-cell 5 is more negative than that of
half-cell 4
○ therefore a positive Ecell value
● VO2+ is then reduced to V3+ (blue) because
○ E value of half-cell 5 is more negative than that of
half-cell 3
○ therefore a positive Ecell value
3+
● V is then reduced to V2+ (violet) because
○ E value of half-cell 5 is more negative than of half-cell 2
○ therefore a positive Ecell value
● The reduction will stop at V2+ because
○ E value of half-cell 5 is less negative than that of half-cell
1
○ therefore a negative Ecell value
20. Understand, in terms of the relevant E values, that the
dichromate(VI) ion, Cr2O72-
A. Can be reduced to Cr3+ and Cr2+ ions using zinc in acidic
conditions
B. Can be produced by the oxidation of Cr3+ ions using
hydrogen peroxide in alkaline conditions (followed by
acidification)
21. Know that the dichromate(VI) ion, Cr2O72- can be converted
into chromate(VI) ions as a result of the equilibrium
Cr2O72- + H2O ⇌ 2CrO42- +2H+
Chromium
● The most stable oxidation states of chromium are +6, +3 and + 2, found in
the species Cr2O72-, Cr3+ and Cr2+ respectively. These can be
interconverted by oxidation and reduction reactions.
● Cr2O72- can be reduced to Cr3+ and Cr2+ ions by reduction with zinc in
acidic conditions.
From chromium +6 to +3 to +2
● Reduction of chromium(VI) by zinc in acidic conditions. The equation is as follows:
● Since the E value for half-equation 1 is more negative than the E value for
half-equation 2. Zn is electron releasing with respect to Cr 2O72-, and therefore the
reaction is thermodynamically feasible.
From chromium +6 to +3 to +2 (Continued…)
● Reduction of chromium(III) by zinc in acidic conditions. The equation is as follows:
● Since the E value for half-equation 1 is more negative than the E value for
half-equation 2. Zn is electron releasing with respect to Cr 3+, and therefore the
reaction is thermodynamically feasible.
From chromium to +3 to +6
● Oxidation of chromium(III) by hydrogen peroxide in alkaline conditions is:
● Since the E value for half-equation 3 is more negative than the E value
for half-equation 4. Cr(OH)3 is electron releasing with respect to H2O2, and
therefore the reaction is thermodynamically feasible.
From chromium to +3 to +6 (Continued…)
● CrO42- is converted to Cr2O72- by acidification. This occurs because there is
an equilibrium between the two chromium(VI)-containing species:
● The oxidation state of vanadium is first reduced from +5 to +4. It is then reformed to its
original oxidation state, showing it has acted as a catalyst for the reaction
29. Understand how a catalytic converter decreases
carbon monoxide and nitrogen monoxide emissions from
internal combustion engines by:
A. Adsorption of CO and NO molecules onto the surface
of the catalyst, resulting in the weakening of bonds
and chemical reaction
B. Desorption of CO2 and N2 product molecules from the
surface of the catalyst
Adsorption
● A solid catalyst works by adsorbing molecules onto an active site on the surface of the
catalyst. These active sites increase the proximity of molecules and weaken the covalent
bonds in the molecules so that reactions occur more easily. This increases the rate of reaction.
● Adsorption occurs inside catalytic converters where carbon and nitrogen monoxide adsorb
onto the surface of the catalyst. This weaken their bonds and allow reactions to occur. As a
result, CO2 and N2 are desorbed from the catalyst
30. Know that a homogeneous catalyst is in the same
phase as the reactants and appreciate that the catalysed
reaction will proceed via an intermediate species
31. Understand the role of Fe2+ ions in catalysing the
reaction between I- and S2O82- ions
32. Know the role of Mn2+ ions in auto catalysing the
- 2-
reaction between MnO4 and C2O4 ions
Homogeneous Catalyst
● Homogeneous catalysts are in the same phase to the species in the
reaction.
○ An example of this is the reaction between S2O82- ions and I- ions where Fe2+ is used as a
catalyst. Without a catalyst, these negative ions would naturally repel each other and
would never react
Homogeneous catalyst (Continued…)
● The catalyst works by combining with
the reactants to produce a reactive
intermediate.
● This changes the reaction pathway
since the enthalpy change of the
formation of the intermediate is
much lower than the enthalpy
change of the original reaction.
● Thus, the activation energy is lower
so the reaction is more feasible.
Autocatalysis
● In some reactions, one of the products can act as a catalyst for the reaction.
● An example of this is the redox reaction between MnO4- ions and C2O42- ions in
acidic conditions, where the Mn2+ ions produced act as a catalyst for the
reaction.
● A small amount of initial heating is required in order to produce some Mn 2+ ions for
autocatalysis. Following this, the rate of reaction increases on its own without further heating.
Exam Questions
Exam Question 1
A precipitate of copper(II) hydroxide dissolves in aqueous ammonia. What is
the formula of the complex ion formed?
A. [Cu(NH3)2]2+
B. [Cu(NH3)4]2+
C. [Cu(NH3)6]2+
D. [Cu(NH3)4(H2O)2]2+
Exam Question 1: Answer
A precipitate of copper(II) hydroxide dissolves in aqueous ammonia. What is
the formula of the complex ion formed?
A. [Cu(NH3)2]2+
B. [Cu(NH3)4]2+
C. [Cu(NH3)6]2+
D. [Cu(NH3)4(H2O)2]2+
Exam Question 2
What is the electronic configuration of the iron cation that can form the
complex ion [Fe(CN)6]4-? [The cyanide ligand has the formula CN-]
A. TiO
B. TiO2
C. K3TiF6
D. K2TiO4
Exam Question 3: Answer
Titanium has the electronic configuration of 1s22s23s23p63d24s2. Which of the
following compounds is unlikely to exist?
A. TiO Answer
B. TiO2 ● Titanium can only lose between 1 to 4 electrons since
C. K3TiF6 they have a configuration of 3d2 and 4s2. It would be
very difficult to lose electrons further from a 3p6
D. K2TiO4 subshell.
● The oxidation number for Ti in:
○ TiO is +2
○ TiO2 is +4
○ K3TiF6 is +3
Exam Question 4
Why is the hexaaquacopper(II) ion, [Cu(H2O)6]2+ blue?
A. The water ligands split the p-orbital energies and p-p electron transitions
emit blue light
B. The water ligands split the d-orbital energies and d-d electron transition
absorbs all but blue light
C. The water ligands split the p-orbital energies and p-p electron transitions
absorb all but blue light
D. The water ligands split the d-orbital energies and d-d electron transitions
emit blue light.
Exam Question 4: Answer
Why is the hexaaquacopper(II) ion, [Cu(H2O)6]2+ blue?
A. The water ligands split the p-orbital energies and p-p electron transitions
emit blue light
B. The water ligands split the d-orbital energies and d-d electron transition
absorbs all but blue light
C. The water ligands split the p-orbital energies and p-p electron transitions
absorb all but blue light
D. The water ligands split the d-orbital energies and d-d electron transitions
emit blue light.
Exam Question 5
Scandium and titanium are both d-block elements, but only titanium is a transition metal
A. Complete the electronic configuration of each of these ions
Sc3+ 1s22s22p6…
Ti3+ 1s22s22p6…
B. Explain why titanium is a transition metal, but scandium is not
C. What is the oxidation number of the d-block element in each of these compounds?
Sc(OH)3…
CaTiO3…
Exam Question 5: Answer
Scandium and titanium are both d-block elements, but only titanium is a transition metal
Sc3+ 1s22s22p6…3s23p6
Ti3+ 1s22s22p6…3s33p63d1
Sc(OH)3… +3
CaTiO3… +4
Exam Question 6
1. What is the meaning of the term ‘ligand’?
2. Give the formula of the complex with the name tetraaquadihydroxoiron(II)
3. Give the name of the complex with the formula [CoCl4]2-
4. The arrangement of d-electrons in the complex with the formula [Cr(H2O)6]3+
can be represented using this diagram. Explain, with reference to this diagram,
why a solution containing this complex is coloured.
Exam Question 6: Answer
1. What is the meaning of the term ‘ligand’?
● A species with a lone pair of electrons that forms a dative bond with a metal ion
2. Give the formula of the complex with the name tetraaquadihydroxoiron(II)
● [Fe(H2O)4(OH)2]
3. Give the name of the complex with the formula [CoCl4]2-
●4.
Tetrachlorocobaltate(II)
The arrangement of d-electrons in the complex with the formula [Cr(H2O)6]3+ can be represented using this diagram. Explain, with reference to this diagram, why a solution containing this complex is coloured.
Exam Question 6: Answer
1. What is the meaning of the term ‘ligand’?
2. Give the formula of the complex with the name tetraaquadihydroxoiron(II)
3. Give the name of the complex with the formula [CoCl4]2-