3.4 chemistry of the d-block transition metals Flashcards
elements of the d-block have their outer electrons in the __ orbitals?
d orbitals
are all d-block elements transition metals?
no
what is a transition metal?
- a d-block element that forms one or more stable ions with partially filled d-orbitals
although zinc is part of the d-block, why is it not a transition element?
because it doesnt have a partially filled d sub-shell as an atom or in its stable ion Zn2+
what are some transition metal characteristics?
- variable oxidation states
- form complex ions
- form coloured ions in solution
- catalyse reactions either as elements or in compounds
what are the two exceptions to the electronic configuration rule that the 4s orbitals are filled before the 3d orbitals?
- chromium
- copper
Cr : [Ar] 3d^5 4s^1
Cu : [Ar] 3d^10 4s^1
when transition metal atoms form ions, what electrons are lost first?
the 4s electrons are lost first
when you write or draw the electronic configuration of any transition metal ion, they always have an empty 4s orbital
write the electronic configuration for Ni^2+
Ni : [Ar] 3d^8 4s^2
Ni^2+ : [Ar] 3d^8
write the electronic configuration for Fe^3+
Fe : [Ar] 3d^6 4s^2
Fe^3+ : [Ar] 3d^5
can transition metals have different oxidation states?
yes
why can transition metas have different oxidation states?
- because the electrons in the 4s and 3d orbitals have very similar energies
- so the energy required to remove/gain any of these electrons is similar
(a relatively similar amount of energy is required to gain or lose different number of electrons)
- the lower oxidation states are found as simple ions e.g Co^2+ or Fe^3+
- the higher oxidation states only exist when the metals are covalently bonded to very electronegative elements such as oxygen e.g CrO4 2- or MnO4 -
what is the most common oxidation states of chromium?
+2, +3 and +6
what is the most common oxidation states of manganese?
+2, +4 and +7
what is the most common oxidation states of iron?
+2 and +3
what is the most common oxidation states of cobalt?
+2 and +3
what is the most common oxidation states of copper?
+1 and +2
what does a transition metal complex consist of?
- a central metal ion surrounded by a number of molecules or ions called ligands
ligand definition
- a small molecule or ion with a lone pair of electrons that coordinate bonds to a central metal atom to form a complex ion
(lone pair donor)
the ligands are attached to the central ion by what?
coordinate bonds
the ligand supplies the two electrons which is what makes it a coordinate bond
when do ligands form coordinate bonds?
(transition metal ions have many orbitals available for bonding, many of which are empty)
- when an orbital, from the ligand, containing a lone pair of electrons overlaps with empty orbitals on the transition metal ion
how are ligands classified?
by the number of coordinate bonds that they can form in complexes
what are monodentate ligands?
- ligands that have one atom which can bond to the metal ion
what are examples of monodentate ligands?
- water
- ammonia
- chloride ion
- cyanide ion
what are bidentate ligands?
ligands that have two atoms which can bond to the metal ion
typically, complexes are either octahedral with six ligands arranged around the central metal ion (more common) or tetrahedral with four ligands (less common)
what is the bond angle of an octahedral shape?
90°
what is the bond angle of a tetrahedral shape?
109.5°
what is the colour of the octahedral complex [Fe(H2O)6] 2+?
pale green
what is the colour of the octahedral complex [Fe(H2O)6] 3+?
yellow
what is the colour of the octahedral complex [Cr(H2O)6] 3+?
dark green
what is the colour of the octahedral complex [Co(H2O)6] 2+?
pink
what is the colour of the octahedral complex [Cu(H2O)6] 2+?
(pale) blue
what is the colour of the octahedral complex [Cu(NH3)4(H2O)2] 2+?
royal blue
- the familiar colour of many Cu2+ aqueous solutions is due to the [Cu(H2O)6] 2+ ion.
- one lone pair of electrons on the oxygen atom from each water molecule is used to form a coordinate bond to the metal ion
what is the colour of the tetrahedral complex [CoCl4] 2-?
blue
what is the colour of the tetrahedral complex [CuCl4] 2-?
yellow-green
when is the [CuCl4] 2- complex formed?
when the Cu2+ ions react with concentrated hydrochloric acid which displaces the water molecules
what does the overall charge on the complex depend on?
the charge on the central ion and the total charge due to the ligands
what is a ligand exchange reaction?
a reaction in which one ligand in a complex ion is replaced by a different one
is the ligand exchange reaction an equilibrium process?
yes
because a ligand exchange reaction complex contains two different ligands, there could be two different arrangements, but usually the two water molecules are opposite each other
ligand exchanges can also lead to a change in geometry of the complex ion
if ammonia solution is added to a solution containing [Cu(H2O)6] 2+, ammonia molecules replace four of the water molecules to form a new complex [Cu(NH3)4(H2O)2] 2+
- this is an equilibrium process
[Cu(H2O)6] 2+ + 4NH3 ⇌ [Cu(NH3)4(H2O)2] 2+ + 4H2O
blue ⇌ royal blue
if concentrated hydrochloric acid is added to a solution containing [Cu(H2O)6] 2+, six water molecules are replaced by four chloride ions
- this is a reversible reaction
- [Cu(H2O)6] 2+ + 4Cl- ⇌ [CuCl4] 2- + 6H2O
- blue ⇌ yellow-green
- concentrated HCl is used because it provides a very high concentration of chloride ions. The high chloride ion concentration shifts the equilibrium to the right giving a yellow-green colour. Adding water shifts the equilibrium to the left and the solution returns to blue
a similar reaction occurs with [Co(H2O)6 2+] and chloride ions, but the colours are different.
- if a large amount of chloride is used, for example by adding concentrated hydrochloric acid, the equilibrium shifts from the pink octahedral complex to the blue tetrahedral complex
- chloride ions are bigger than water molecules so there isnt room to fit six of them around the central metal ion
- [Co(H2O)6 2+ + 4Cl- ⇌ [CoCl4] 2- + 6H2O
- pink ⇌ blue
transition metal ions are only coloured when _________?
they form complexes
without ligands, all d orbitals in a transition metal ion have the same energy (they are degenerate)
how do transition metal ions form colour?
- when ligands approach the metal ion, they cause the energy of three of the d orbitals to become different to the other two. this splits the d orbitals into two sets: three of lower energy and two of higher energy
- an electron in a 3d orbital can move from a lower energy set to a higher energy set if it can gain sufficient energy
- when visible light is passed through a solution of this ion, some of the energy is absorbed which promotes an electron to a higher 3d orbital
- only one frequency (colour) of light is absorbed, which corresponds to the energy gap between the orbitals (∆E = hf)
- the colour you see is made up of the light frequencies that are not absorbed i.e those that are reflected
- when light of a particular colour is absorbed, its complimentary colour is reflected
why are compounds containing the complex [Cu(H2O)6] 2+ typically pale blue?
as they absorb light in the red region of the spectrum
the energy difference, ∆E, between the split 3d orbitals, and as such the colour, depends on what?
- the ligand
- the coordination number
- the transition metal ion
- the oxidation state of the metal
(different ligands cause different splitting of orbitals, so different frequencies are absorbed (giving a different ∆E) and different colours are produced)
are all complexes coloured?
no
- e.g Cu+, Sc3+
- copper (I) complexes have an electronic configuration with a full d sub-shell, while Sc3+ ions have an empty d sub-shell, meaning that electrons cannot move from lower to higher orbitals
- therefore copper (I) and scandium (III) complexes appear colourless
what is the colour of aqueous solutions of compounds containing the ion Cr3+?
(dark) green
what is the colour of aqueous solutions of compounds containing the ion Cr2O7 2-?
orange
what is the colour of aqueous solutions of compounds containing the ion Fe 2+?
pale green