IB Chemistry III Test

Transition Metals – Periodicity and Atomic Absorption

15 Jan. 2009

13.1 Trends across Period 3

13.1.1: Explanations of Compounds

Compound and Details

Na2O MgO Al2O3 SiO2 P4O10 (P4O6) SO3 (SO2) Cl2O7 (Cl2O)
State at Liquid
25oC Solid Solid Solid Solid Solid (Solid)(Gas) Liquid (Gas)
Covalent,
Ionic but
Ionic Ionic bondin Diamond- Covalent, Covalent, Covalent,
bonding bonding; g; like simple simple simple
Explanation ; lattice lattice lattice structure molecular molecular molecular
Conductivity Good Good Good Very poor None None None
Ionic – Diamond
Ionic – “sea” structure Covalent – Covalent –
“sea” of Ionic – of allows little Covalent – no no
electro “sea” of electro electron no free free free
Explanation ns electrons ns flow electrons electrons electrons

13.1.2 Reactions of Chlorine and Chlorides in Water

Chlorine – Forms acidic HCL

Cl2O7 – Forms acidic HCLO4
NaCl and MgCl2 – Dissolve Easily
Chlorides of Al, Si, P, and S – Form fumes of HCL

13.2 First-row d-block elements

13.2.1 Transition Elements

Transition elements display variable oxidation numbers (such as

Cu, which forms +2 and +3 cations), form complex ions, create
vibrantly colored compounds, and serve as effective catalysts.

13.2.2 Sc and Zn are anomalous

Sc – 4s23d1: Only forms +3 ion (because it is most stable when losing

both the s electrons and the single d electron)
Zn - 4s23d10: Only forms +2 ion (because it is most stable when losing
the two s electrons only, and retaining its full d orbitals)

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13.2.3 Variable Oxidation Number

All transition elements (except Sc) can show an oxidation number

of +2 because of their two 4s electrons, which are easily removed. The
d and s orbitals are of very close energy level, so many elements lose
d electrons almost as easily as s electrons. Common variations:

V: +2, +4, +5
Cr: +2, +3, +6
Mn: +2, +4, +7
Fe: +2, +3
Cu: +1, +2, +3
13.2.4 Ligands

Ligand: atom or ion or molecule that bonds with a metal

cation to form a complex ion. Ligands can be anions, or neutral (like
NH3 or H2O), but must contain a non-bonding pair of
electrons.
13.2.5 Formation of d-block complexes

To form a complex ion, the ligand creates an electrostatic

field around the metal ion that splits the d orbital into two
separate energy levels. They absorb energy in either large or small
amounts.

Example formation: [Fe(H2O)6]+3.

Small ∆o: Electrons require little energy to move to a

higher-level d orbital, and thus split into a diamagnetic
state.

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 Large ∆o: It would require more energy to split to a higher
level than to pair electrons in lower energies, so the
complex becomes paramagnetic.

13.2.6 Cause of color

When the d orbitals of a metal split due to a ligand’s electrostatic

field, those in the lower level can absorb energy. Depending on the
extent of that absorption, different wavelengths of visible light are
absorbed. Depending on how much energy is absorbed, varied
frequencies of light will also be absorbed by the electrons, resulting in
a color formed by the remaining, reflected light.

Remember that wavelength is inversely

proportional to frequency (high wav = low freq)

• When a primary color (R, G, B) is removed, the combination of

the remaining two is seen. (eg: Red is absorbed, so G+B= Cyan
is left.)
• When a secondary color (Yellow, Cyan, Magenta) is removed, the
non-involved primary color is seen. (eg: Yellow is absorbed. This
means that R+G are gone—so blue is seen.)

Wavelength Table:
700 nm – Red
Orange – 600 nm
Yellow – 570 nm
510 nm – Green
475 nm – Blue

Although the internet says 475 for blue and 510 for green, if they tell
you 500, assume blue. It’s more common. Anything higher than
about 530 is probably green.

13.2.7 Examples of Catalytic Action

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 Heterogeneous: Solid catalyst, non-solid reagents
1. Breakdown of hydrogen peroxide: H2O2 –MnO2 2H2O + O2
2. Contact Process: SO2 + O2 –V2O5 2SO3
3. Haber Process: 3H2 + N2 –Fe 2NH3
4. Hydrogenation: C2H4 + H2 –Ni C2H6
5. Catalytic Converters using Pd, Pt, and Rh.

Homogeneous: Catalyst in same state as reagents

Esterificaton: Carboxylic acid + alcohol –H+ Ester

13.2.8 Economics

The metal catalysts in Contact and Haber Processes are very

useful from an economic standpoint: they increase the speed and
decrease the activation energies of reactions, requiring less time and
less input to create more output. This makes the reactions more
efficient, which means they are more cost-effective.

Atomic Absorption

A.8.1. Spectrochemical series

Ligand ability to split orbitals.

I- < Br- < Cl- < OH- < H2O < NH3 < CN-
High-spin----low spin
Least splitting-----most splitting

A.8.2
Different metal ions produce different colors.
Oxidation # determines the # of electrons that can change energy
levels by absorbing light—if there are no electrons to absorb energy, or
all the levels are filled, then no light will be absorbed.
Ligand determines splitting and spin: a low-spin molecule needs a lot
of energy to excite to a higher level—which means it’ll absorb a lower
wavelength of light.
Energy absorption determines color change (whatever is not absorbed
is left behind as colored light)

High-wavelength light (red, 700 nm)  low-E absorption

Low-wavelength light (blue, 500 nm)  high-E absorption

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A.8.3

Organic models containing a double bond absorb more UV and

visible radiation because of pi electrons, which are free to excite
to higher levels and move around more.

A.8.4 and A.8.5

UV spectroscopy is used only to detect pi (double and triple)

bonds. That’s all.

The more bonds present, (eg. 1 double bond, 5 double bonds, ten…),
the lower-energy (higher wavelength) light can be absorbed. Since UV
light is of higher energy, this means that molecules with more
double bonds will absorb less UV and more visible.

Conjugated bonds (alternating between double and single)

absorb UV easily.

A.8.6

Absorbance and Concentration are directly related. Everything else in

the formula is a constant.

Good luck!