3.4 D-block Flashcards
Define a d-block element
- group of elements whose outer electrons are found in d-orbitals
Why do chromium and copper fill their d orbitals before s?
- completely full or half full d-sub shell is more stable than a partially filled d sub level
Define a transition metal
- d-block element that forms a stable ion with an incomplete d-sub shell
What is a transition metal complex?
- central metal ion surrounded by coordinately bonded ligands
Define a ligand
- small molecule with a lone pair that can bond to a transition metal ion
Define a complex ion
- a transition metal bonded to one or more ligands
Define a coordinate bond
- a bind where both electrons are provided for by the same atom
Define the coordinate number
- number of coordinate bonds formed
Features of transition metal complexes
- small with very large positive charges
- many empty bonding orbitals
- electron-rich molecules have lone pairs so they can from coordinate bonds with empty orbitals in transition metal ion
Monodentate and bidentate ligands
Mono: one atom that can bond to metal ion
Bi: 2 atoms bonding to metal ion (ligand able to donate 2 lone pairs)
[Fe(H2O)6]2+
Pale green
[Fe(H2O)6]3+
Yellow
[Cr(H2O)6]3+
Dark green
[Co(H2O)6]2+
Pink
[Cu(H2O)6]2+
Blue
[Cu(NH3)4(H2O)2]3+
Royal blue
[CoCl4]2-
Blue
[CuCl4]2-
Yellow green
What are stereoisomers
- pairs of molecules with same formula but different orientation of functional groups in 3D space
Ligand names
1 - mono
2 - di
3 - tri
4 - tetra
5 - penta
6 - hexa
Ligand group names
H2O - aqua
NH3 - ammine
OH- - hydroxo
Cl- - chloro
F- - fluoro
CN- - cyano
Cis isomer
Same side
Trans isomer
Diagonal
Where do the colours of transitional metal complexes come from?
- there is repulsion between electrons present in ligands and electrons in d orbitals
- which destabilises the orbitals causing them to split into 3 low energy orbitals and 2 high energy
- electrons move from low to high energy gaining energy by the absorption of light to move to higher energy level
- colours seem are due to unabsorbed frequencies
Properties of d-block metals
- good conductors of heat and electricity
- high melting and boiling point
- malleable
- ductile
- shiny
- strong with high tensile and compressive strength
Properties of transition metals
- variable oxidation states
- have catalytic activity
- form coloured complexes
- other metal properties
What is meant by oxidation state?
- hypothetical charge of an atom if all of its bonds to other atoms were fully ionic
Cr3+
Green
Cr2O7 2-
Orange
CrO4 2-
Yellow
Co2+
Pink
Fe2+
Pale green
Fe3+
Red brown
Cu2+
Pale blue
Explain the nature of ligands
- different ligands have different effects on the energies of the d-orbitals of the central ion
- some ligands have strong electrical fields which cause a large energy gap when d-orbitals split
Order of smallest to largest split
Cl-
F-
OH-
H2O
NH3
CN-
Impact of oxidation of metal on transition metal complexes
- as oxidation increases so does the amount of splitting of the d-orbital
- changes of oxidation state change the colour of light absorbed so therefore colour of light seen
Explain how the coordination of the ion impacts its splitting
- splitting is greater in octahedral than tetrahedral
- only normally change coordination if change ligand, which will change colour too
—> change cannot be isolated
Colour change when cobalt solution is oxidised
- rapid darkening of straw coloured to deep red brown when cobalt solution oxidised
Examples of transition metal catalysts
- iron in the Haber process
- nickel to make margarine in the dehydrogenation of vegetable oils
- vanadium oxide in the contact process
- manganese oxide in the catalytic decomposition of hydrogen peroxide
Define a homogenous catalyst and how they work
- same physical state as reactions
—> use variable oxidation states to oxidise/reduce a reactant, making it more reactive
—> the transition metal can then be converted back to its original oxidation state by reaction with another molecule
Define a heterogenous catalyst and how they work
- different physical state to reactants
—> partially filled d-orbitals
—> catalyst provides a solid surface on which reactants can be absorbed and brought closer together for more opportunity to react
—> molecules with lone pairs can form coordinate binds to the metal atom because there are available empty d-orbitals to bond ti
Reactions of Cr3+ with OH- ions
- green
- grey-green ppt when OH- added
- ppt dissolve to deep green solution when excess OH- added
Reaction of Fe2+ with OH- ions
- pale green
- dark green ppt when OH- added
- no further change when excess OH- added
Reaction of Fe3+ with OH- ions
- yellow
- red-brown ppt when OH- added
- no further change when excess OH- added
Reaction of Cu2+ with OH- ions
- pale blue
- pale blue ppt when OH- ions added
- no further change when excess OH- ions added
Reaction of Mn2+ with OH-
- pale pink solution to off white ppt
- does not dissolve in excess
Zn2+ reaction with OH-
- colourless solution to white ppt
- ppt dissolves in excess to give colourless solution
Cr3+ with NH3
- blue/purple solution to muddy green ppt
Mn2+ with NH3
- pale pink solution to off white ppt
- does not dissolve in excess
Fe2+ with NH3
- pale green solution to dark green ppt
- turns brown by aerial oxidation
Fe3+ with NH3
- yellow solution to reddy-brown ppt
Ni2+ with NH3
- pale green solution to pale green ppt
- ppt dissolve in excess to give blue solution
Cu2+ with NH3
- blue solution to pale blue ppt
- ppt dissolves in excess to give deep blue solution
Zn2+ with NH3
- colourless solution to white ppt
State how enthalpy of formation values give an indication of stability
- the more negative the enthalpy change the more stable the oxide
Describe a test to show the presence of iron (III) ions in a solution of Fe2SO4.7H2O
- add aqueous NaOH
- give red brown ppt
Describe how aqueous sodium hydroxide can be used to distinguish between aqueous iron (II) sulphate and iron (II) sulphate
- iron (II) ions give green ppt
- iron (III) ions give red brown ppt
Construct the equation for the oxidation of acidified iron (II) ions by oxygen
4Fe2+ + O2 + 4H+ —> 4Fe3+ + 2H2O
Explain why the H-O-H bind angle in the water ligand is 107° rather than 104.5°
- water molecules have 2 lone pairs and 2 bond pairs
- water ligands have 1 lone pair and 3 bond pairs
- lone pairs repel more than bond
Explain why the complex ions [Fe(H2O)6]3+ and [Fe(H2O)5(OH)]2+ are not the
same colour.
Different ligands cause different splitting therefore different frequencies of light are absorbed
Suggest how you would select an appropriate wavelength to find the
concentration of [Fe(H2O)6]3+ in the equilibrium mixture.
Find the wavelength absorbed by [Fe(H2O)6] but not [Fe(H2O)5(OH)]
Explain why CO is a good reducing agent
It has carbon in its 2+ state but its most stable state ins 4+
Colour change when aqueous NaOH added to potassium dichromate
Orange to yellow
Observations when silver nitrate is added to [CoCl4]2-
- white ppt of silver chloride
How would you distinguish Mg2+, Fe2+, Cr3+ and Pb2+?
- add excess NaOH
- Mg(OH)2 keeps white ppt but Pb(OH)2 dissolves
- Fe(OH)2 keeps green ppt but Cr(OH)3 dissolves
—> lead and chromium are amphoteric
What can be said about substances that dissolve when excess NaOH is added?
They’re amphoteric