2P32 Inorganic Chemistry

Lecture 27 Chemistry of the Alkaline Metals

(Group 1A).

1. Alkaline metals
2. Crown ethers and Valinomycin host guest chemistry
3. The alkaline metals - melting points and lattice
energies.
4. The alkaline metals general properties
5. Fireworks

1. Alkaline Metals

Ion Cell (mM) Blood(mM)

K+ 139 4
Na+ 12 145
Cl- 4 116
X- 138 9
Communication between cells is mediated by nerve impulses: signals electrically
transmitted as traveling waves of ionic currents made possible by
concentration gradients of ions.

How do biochemical processes recognize the difference between Na+ and K+

when their chemistry is much alike?

Na+ - 116 pm

K+ - 152 pm

The sizes are different and this does not affect their chemistry, but think of
them traveling through a channel for a specific ion.

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 The Nobel Prize was awarded to Bill Mckennan in 2003 for determining what the
bacterial K+ channel looks like.

From the cytosolic side, the pore opens up into a vestibule; the vestibule
facilitates transport by allowing the K+ ions to remain hydrated even though they are
Only 2 of the identical subunits are shown
in the middle of the membrane.

Bacterial K+ Channel
Structure of the selectivity filter explains the ion selectivity.

For K+ to enter the filter, it must lose most of its bound water molecules

(hydration sphere).

It then interacts with the carbonyl oxygen's lining the selectivity pore.

These are rigidly spaced at the exact distance to accommodate a K+ ion.

Na+ unable to enter the filter.

Carbonyl oxygen's are too far away from the smaller Na+ ion to compensate for

the energy expense associated with the loss of water molecules required for

entry.

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 K+ loses its bound water and interacts with the carbonyl oxygen atoms

Mutual repulsion of the ions as they move through the channel in

single file helps them move into the extracellular fluid

Ions are hydrated

in the vestibule

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2. Crown Ethers, Cryptands and Valinomycin
Charles Pederson 1960s at DuPont (during his last 9 years)
flexible
bind alkali metal ions

O O

O O O
O -M
N
A
JE A
H
L
IE
R C
N P
S
E
L
R
A
H N
E
S
R
D

K+
+ K+
O O O O

O O

18-Crown-6 18-Crown-6-K+ complex

(cavity organised by K+)

Oxygen atoms are capable of acting as Lewis bases due to the presence of
the lone pairs (e.g. in hydrogen bonding between water molecules or hydration of a
metal ion in aqueous solution, see below).
The interaction with metal ions with ethers is also important:

In regular ethers, only weak complexes are formed.

However, in certain polyethers (where multiple interactions are possible) the

complexes are much stronger.

18-Crown-6 Complex Hydration of a metal

ion

These ethers are called "crown ethers" due to their shape.

They are based on repeating -OCH2CH2- units, derived from ethylene glycol
HOCH2CH2OH
The name 18-crown-6 indicates that there are 18 atoms in the ring, 6 of which
are oxygen.

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Dionaea muscipula (Venus Flytrap)

An example of a highly preorganized host

These compounds are important co-solvents.

The interior of the cavity is water like, whereas the exterior is hydrocarbon
like.
So a metal ion inside the cavity can be "carried" into an organic solvent.
This allows ionic systems such as KF to be dissolved in organic solvents and used
as reagents where the metal ion is in a complex, but the anion is unsolvated or
naked and therefore quite reactive.
Varying the size of the crown ether varies the cavity size and some metal ions
fit better than others.
For example, 18-crown-6 is an good fit for K+

12-Crown-4 is selective for Li+ ions

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Host-Guest Chemistry
The characteristic chemistry of crown ethers involves complexation of the
ether oxygens with various ionic species.
This is termed "host-guest" chemistry, with the ether as host and the ionic
species as guest.
Crown ethers may be used as phase-transfer catalysts and as agents to
promote solubility of inorganic salts in organic solutions.
For example, "purple benzene" is a solution of benzene, 18-crown-6, and
potassium permanganate that finds utility as an oxidizing agent.
The crown ether dissolves in benzene, the potassium ion complexes with the
crown ether, and the permanganate is forced to dissolve in the benzene in
order to ion-pair with the potassium ion.
This type of chemistry (host-guest) is found in nature with cyclodextrins and
macrocyclic polyether antibiotics.

Specific Applications

1. Ion recognition approach to volume reduction of alkaline tank waste by

separation and recycle of sodium hydroxide and sodium nitrate (U. S.
Department of Energy, Environmental Science Management Program)
2. Novel caged crown ligands for waste remediation: Toxic heavy metals in
the Rio Grande river valley (maquilladora region).

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Valinomycin a Natural Macrocycle

Valinomycin (VM) is a dodecadepsipeptide, made up of twelve alternating amino

acids and hydroxy acids to form a macrocyclic molecule.

It is a member of the group of natural neutral ionophores because it doesn't have

a residual charge.
O

N O
O
O H O

N
O H

VM is highly selective towards potassium N H

O
O

ions over sodium ions. This selectivity is O

important in biological systems because VM O

O
H
O
N

transports potassium ions across cell N

H O

membranes (this is the antibiotic action).

O H
O
O
O N
O

Valinomycin bound to a Potassium Ion

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Mechanism of Ionophore Action

This black circle depicts the circular valinomycin molecule. Note that K+ ions bind
to valinomycin and are shuttled back and forth across the membrane. In the
absence of a potassium specific ionophore like valinomycin, K+ only rarely crosses a
lipid bilayer. In the presence of valinomycin, K+ is freely permeable.

3. Melting points and lattice energy of the alkaline metals (Group 1A).

NaF highest lattice energy 9960C

CsF 7030C
CsI 6210C
CsClO3 2500C
Remember the lattice energy is the energy required to change 1 mol of solid to 1
mole of gaseous atoms.
Two factors affect the magnitude of the lattice energy:
Ionic Charge, the more charged the ions, the greater is the lattice energy.
Interionic distance the smaller this distance, the greater is the lattice energy.
For a given cation or anion, we can combine these factors into what is known as a
charge-to-radius ratio or the charge density, As Z+/r or Z-/r increases, so does
the lattice energy.
Compare NaF to CsF can see as the ionic radius of the cation increases, the
lattice energy decreases.
Compare, CsF, CsI, CsClO3, as the anion radius increases the lattice energy
decreases.

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4. The Alkali Metals General Properties

All are extremely reactive with water remember the U-tube video!

Li

Na

Rb Rubidium brilliant red flame test it is used in fireworks to give the purple
color.

Cs Cesium latin word for sky flame test is sky blue color

Fr Francium- this is a highly radioactive alkali metal that is found in very small
amounts in uranium and thorium ores. 223Fr is the longest lived isotope and it
has a half life of 22 minutes.

5. Fireworks

Fireworks generate three very noticeable forms of energy:

a tremendous release of sound, bright light, and heat.

The tremendous booms heard at ground level are the result of the rapid release

of energy into the air, causing the air to expand faster than the speed of sound.

This produces a shock wave, a sonic boom.

The colors are produced by heating metal salts, such as calcium chloride or

sodium nitrate, that emit characteristic colors. The atoms of each element

absorb energy and release it as light of specific colors. The energy absorbed by

an atom rearranges its electrons from their lowest-energy state, called the

ground state, up to a higher-energy state, called an excited state.

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 The excess energy of the excited state is emitted as light, as the electrons
descend to lower-energy states, and ultimately, the ground state.
The amount of energy emitted is characteristic of the element, and the amount
of energy determines the color of the light emitted.
For example, when sodium nitrate is heated, the electrons of the sodium atoms
absorb heat energy and become excited.
This high-energy excited state does not last for long, and the excited electrons
of the sodium atom quickly release their energy, about 200 kJ/mol, which is the
energy of yellow light.

The amount of energy released, which varies from element to element, is

characterized by a particular wavelength of light. Higher energies correspond to
shorter wavelength light, whose characteristic colors are located in the
violet/blue region of the visible spectrum. Lower energies correspond to longer
wavelength light, at the orange/red end of the spectrum.

The colors you see exploding in the sky are produced by the elements with the
characteristic emissions listed in the table.

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 Wavelength
Colour Compound
(nm)
strontium salts, lithium salts
red
lithium carbonate, Li2CO3 = red 652
strontium carbonate, SrCO3 = bright red

calcium salts
668
orange calcium chloride, CaCl2

yellow sodium salts

610-621
sodium chloride, NaCl

green barium compounds + chlorine producer

589
barium chloride, BaCl2

blue copper compounds + chlorine producer

505-535
copper(I) chloride, CuCl

purple mixture of strontium (red) and

420-460
copper (blue) compounds or Rubidium

silver burning aluminum, titanium, or magnesium

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