Inorganic chemistry

Group 1 Summary

1. Malleable, softer down column

2. Reactivities towards oxygen and water increases down column
a. Lithium oxide, sodium peroxide, other superoxides (O 2-)
3. Lithium does not replace proton in phenylethyne but others do
4. Ionic salts, ionic halides (not hydrolysed), basic oxides and hydroxides, hydrides
are ionic, basic and strong reducing agents
5. Thermal stabilities of carbonates, nitrates, sulfates, peroxides, superoxides
increase down column
6. Reverse order of reactivity with nitrogen gas and carbon. Lithium forms purple
nitride, only lithium and sodium react to form carbides M 2C2 (high lattice
enthalpies of nitride and carbide anions associated with small cations)
7. Higher charge/size ratio for lithium ->
a. Hydride more thermally stable
b. Carbonate much less stable
c. Salts much more soluble in organic solvents
d. Lithium and sodium form a number of hydrated solid salts, potassium
forms a few and Rb and Cs none
8. Solubilities of hydroxides in water increase down the column
9. Alkali metals do not form complexes with ligands e.g. NH 3 and cyanide, but
polydentate ligands e.g. crown ethers and cryptands with oxygen and nitrogen
donor atoms form stable complexes -> primarily electrostatic bonding, relative
sizes of cation and cavity is important.
e.g. for 18-crown-6 ether, order of stability Li+<Na+<K+>Rb+>Cs+
Smaller ring sizes (12-crown-4, 15-crown-5) preference for Li+, larger ring sizes
preference for Rb+ and Cs+ (24-crown-8)
10. Lithium alkyls are widely used as reagents in organic chemistry because they are
readily synthesised, soluble in organic solvents and provide a slightly more
reactive source of carbanions than Grignard reagents.
This is because alkyl lithium compounds form oligomers in the form of rings or
polyhedra which have hydrocarbon residues dominating the surface. Sodium and
potassium alkyls are more ionic and generally adopt infinite 3D structures in
solid state, not soluble in hydrocarbons and extremely air/moisture sensitive.

Anomalous properties associated with lithium:

High atomisation enthalpy, high (larger negative) hydration enthalpy (of Li+), small size
-> lattice energy

1. Reacts very slowly with water but is only alkali metal to form nitride
2. Lithium salts are less soluble in water but more soluble in organic solvents
 3. Salts are much less thermally stable because lattice energy of oxide which is
formed is much greater than those of original salts
e.g. decomposition of carbonate to lithium oxide (higher temperature for others),
decomposition of lithium hydroxide to lithium oxide (doesn’t happen for others)
4. Greater electronegativity of lithium: formation of less polar organometallic
compounds with oligomeric structures rather than 3D infinite structures
5. High charge to size ratio (of Li+): more stable complexes with simple ligands
containing O and N donors

Physical properties

1. Li: white metal, least dense known, soft but hardest of the group
2. Na: soft, fusible, volatile, denser but softer than lithium
3. Soft, fusible volatile metals like lithium, increasing in density and softness but
decreasing in melting point

Flame tests

1. Red
2. Yellow
3. Lilac
4. Red-violet
5. Like Rb

Action of air (a. cold b. when heated)

1. Lithium
a. Tarnishes
b. Burns at 200 dc to form oxide with dazzling flame
2. Sodium
a. tarnishes quickly (oxidation), coating of hydroxide formed in moist air,
stored in oil
b. burns readily to form oxide and peroxide
3. others
a. tarnish quickly due to oxidation, white coating of hydroxide formed in
moist air
b. burn with increased readiness to peroxides and superoxides

Action on water

1. Slow reaction yielding LiOH and hydrogen

2. Vigorous reaction, does not ignite if in small quantity
3. Very vigorous, hydrogen igniting at once
4. Explosive

Oxides
 1. Li2O – reacts slowly with water to LiOH, white, mp 1570 dc, antifluorite structure
2. Na2O – white deliquescent solid, combines vigorously with water, mp 1132 dc,
anti-fluorite structure
3. K2O, like Na2O, mp 740 dc, hygroscopic, pale yellow, antiflourite, v soluble water,
sol ethanol
4. Like Na2O, anti fluorite, pale yellow mp 400 dc (decomp)
5. Anti fluorite, orange, mp 490 dc

The alkali metal sesquioxides are exceptions and contain both peroxide, and superoxide
ions, e.g., Rb2O3 (dark, paramagnetic, decomposition temperature between that of oxide
and peroxide)

Hydrides

 Alkali metals do not combine v readily with hydrogen under atm pressure,
Lithium forms hydride at 973K, other alkali metals lower temperature ~673K
 Ionic character of bonds increases with increasing atomic number of metal,
stability decreases (due to lattice energies)
 Strong reducing agents, reactivity increases as stability decreases (e.g. reacting
with oxygen)

Hydroxides (MOH)

All M react with water to form hydroxide, evolving hydrogen. Strongly alkaline and
caustic substances, v soluble and deliquescent.

1. White crystalline, mp 471 dc, not deliquescent, not v soluble in water,

hygroscopic, absorbs CO2 from air, sparingly sol in ethanol
2. Absorbs CO2 from air, thalium iodide structure, mp 323 dc
3. Beta TlI structure, reacts readily with CO2, mp 360 dc
4. Mp 301 dc, only absorbs CO2 at high pressures
5. Pale yellow, only absorbs CO2 at high pressures

Nitrides

1. Direct combination of elements, purple hexagonal crystals, v water sensitive

liberating ammonia
2. Synthesised, unstable
3. Not formed

Halides

E.g. chlorides (NaCl structure)

Li doesn’t react with chlorine whereas the rate of reaction increases as atomic number
of elements increases (MH + Cl2 -> salt + HCl)
 1. Deliquescent, v soluble in water, forms hydrates, sol ethanol and hydrogen, mp
610 dc
2. Anhydrous above 0.15 dc, stable, not deliquescent, mp 801 dc
3. Deliquescent, v sol water, sp sol ethanol, mp 773 dc
4. Mp 718 dc, v sol water, sp sol etoh, forms polyhalides in solid state
5. CsCl structure, mp 646 dc, v sol water, sol ethanol, forms polyhalides in solid
state

Liquid ammonia reactions

(reducing agents)

http://www.ucc.ie/academic/chem/dolchem/html/dict/alkynes.html

Reaction with ethyne

Can take H off, leaving acetylide ion, evolving hydrogen gas.

HCCH + 2Na ==> 2HCCNa + H2
(white, ionic solid)

https://en.wikipedia.org/wiki/Sodium_amide

Making sodium amide (salt, infinite polymer, white) using Iron III catalyst through
electride intermediate, forming hydrogen gas

Complexes

 Multidentate crown ethers or cryptands (3D equivalents of crown ethers contain

nitrogen atoms, hide cation, lone pairs inwards cryptands shield cations and
complex even more effectively than crown ethers) can be used as ion carriers or
added to organic solvents to dissolve inorganic salts
o Form electride complexes (black, paramagnetic), formula M +[(crown
ether)e-]
o Macrocyclic recalls chelate effect
o Large size and hydrophobic complexed cation -> crown ether complexing
can lead to salts becoming soluble even in organic solvents with no donor
atoms
o Stabilities essentially enthalpy based, entropies of complexing even in aq
solution are minimal
o Cryptand -222 shifts disproportionation equilibrium of Na to the RHS,
therefore producing golden yellow solid [Na(cryptand-222)] +Na- (if 2:1
ratio, if less sodium then electride)
https://en.wikipedia.org/wiki/Electride

Reaction with Napthalene (in ethereal solvent usually)

https://en.wikipedia.org/wiki/Sodium_naphthalenide

Dark green salt, basic, reducing agent