15: Transition Metals Flashcards
What are d-block elements?
Element in the d-block
Found in the middle of the periodic table
What is a transition metal?
D-block elements that can form one or more stable ions with incompletely filled d-orbitals
What is in the d-subshell?
5 orbitals that hold 10 electrons
Which period 4 d-block elements are transition metals?
All but scandium and zinc
What are the notable differences in the normal electron configuration in period 4?
Copper and chromium
How do electrons fill and leave the period 4 d-block elements?
Fills and leaves 4s before 3d
What is the electron configuration of Chromium?
[Ar] 3d5 4s1
What is the electron configuration of Copper?
[Ar] 3d10 4s1
What is [Ar]?
The electron config of Argon
1s2 2s2 2p6 3s2 3p6
What is the electron confid of Ti, Ti2+ and Ti3+ ?
Proton number = 22
Ti: [Ar] 3d2 4s2
Ti2+: [Ar] 3d2
Ti3+: [Ar] 3d1
Why is scandium not a transition metal?
Only forms Sc3+ which has an empty d subshell
What is the electron config of Sc and Sc3+?
Sc: [Ar] 3d1 4s2
Sc3: [Ar]
Why is zinc not a transition metal?
Only forms Zn2+ which has a full d subshell
What is the electron config of Zn and Zn2+?
Zn: [Ar] 3d10 4s2
Zn2+: [Ar] 3d10
How many oxidation states do transition metals typically have?
Multiple
What is requireed to form a compound or complex with an ion?
Energy out when it forms must be greater than energy to remove outer electrons to form the ion (ionisation energy)
Why can transition metals form ions with different oxidation numbers?
4s and 3d are at similar energy levels
Not large increase in ionisation energy to remove successive electrons
Therefore multiple can be removed
How does ionic charge affect energy released when ions form a complex or compound?
Greater the ionic charge the more energy is released when a compound or complex forms
What are the energy factor to take into consideration with larger ionic charge?
Greater energy given out when compound and complex forms
More energy to remove outer electrons, energy released counteracts this
What is a complex?
Complex ion is a metal ion surrounded by dative covaltently coordinately bonded ligands
What is a dative covalent bond?
Covalent bond in which both electrons in the shared pair come from the same atom
What is a ligand?
Atom, ion or molecule that donates a pair of electrons to a central metal atom or ion
Has at least one lone pair of electrons
Why does a ligand require a lone pair of electrons?
Required for the formation of a dative covalent bond
What is a monodentate ligand?
Ligands which only form one bond to the central metal ion
What is a bidentate ligand?
Ligands that can each form 2 dative covalent bonds with the central metal ion
What is a multi or polydentate ligand?
More than two lone pairs over a molecule that can be used to form dative covalent bonds to the metal ion
What is the overall charge on the complex ion?
Oxidation number of complex
How are the oxidation numbers in a complex calculated?
Oxidation number of metal ion = total oxidation number - sum of charges of ligands
What is the coordination number?
Number of dative covalent bonds formed with the central metal ion in the complex
What are the normal coordination numbers?
4 or 6
When is the coordination number 6?
Ligands are small
H2O, OH-, NH3
When is the coordination number 4?
Larger ligands
Cl-
Why are the ligands as far away from eachother as possible in a complex?
Electrons in dative covalent bonds repel eachother as much as possible
What is the shape seen in a complex with coordination number 6?
Octahedral - 6 bonding pairs
90º bond angle
What is the shape of a complex with a coordination number of 4?
Tetrahedral - 109.5º
OR
Square planar - 90º
Which ligands show cis/trans isomerism?
Octahedral and square planar
What is the cis isomer of a ligand?
Same groups are on the same side
What is the trans isomer of a ligand?
Same groups are oppoisite eachother
What is cis-platin?
Anti-cancer drug
Square planar - two chloride and two ammonia groups
Chloride are on same side, if trans then would not affect cancer cells
What occurs to the 3d subshell when ligands bond to metal ions?
3d orbitals split into two different energy levels
How does the 3d subshell split?
3 orbitals remain at ground state
2 promoted to higher energy level
How much does the 3d subshell split?
Varies depending on the elements involved
What occurs to electrons in the ground state of the split 3d subshell?
Electron absorbs energy of specific frequency to be promoted
Frequency is in visible light
All other frequencies reflected giving colour
How does the frequency of light required to promote change when the excited orbitals have a larger energy gap?
Frequency increases to provide extra energy
What does the energy gap between the split 3d subshell depend on?
Metal ion present
Oxidation number
Ligands
Coordination number
What occurs to give a coloured complex its colour?
Absorbs light of certain frequency for promoting electron
All other frequencies are reflected
Reflected is the colour observed
What is the concept of complementary colours for ligands?
Absorb a certain colour
Complementary colour is the opposite in colour wheel, this is what is seen when all not absored is reflected
What colour does [Cu(H2O)6]2+ turn if it absorbs red light?
Blue solution
What is the colour of compounds with full or empty 3d orbitals?
White or colourless
No energy is absorbed
What occurs when a transition metal ion is dissolved in water?
Transition metal ion forms aqueous complex in solution
Ion surrounded by water ligands
Coloured are easily identifiable
What is the colour of the aqueous complex of V5+ (VO2+)?
Yellow
What is the colour of the aqueous complex of V4+ (VO2+)?
Blue
What is the colour of the aqueous complex of V3+?
Green
What is the colour of the aqueous complex of V2+?
Violet
What is the colour of the aqueous complex of Cr+6 in Cr2O72-?
Orange
What is the colour of the aqueous complex of Cr3+?
Green
What is the colour of the aqueous complex of Fe3+?
Yellow
What is the colour of the aqueous complex of Fe2+?
Pale green
What is the colour of the aqueous complex of Co2+?
Pink
What is the colour of the aqueous complex of Cu2+?
Pale blue
Which oxidation states can vanadium exist as in solution?
+2
+3
+4
+5
What is the equation of the vanadium ion when its oxidation state is +5?
VO2+
What is the equation of the vanadium ion when its oxidation state is +4?
VO2+
What is the ionic half-equation between the +5 and +4 oxidation states of Vanadium?
VO2+ + 2H+ + e- ⇔ VO2+ + H2O
What is the ionic half-equation between the +4 and +3 oxidation states of Vanadium?
VO2+ + 2H+ + e- ⇔ V3+ + H2O
What are they probably going to ask about with vanadium?
Reduction potentials (E) Whether redox reactions occur
What are the common oxidation states of chromium?
+2
+3
+6
What is the colour of the aqueous complex of Cr+6 in CrO4-?
Yellow
What are the +6 Chromium ions said to be?
Good oxidising agents
Easily reduced to Cr3+
What is the colour of the aqueous complex of Cr2+?
Blue
What can be used to reduce dichromate (VI) ions?
Zinc and dilute acid
Reduces Cr3+ to Cr2+
Why does Cr2+ have to be made in an inert environment?
Unstable in air
Unstable as it oxidises straight back to Cr3+ in air
How are Cr3+ ions oxidised to dichromate (VI) ions?
Hydrogen peroxide in an alkaline solution
What does amphoteric mean?
Compound or species which can react as both a base and an acid
What is a feature of chromium (III) hydroxide?
Amphoteric
What happens when you react aqueous chromium 3+ with sodium hydroxide?
[Cr(H2O)6]3+ + 3OH- → [Cr(OH)3(H2O)3] + 3H2O
Green solution → grey-green precipitate
Which is the charge of complexes which are precipitates?
Neutral
What occurs when you react aqueous chromium 3+ with ammonia?
[Cr(H2O)6]3+ + 3NH3 → [Cr(OH)3(H2O)3] + 3NH4+
green solution → grey-green precipitate
What occurs when you react chromium hydroxide precipitate with excess sodium hydroxide?
[Cr(OH)3(H2O)3] + 3OH- → [Cr(OH)6]3- + 3H2O
Grey-green precipitate → dark green solution
What kind of reaction is it when non-excess of NaOH or NH3?
H2O ligands are deprotonated to OH-
What occurs to chromium hydroxide precipitate when acid is added?
[Cr(OH)3(H2O)3] + 3H+ → [Cr(H2O)6]3+
grey-green precipitate → green solution
Protonation
What are the reactions between aqueous chromium 3+ complex and sodium hydroxide or ammonia?
Acid-base reactions
Not ligand exchange
What occurs when excess ammonia is added to the chromium hydroxide precipitate?
[Cr(OH)3(H2O)3] + 6NH3 → [Cr(NH3)6]3+ + 3OH- + 3H2O
Ligand exchange reaction
How is chromium (II) ethanoate formed?
Orange sodium dichromate (VI) is reduced with zinc in acid solution to form green Cr (III) solution and then to blue Cr (II) solution
Sodium ethanoate mixed with solution and chromium(II) ethanoate red precipitate
Has to be done in inert environment
Why does the formation of chromium(II) ethanoate need to be done in an inert environment?
Cr2+ is very easily oxidised
Prevents oxygen from oxidising it
What is the experimental procedure of the production of chromium(II) ethanoate?
Slowly add HCl to a flask with sodium dichromate(VI) and zinc mesh
Once blue colour seen, pinch rubber tube shut so hydrogen cannot escape
Pressure forces Cr2+ through glass tube into flask with sodium dichromate(VI)
Blue solution reacts with sodium ethanoate to form a red precipitate of chromium ethanoate
Filter precipitate and wash with water, then ethanola and ether
All in inert atmosphere
What does zinc mesh do in the production of chromium(II) ethanoate?
Zinc reduces the dichromate(IV) ions
Reacts with acid to produce hydrogen gas which goes into beaker of water
What is ligand exchange?
One ligand which can be swapped for another ligand
Causes colour change
What occurs to the complex in ligand exchange if the ligands are of similar size?
Coordination number and shape doesn’t change
What occurs if a uncharged small ligand is substituted for a larger charged ligand?
Change of coordination
Change of shape
What equilibrium is formed between dichromate(VI) and chromate(VI)?
2CrO42- + 2H+ ⇔ Cr2O72- + H2O
Yellow ⇔ orange
What is the reaction to reduce dichromate(VI) ion using zinc metal?
Cr2O72- + 14H+ + 3Zn → 3Zn2+ + 2Cr3+ + 7H2O
Orange → Green
What is the reaction for Cr3+ to form Cr2+?
2Cr3+ + Zn → Zn2+ + 2Cr2+
Green → Blue
What is the reaction between Cr3+ to form Chromate(VI) ions?
2Cr3+ + 10OH- + 3H2O → 2CrO42- + 8H2O
Green → Yellow
What occurs to the copper aqueous complex form when reacted with Cl-?
[Cu(H2O)6]2+ + 4Cl- → [CuCl4]2- + 6H2O
Pale blue → yellow
What is the colour of the aqueous cobalt solution?
[Co(H2O)6]2+
Pale pink
What is the colour of the copper chloride complex?
[CuCl4]2-
Yellow
What is the colour of aqueous cobalt chloride?
[CoCl4]2-
Blue
What is formed when aqueous copper reacts with excess ammonia?
[Cu(H2O)6]2+ + 4NH3 → [Cu(NH3)4(H2O)2]2+ + 4H2O
Pale blue → Deep blue
Why does carbon monoxide poisoning occur because of ligand exchange?
Carbon monoxide forms strong dative bond with iron in haemoglobin
Prevents the oxygen from bonidng to the iron and hence it cannot be carried
What bonds are broken and formed in ligand exchange?
Dative bonds between ligand and metal ion are broken and formed
What is the enthalpy change in ligand exchange?
Strength of dative bonds broken/formed are of similar strength
Enthalpy change is very small
How do the types of ligands affect the likeliness ligand exchange will occur?
Poly or bi dentate ligands causes increase of particles in complex
This increases entropy in the complex so more likely to occur
What is type of ligand is EDTA?
Hexadentate ligand
What is a metal-aqua ion?
Metal ion complex that only contains water ligands
How can you reverse the deprotonation of ligands?
Acid
What is the reaction between copper aqueous solution and hydroxide ions?
[Cu(H2O)6]2+ + 2OH- → [Cu(OH)2(H2O)4] + 2H2O
Pale blue solution → blue precipitate
What is the reaction between copper aqueous solution and ammonia?
[Cu(H2O)6]2+ + 2NH3 → [Cu(OH)2(H2O)4] + 2NH4+
Pale blue solution → blue precipitate
What is the reaction between copper hydroxide and excess ammonia?
[Cu(OH)2(H2O)4] + 4NH3 → [Cu(NH3)4(H2O)2]2+ + 2OH- + 4H2O
blue precipitate → deep blue solution
What is copper hydroxide?
[Cu(OH)2(H2O)4] or Cu(OH)2 (aq)
Solid precipitate
What is the reaction between the iron (II) aqueous solution and hydroxide?
[Fe(H2O)6]3+ + 3OH- → [Fe(OH)2(H2O)4] + 2H2O
Pale green solution → green precipitate which darkens on standing to orange precipitate
What is the colour of the [Fe(OH)2(H2O)4] precipitate?
Darkens as oxidised by water and oxygen in air to form iron (III) hydroxide
What is the reaction between iron (II) aqueous solution and ammonia?
[Fe(H2O)6]2+ + 2NH3 → [Fe(OH)2(H2O)4] + 2NH4+
What is the reaction between iron (III) aqueous solution and hydroxide?
[Fe(H2O)6]3+ + 3OH- → [Fe(OH)3(H2O)3] + 3H2O
yellow solution → orange precipitate which darkens on standing
What is the reaction between iron (III) aqueous solution and ammonia?
[Fe(H2O)6]3+ + 3NH3 → [Fe(OH)3(H2O)3] + 3NH4+
yellow solution → orange precipitate which darkens on standing
What is the reaction between cobalt (II) aqueous solution and hydroxide?
[Co(H2O)6]2+ + 2OH- → [Co(OH)2(H2O)4] + 2H2O
pale pink solution → blue precipitate which turns brown on standing
What is the reaction between cobalt (II) and ammonia?
NOT excess
[Co(H2O)6]2+ + 2NH3 → [Co(OH)2(H2O)4] + 2NH4+
pale pink solution → blue precipitate which darkens to brown
What is the reaction between cobalt hydroxide and excess ammonia?
[Co(OH)2(H2O)4] + 6NH3 → [Co(NH3)6]2+ + 2OH- + 4H2O
blue or pink precipitate → yellow-brown solution
oxidises on standing to [Co(NH3)6]3+ ions
What is a catalyst?
A catalyst is a substance that speeds up a chemical reaction, but is not consumed by the reaction
Lowers the Ea of a reaction
Why are transition metlas good catalysts?
Change oxidation number by gaining or losing electrons in d-orbitals
Therefore can transfer electrons to speed up reactions
What is a homogenous catalyst?
Catalysts in the same physical state as the reactants
Which phase are homogeneous catalysts usually in?
Aqeuous catalyst for a reaction between two aqueous solutions
How do homogeneous catalysts usually work?
Combines with reactants to form an intermediate species
Intermediate then reacts to form products and reforms the catalyst
Why does the formation of an intermediate whilst using homogeneous catalysts increase the rate of reaction?
Activation energy neeeded to form intermediates (and products from it) is lower than to make products directly
What is autocatalysis?
Reaction is catalysed by one of the products which form
Why is the reaction between iodide (I-) and peroxodisulphate (S2O82-) slow?
Both are negatively charged so they repel each other
Less likely to collide and react
What is a heterogeneous catalyst?
Catalyst in a different phase from the reactants
What are the typical phases when a heterogeneous catalyst is used?
Reactants are gases or in solution
Catalyst is a solid
Where does a reaction occur on a heterogeneous catalyst?
Reaction occurs on the surface of the catalyst
Why are transition metals good heterogeneous catalyst?
Use partially filled d-orbitals to make weak bonds with the reactant molecules
How do heterogeneous catalysts?
Reactant molecules attracted and are adsoped onto the surface on the solid catalyst
Catalyst activates molecules so react more easily, weakens the bonds of the reactant causing it to break and the products to form
Product molecules leave surface of catalyst by desorption
Why is it important that heterogeneous catalysts do not form strong bonds with the reactants?
Prevents the reactants or products formed staying bound to the catalyst
This would mean it cannot be reformed or reused
Why does an aqueous complex react with a solution of EDTA4- ions?
EDTA is hexadentate, water is monodentate
Increases number of particles as EDTA complex forms
Increase in disorder/entropy
EDTA Complex is therefore more complex
[M(H2O)6] + EDTA → [M(EDTA)] + 6H2O