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A-level Chemistry: 3.2.5 Transition Metals Part 2

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This flashcard set covers key concepts in redox titrations involving potassium manganate(VII) and iron(II) ions, including reaction conditions, indicators, and common errors. It also explores ligand substitution reactions and coordination chemistry of transition metal complexes, with emphasis on electron configurations and shape prediction limitations.

Ligand Substitution

If ligands are ____, they'll be a change in co-ordination number and shape

If ligands are different sizes, they'll be a change in co ordination number and shape

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Key Terms

Term
Definition

Ligand Substitution

If ligands are ____, they'll be a change in co-ordination number and shape

If ligands are different sizes, they'll be a change in co ordination number and shape

Ligand substitution reactions can be easily reversed. State when they can't be.


When new complex ion is more stable than old one


Give 2 examples of when ligand substitution reactions can't be easily reversed

  • If new ligands form stronger bonds with central metal ion than old ligands did

  • Multidentate ligands form more stable complex...

Explain why enthaply change for a ligand substitution reaction is usually very small

When ligand exchange reaction occurs, strength of co-ordinate bonds broken is often very similar to strength of new co-ordinate bonds being made

Why is this reaction considered irreversible when it is actually reversible?

  • Equilibrium lies so far to the right

  • [Ni(NH2CH2CH2NH2)3]2+ is much more stable than [Ni(NH3)6]2+

What explains why multidentate ligands always form much more stable complexes than monodenate ligands?

The chelate effect

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TermDefinition

Ligand Substitution

If ligands are ____, they'll be a change in co-ordination number and shape

If ligands are different sizes, they'll be a change in co ordination number and shape

Ligand substitution reactions can be easily reversed. State when they can't be.


When new complex ion is more stable than old one


Give 2 examples of when ligand substitution reactions can't be easily reversed

  • If new ligands form stronger bonds with central metal ion than old ligands did

  • Multidentate ligands form more stable complexes than monodentate ligands

Explain why enthaply change for a ligand substitution reaction is usually very small

When ligand exchange reaction occurs, strength of co-ordinate bonds broken is often very similar to strength of new co-ordinate bonds being made

Why is this reaction considered irreversible when it is actually reversible?

  • Equilibrium lies so far to the right

  • [Ni(NH2CH2CH2NH2)3]2+ is much more stable than [Ni(NH3)6]2+

What explains why multidentate ligands always form much more stable complexes than monodenate ligands?

The chelate effect

Explain what the chelate effect is

  • When monodentate ligands are substitued with bidentate/multidentate ligands, the no. of particles in solution ↑

  • More particles = greater entropy

  • Reactions that result in greater entropy are more likely to occur

Difficult to reverse these reactions ∵ reversing = decrease in entropy

Transition metals can exists in ___ ______ _____

variable oxidation states

Describe how vanadium(V) ions can be reduced

By adding them to zinc metal in an acidic solution

Write the equation for when VO2+(aq) reacts with Zn(s)

Write the equation for when VO2+(aq) reacts with Zn(s)


Write the equation for when V3+(aq) reacts with Zn(s)


What does the redox potential of ion/atom tell you?

How easily the ion/atom is reduced to lower oxidation state

(same as electrode potentials)

Larger redox potential, less ion will be & more likely
it's to be
_____

Larger redox potential, less stable ion will be & more likely it's to be reduced

Redox potential of an ion _ always be same as its standard electrode potential

WON'T

What is the redox potential for a transition metal ion, when it changes from a higher to a lower oxidation state, influenced by?

  • pH

  • ligand

Explain how different ligands affect redox potentials (& make them differ from standard electrode potentials)

  • Standard electrode potentials are measured in aqueous solution = aqueous ions will be surrounded by water ligands

  • Different ligands may make redox potential larger or smaller depending on how well they bind to a metal ion in particular oxidation state

Explain how different pHs affect redox potentials

  • Some ions need H+ to be present in order to be reduced

  • Others release OH- ions into solution when they are reduced

  • pH of solution affects size of redox potential for these reactions

  • Redox potentials will be large in more acidic solutions, making ion more easily reduced

What reaction does Tollens' reagent use to distinguish between aldehydes and ketones? State the equation

Tollens' reagent reacts with aldehydes to form a silver mirror, but does not react with ketones.

Reaction equation: RCHO + 2[Ag(NH₃)₂]⁺ + 3OH⁻ → RCOO⁻ + 2Ag(s) + 4NH₃ + 2H₂O

Describe how Tollens' reagent is prepared

Add ammonia solution to silver nitrate solution to form colourless solution containing complex ion [Ag(NH3)2]+

Describe what happens when aldehyde is added to Tollens' reagent

  • Tollens' reagent reacts to give silver mirror on inside of test tube

  • Aldehyde is oxidised to carboxylic acid, Ag+ ions are reduced to silver metal

Write the equation for when Tollen's reagent reacts with an aldehyde (RCHO)

RCHO + 2[Ag(NH₃)₂]⁺ + 3OH⁻ → RCOO⁻ + 2Ag(s) + 4NH₃ + 2H₂O

Titrations using Transition Element Ions are _ Titrations

Redox

Titrations with Transition Metals

What can you use the titrations to find out?

How much oxidising agent is needed to exactly react with a quantity of reducing agent

Titrations with Transition Metals

Suggest an oxidising agent you can use

aqueous potassium manganate(VII)

Titrations with Transition Metals

Suggest why aqueous potassium manganate(VII) is used as an oxidising agent

  • Contains purple manganate(VII) ions

  • Strong acidic conditions are needed for manganate(VII) ions to be reduced

Titrations with Transition Metals

Suggest 2 reducing agents you can use

  • aqueous Fe2+ ions

  • aqueous C2O42- ion

Titrations with Transition Metals

Describe a method

  1. Measure quantity of reducing agent using a pipette & add to conical flask

  2. Using a measuring cylinder, add 20 cm3 of dilute sulfuric acid to flask

    • This is in excess

  3. Add oxidising agent to reducing agent using burette

    • Swirling conical flask

  4. Oxidising agent added reacts with reducing agent

    • Reaction continues until all reducing agent is used up

    • Next drop added = mixture becomes colour of oxidising agent

  5. Stop when mixture in flask becomes tainted with colour of oxidising agent (end point) and record volume of oxidising agent added

    • Rough titration

  6. Do some accurate titrations

    • Do a few until you get 2 or more reading are within 0.10 cm3 of each other

Why do transition metals and their compounds make good
catalysts?

  • ∵ change oxidation states by gaining or losing electrons within d orbitals

  • ∴ can transfer electrons to speed up reactions

What is the catalyst used in the Contact Process to make sulfuric acid?

Vanadium(V) oxide

Why is vanadium(V) oxide used as a catalyst in the Contact Process?

  • ∵ it's able to oxidise SO2 to SO3 and it can be reduced to vanadium(IV) oxide

  • & then it's oxidised back to vanadium(V) oxide by oxygen to react all over again

Describe and state the 1st equation that occurs in the Contact Process. Include state symbols.

Describe and state the 2nd equation that occurs in the Contact Process. Include state symbols.

What are heterogenous catalyst?

A catalyst that's in a different phase from the reactants

i.e. in a different physical state

Where do reactions occur on in heterogenous catalysts?

Occur on on active sites on surface of heterogenous catalyst

Explain why increasing SA of a catalyst increases the rate of a reaction

Increases no. of molecules that can react at same time

What are often used to make the area of catalyst as large as possible?

Support mediums

Explain how support mediums help to minimise the cost of a reaction?

∵ only small coating of catalyst is needed to provide large SA

Name 2 heterogeneous catalysts

  • Iron in Haber Process (for making ammonia)

  • Vanadium(V) oxide in Contact Process

State the overall equation for the Haber Process. Include the catalyst and state symbols.

N₂(g) + 3H₂(g) ⇌ 2NH₃(g)  [Fe catalyst]

State the overall equation for the Contact Process. Include the catalyst and state symbols.

2SO₂(g) + O₂(g) ⇌ 2SO₃(g)  [V₂O₅ catalyst]

How do heterogenous catalyst work?

By adsorbing reactants onto active sites located on their surfaces

Describe catalyst poisoning

Impurities (in reaction mixture) bind to catalyst's surface and block reactants from being adsorbed

Explain how catalyst poisoning slows down the rate of a reaction

Catalyst poisoning reduces SA of catalyst available to reactants

Explain why catalyst poisoning increases cost of chemical process

  • ∵ less product can made in certain time or with a certain amount of energy

  • Catalysts may need replacing or regenerated = costs money

Name a substance that poisons the iron catalyst in the Haber Process

sulfur

Explain how sulfur poisons the iron catalyst in the Haber Process

  • Hydrogen in Haber process is produced from methane

  • Methane is obtained from natural gas - contains impurities like sulfur compounds

  • Any sulfur not removed is adsorbed onto iron forming iron sulfide = stops iron catalysing reaction efficiently

What are homogenous catalysts?

Catalysts that are in the same physical state as reactants

Usually the homogenous catalyst is an _ catalyst for a reaction between 2 aqueous solutions

aqueous

Describe how homogenous catalysts work

Work by combining with reactants to form an intermediate species which reacts to form products and re-form the catalyst

Why does the enthalpy profile for a homogeneously catalysed reaction contain 2 humps?

2 steps in reaction

Activation energy needed to form intermediates is lower than…

that needed to make products directly from reactants

______ reaction between iodide ions and peroxodisulfate (S2O82-) ions take place ________

Redox reaction between iodide ions and peroxodisulfate (S2O82-) ions take place very slowly

Why does the redox reaction between iodide ions and peroxodisulfate (S2O82-) ions take place very slowly?

  • ∵ both ions negatively charged

  • Ions repel each other & so its unlikely they'll collide and react

State the equation for when iodide ions and peroxodisulfate ions react together


Name a catalyst that speeds up the reaction between iodide ions and peroxodisulfate ions

Fe2+ ions

Explain why adding Fe2+ ions speeds up the reaction between iodide ions and peroxodisulfate ions

∵ each stage of reaction involves a positive and a negative ion = no repulsion

Describe and state the 1st equation that occurs when Fe2+ ions is added to iodide ions and peroxodisulfate ions. Include state symbols.

Fe2+ are oxidised to Fe3+ ions by S2O82- ions

Describe and state the 2nd equation that occurs when Fe2+ ions is added to iodide ions and peroxodisulfate ions. Include state symbols.

Newly formed intermediate Fe3+ ions now easily oxidise the I- ions to iodine & catalyst is regenerated

Mn2+ ions _ the reaction between C2O42– and MnO4–

Mn2+ ions autocatalyse the reaction between C2O42– and MnO4–

Explain what it meant by an autocatalysis reaction

  • A product of a reaction that acts as a catalyst for the reaction

  • Means that as a reaction progresses and the amount of product increases = reaction speeds up

Write the overall equation for when Mn2+ ions autocatalyse the reaction between C2O42– and MnO4–

2MnO₄⁻(aq) + 5C₂O₄²⁻(aq) + 16H⁺(aq) → 2Mn²⁺(aq) + 10CO₂(g) + 8H₂O(l)

Describe and state the 1st equation that occurs when Mn2+ ions is added to C2O42– and MnO4–. Include state symbols.

Mn2+ oxidised to Mn3+ by MnO4- ions

Describe and state the 2nd equation that occurs when Mn2+ ions is added to C2O42– and MnO4–. Include state symbols.

Mn3+ reduced to Mn2+ (re-form catalyst ions) by C2O42- ions

Draw [Cr(en)3]3+ & state its shape and co-ordination number

Octahedral & 6

Draw [Co(en)2Cl2]+ & state its shape and co-ordination number

Octahedral & 6

Draw two geometric isomers of [NiCl2(H2O)4]

Draw two geometric isomers of square planar complex [PtCl2(NH3)2]

cis isomer = cisplatin

Draw the two optical isomers of octahedral complex [Fe(C2O4)3]3-

State the charge of :CN- ligand

-1

State the charge of :OH- ligand

-1

Draw the structure of the ethanedioate ion, C2O42-. Explain how this ion is able to act as a ligand. (2)

lone pair(s) on O– / O

Draw the structure of the 1,2-diaminoethane (en)

Give an example of complete ligand substitution when the co-ordination number and shape doesn't change. Include the colour change & shape.

[Cu(H₂O)₆]²⁺ (pale blue, octahedral) → [Cu(NH₃)₆]²⁺ (deep blue, octahedral)

Give an example of incomplete ligand substitution when the co-ordination number and shape doesn't change. Include the colour change & shape.

[Cu(H₂O)₆]²⁺ (pale blue, octahedral) → [Cu(H₂O)₄(NH₃)₂]²⁺ (deep blue, octahedral)

Give an example of complete ligand substitution when the co-ordination number and shape changes. Include the colour change & shape.

[Cu(H₂O)₆]²⁺ (pale blue, octahedral) → [CuCl₄]²⁻ (yellow-green, tetrahedral)

Ligand Substitution

Write an equation where a monodentate ligand replaces a monodentate ligand e.g. with [Fe(H2O)6]3+ with CN-

[Fe(H₂O)₆]³⁺ + 6CN⁻ → [Fe(CN)₆]³⁻ + 6H₂O

Ligand Substitution

Write an equation where a bidentate ligand replaces a monodentate ligand e.g. with [Cu(H2O)6]2+ and ethane-1,2-diamine

[Cu(H₂O)₆]²⁺ + 3en → [Cu(en)₃]²⁺ + 6H₂O

Ligand Substitution

Write an equation where a multidentate ligand (that's not a bidentate ligand) replaces a monodentate ligand e.g. with [Cr(NH3)6]3+

[Cr(NH₃)₆]³⁺ + EDTA⁴⁻ → [Cr(EDTA)]⁻ + 6NH₃

When using potassium manganate(VII) in redox titrations with iron(II) ions it is essential that the reaction mixture is acidified. Explain why. (1)

ensures all MnO4- reacts to form Mn2+ / stop formation of MnO2 / becomes colourless

Explain why an indicator is not needed in a redox titration with e.g. potassium manganate(VII) & iron(II) ions (1)

It's self-indicating

Suggest one reason why the colour of potassium manganate(VII) can be a source of error when using a volumetric flask to prepare a standard solution (1)


Difficult to see meniscus


State the equation for when dichromate(VI) ions react with iron(II) ions


Cr2O72- + 14H+ + 6Fe2+ → 2Cr3+ + 7H2O + 6Fe3+


Suggest one reason why electron pair repulsion theory cannot be used to predict the shape of the [CoCl4]2- ion (1)

Too many electrons in d sub-shell

The redox reaction between acidified potassium manganate(VII) and sodium ethanedioate: Sketch a graph to show how the concentration of MnO4− ions varies with time in this reaction. Explain the shape of the graph. (4)

  • Starts slowly with low rate

    • ∵ -ve ions collide so high Ea​

  • Rate increases as autocatalyst (Mn2+) forms

  • Rate decreases as concentration of MnO4− ions / reactant(s) decreases (OR reactants are being used up)

When the complex ion [Cu(NH3)4(H2O)2]2+ reacts with 1,2-diaminoethane, the enthaply change is appromimately zero. Suggest why. (2)

  • Cu-N bonds formed have similar enthaply/energy to Cu-N bonds broken

  • And same no. of bonds broken & made

State the colour change for when iron(II) ethanedioate is titrated against potassium managante(VII) (burette)

Colourless to pale pink

∵ tiny excess of MnO4- (manganate(VII)) ions present

Give 2 reasons why the use of a spectrometer is the most appropriate method for measuring the concentration of coloured ions (2)

  • Rapid determination of concentrations

  • Doesn't use up any of the reagent

Write an equation for the reaction that occurs between an aqueous solution of aluminium chloride and an excess of aqueous diaminoethane. Describe the appearance of the aluminium-containing reaction product. (3)

2[Al(H2O)6]3+ + 3H2NCH2CH2NH2 → 2Al(H2O)3(OH)3 + 3[H3NCH2CH2NH3]2+

White precipitate