Transition Metals Flashcards

1
Q

Transition metal

A

Any of the set of metallic elements occupying the central d block of the periodic table

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2
Q

What is a transition metal defined as?

A

An element that has an incomplete d subshell either in the element or in one of its ions

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3
Q

What are the common properties of the transition metals (period 4)?

A
  • they form complex ions
  • their ions are coloured
  • they show catalytic activity
  • their oxidation states are variable
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4
Q

Why is scandium not considered a transition metal?

A

The normal scandium ion formed has no electrons in the d orbital

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5
Q

Why is zinc not considered a transition metal?

A

Normal zinc ions have a complete d subshell

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6
Q

Complex ions with water ligands are called

A

Metal-aqua ions. They may be represented as Cu^2+ (aq) for example

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7
Q

From Mn^2+ to Cu^2+ the reactivity of divalent (2+) metal-aqua ions

A

Increases

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8
Q

Complete ligand substitution

A

All ligands are replaced

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9
Q

Incomplete ligand substitution

A

Only some ligands are replaced

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10
Q

Is the substitution of a Cu^2+ aqua complex with ammonia complete or incomplete?

A

Incomplete because the complex ion with four ammonia and two water molecules is energetically more stable than the complexes with six water or six ammonia molecules

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11
Q

Is the reaction of ligand substitution reversible or irreversible?

A

Reversible

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12
Q

Why is there a change in coordination number when halide ions undergo ligand substitution with complexes containing water and/or ammonia ligands only?

A

Halide ions are larger than water and ammonia ligands, therefore the metal ions can only coordinate 4 halide ions. Coordination number changes from 6 to 4

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13
Q

Give two examples of bidentate ligands

A

Ethylenediamine (H2NCH2CH2NH2) and ethanedioate (oxalate) (C2O4)^-

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14
Q

Give two examples of multidentate ligands

A

Ethylenediaminetetraacetate (EDTA^4-) and sarcophagine (SAR)

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15
Q

What are multidentate ligands also known as? Why?

A

Chelating agents as they form very stable complexes with transition metal ions

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16
Q

What is a ligand?

A

A molecule or ion that can form a coordinate bond to a metal by donating a pair of electrons

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17
Q

A complex ion is

A

A metal ion surround by ligands

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18
Q

Give an example of a linear complex

A

[Ag(NH3)2]^+, complex formed in Tollen’s reagent

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19
Q

Why are certain colours produced in transition metal compounds?

A

Some wavelengths of light are absorbed and others are reflected or transmitted

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20
Q

Quanta

A

Single packets of energy in light photons

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21
Q

Frequency

A

The number of wavelengths of light passing a particular point in one second

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22
Q

When light is absorbed, electrons in the d orbital…

A

… move from the ground state to an excited state

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23
Q

When light is absorbed, what factors affect the value of ΔE?

A
  • the ligand size
  • the strength of the ligand-metal bond in the complex
  • the shape of the complex
  • the coordination number
  • the oxidation state of the metal in the central ion
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24
Q

The colour of a transition metal complex ion is due to

A

the absorption of light with energy that can excite an electron from a 3d orbital of lower energy to one of higher energy

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25
When transition metal atoms form complex ions, what happens to the d orbital?
It is 'split' into two levels, one of higher energy and one of lower energy. This is because the electrons in the ligand repel the electrons in the 3d orbitals which are in close proximity.
26
What are strong-field ligands?
Ones that induce a large ΔE, e.g. CN^-, CO and P(C6H5)3
27
What are weak-field ligands?
Those that induce a small ΔΕ, e.g. NH3, H2O and Cl^-
28
What does the amount of light absorbed by a coloured solution depend on?
- the nature of the ion (relates to ΔE) - the concentration of the solution - the distance the light has to travel through the solution (path length)
29
What effect does a greater concentration have on the intensity of colour in a solution?
The colour will be more intense as there are more ions present in a given volume, meaning more will interact with the light
30
What effect does a longer path length have on the intensity of colour in a solution?
Colour will be more intense as the light has to travel a greater distance, meaning more ions will interact with the light
31
Spectrophotometer
An instrument used to carry out spectroscopy - the analysis of a compound by detecting its response to electromagnetic radiation
32
Colorimeter
An instrument that measures the absorption of a range of radiation
33
Complementary colour
A colour that a sample will absorb most
34
Th concentration of coloured ions in solution can be determined by
using a colorimeter or spectrophotometer. The path length and nature of the coloured ion must be kept constant, the concentration can be determined by comparing to standard solutions
35
Oxidation state
The charge that an element would have if it were totally ionically bonded. For an ion, it is the charge on the ion. In a covalent compound, it is the theoretical number assigned to each at atom in a molecule if it were an ionic compound.
36
What does the ease of oxidation and redox potential for a transition metal depend on?
pH and nature of the ligand
37
What species is reduced when distinguishing between aldehydes and ketones?
[Ag(NH3)2]^+ (Tollens' reagent) is reduced to metallic silver
38
In redox titrations with potassium manganate to estimate the number of iron(II) ions in solution, why is hydrochloric acid not used when acidifying the reaction mixture?
It can be oxidised to chlorine by manganate(VII) ions
39
In redox titrations with potassium manganate to estimate the number of iron(II) ions in solution, why is nitric acid not used when acidifying the reaction mixture?
It is an oxidising agent and may oxidised the substance being analysed
40
In redox titrations with potassium manganate to estimate the number of iron(II) ions in solution, why is conc. sulphuric acid not used when acidifying the reaction mixture?
It may oxidised the substance being analysed
41
In redox titrations with potassium manganate to estimate the number of iron(II) ions in solution, why is ethanoic acid not used when acidifying the reaction mixture?
It is a weak acid, so the concentration of hydrogen ions will be insufficient
42
What is the colour change at the end point of the titration between dichromate(VI) ions and iron(II) ions
From orange to blue/green
43
What is the general sequence for redox titration calculations?
1 - write the half equations for oxidant and reductant 2- deduce the equation for the overall reaction 3 - calculate the number of moles of manganate or dichromate used 4 - calculate the ratio of moles of oxidant to moles of reductant from the redox equation 5 - calculate the number of moles in the sample solution of reductant 6 - calculate the number of moles in the original solution of reductant 7 - determine either the concentration of the original solution or the percentage of reductant in a known quantity of sample
44
Adsorption
The process in which (usually) a gas bonds to the surface of a solid catalyst. The gas (or its products) is released after reaction occurs
45
Desorption
The process in which a substance (usually a gas) is released from the surface of a solid catalyst following reaction
46
Why can adsorption of a reactant onto a metal surface speed up a reaction?
- It weakens the bonds within the reactant molecules, reducing the activation energy. - It can cause a reactant molecules to break up into more reactive fragments, again reducing the activation energy. - It can hold a reactant in a particular position, increasing the chance of a favourable collision. - It can give a higher concentration of one reactant on the catalyst surface, increasing the chance of a favourable collision with another reactant
47
Why is tungsten rarely used as a catalyst in heterogeneous catalysis?
It forms a very strong bond with some molecules, meaning that the product molecule will not be released and the reaction will not proceed
48
What are two ways to maximise the surface area of a catalyst in heterogeneous catalysis?
- use a support medium, ADD TO - use a fluidised bed, gases are blown through a very fine powder, powder 'floats' separating catalyst particles, so all surface area is available for reactions
49
In heterogeneous catalysis, what is catalyst poisoning?
When impurities are absorbed onto the surface, blocking active sites and reducing the effectiveness of the catalyst; this has a cost implication
50
How is catalyst poisoning prevented in catalytic converters?
Aluminium oxide is mixed with the catalyst. The aluminium oxide 'stores' the sulphur oxides under oxidising (running) conditions, and converts them to hydrogen sulphide under reducing accelerating conditions. This removes the sulphur periodically, so that it does not permanently poison the catalyst.
51
What metals do catalytic converters contain?
A mixture of the metals palladium, platinum and rhodium, coated into a cerium oxide. These remove the unwanted products of combustion
52
What are the conditions used in industry for the production of methanol?
A mixture of H and CO in a 2:1 ratio is passed over the catalyst chromium(III) oxide, Cr2O3, under high pressure at high temperature
53
Why are catalysts used in industrial processes?
To increase the rate of reaction, allowing a much lower temperature to be used, yet maintaining sufficient output for the process to be cost-effective
54
Haber process
Manufacturing process for the production of ammonia from nitrogen and hydrogen
55
What is the catalyst used in the Haber process?
Iron is used as the heterogeneous catalyst. It is mixed with aluminium oxide and potassium oxide, which act as promoters. These are present in smaller amounts than the iron and improve the efficiency of the catalyst.
56
The hydrogen used for the Haber process is obtained from methane, so trace amounts of steam and carbon monoxide are found as impurities in the hydrogen. How is the carbon monoxide removed?
By heating with an excess of steam in a two-stage process, first with an iron oxide catalyst and then with a zinc/copper catalyst. The products are carbon dioxide, which is easier to remove from the mixture, and hydrogen, which is used in the process.
57
The contact process
The industrial process used to make sulphuric acid from sulphur, oxygen and water
58
In the contact process, why is a vanadium(V) pentoxide catalyst, V2O5 used instead of platinum?
V2O5 is cheaper and less prone to poisoning by impurities
59
Write out the two equations for the reactions that occur during the contact process
V2O5(s) + SO2(g) → 2VO2(s) + SO3(g) 4VO2(s) + O2(g) → 2V2O5(g)
60
What is a heterogeneous catalyst?
A catalyst that is in a different phase to the reactants
61
What is a homogenous catalyst?
A catalyst that is in the same phase as the reactants
62
Autocatalysis
The ability of one of the products of a reaction to catalyse the reaction producing it. In autocatalysis the initial reaction rate increases, as more catalyst is produced
63
What are the equations showing how Fe^2+ ions catalyse the reaction between I^- and S2O8^2-?
2Fe^2+ + S2O8^2- → 2Fe^3+ + 2SO4^- 2Fe^3+ + 2I^- → 2Fe^2+ + I2
64
Why is the oxidation of iodide ions by peroxodisulphate ions slow, despite it being energetically favourable?
Both ions are negatively charged, so unlikely to make successful collisions with each other. This is why iron(II) ions are used as a catalyst
65
Homogeneous catalysis proceeds via an
intermediate (or intermediates)
66
Transition metal ions taking part in homogeneous catalysis usually go through a
temporary change in oxidation state