Chemical properties of alkali metals

1.Alkali metals react with dry hydrogen to form hydrides.

a.These hydrides are ionic in nature

b.These hydrides of alkali metals react with water to form corresponding hydroxides and hydrogen gas.

LiH+ H2O->LiOH+H2

c.These hydrides are strong reducing agents and their reducing nature increases down the group.

d.Alkali metals also form complex hydrides such as LiAlH 4 which is a good reducing agent.Alkali metal
hydrides do not exist in water and this reaction with any other agent is carried out in protic solvent.

e.Fused alkali metal hydrides on electrolysis produce H2 gas at anode.

2.Formation of oxides and hydroxides.

a.These are most reactive metals and have strong affinity towards O2 ,they form oxides on surface.They
are kept under kerosene or paraffin oil to protect them from air.

b.When burnt in air (O2) ,li forms Li20 , Na forms Na 2O2 and other alkali metals form superoxides.

Diagonal relationship

The first element in group one, Lithium, and the first in group two, Group 1 2 13 14
Beryllium, behave differently to other members of their groups. Their
behaviour is like the second element of the next group. So lithium is Period 2 Li Be B C
similar to magnesium, and beryllium is similar to aluminum. [source?]
Period 3 Na Mg Al Si
In the periodic table this is known as a 'diagonal relationship'. The
diagonal relationship is because of similarities in ionic sizes and
charge/radius ratio of the element. The similarity between lithium and
magnesium is because of their similar sizes:[source?]

Radii, Li=152pm Mg=160pm

Lithium[Lithium has many different behaviours to other elements in group one. This difference caused
by:

1. the small size of the lithium atom and its ion.

2. the higher polarization power of li
+ (i.e. charge size ratio). This means increased covalent character of its compounds which is
responsible for their solubility in organic solvents

3. high ionisation enthalpy and high electronegative character of lithium as compared to other
alkali metals

4. non availability of d-orbitals in its valence shell

5. strong intermetallic bonding

Some of the ways in which lithium behaves differently from other members of are:[source?]

1. Lithium is harder than sodium and potassium which are so soft that they can be cut by a knife.

2. The melting and boiling points of lithium are higher.

3. Lithium forms monoxide with oxygen, other alkali form peroxide and superoxide.

4. Lithium combines with nitrogen to form nitrides, while other alkali metals do not.

5. Lithium Chloride is deliquescent and crystallizes as a hydrate LiCl.2H2O. Other alkali metal
chlorides do not form hydratess

Alkali metal
The alkali metals are a group (column) in the periodic table consisting of the chemical
elements lithium (Li), sodium (Na), potassium (K),[note 1] rubidium (Rb), caesium (Cs),[note
2]
and francium (Fr). This group lies in the s-block of the periodic table of elements as all alkali metals
have their outermost electron in an s-orbital: this shared electron configuration results in them having
very similar characteristic properties. Indeed, the alkali metals provide the best example of group
trends in properties in the periodic table, with elements exhibiting well-
characterised homologous behaviour.
The alkali metals are all shiny, soft, highly reactive metals at standard temperature and pressure and
readily lose their outermost electron to form cations with charge +1. They can all be cut easily with a
knife due to their softness, exposing a shiny surface that tarnishes rapidly in air due to oxidation by
atmospheric moisture and oxygen (and in the case of lithium, nitrogen). Because of their high reactivity,
they must be stored under oil to prevent reaction with air, and are found naturally only in salts and
never as the free elements. Caesium, the fifth alkali metal, is the most reactive of all the metals. In the
modern IUPAC nomenclature, the alkali metals comprise the group 1 elements,[note
3]
excluding hydrogen (H), which is nominally a group 1 element but not normally considered to be an
alkali metal as it rarely exhibits behaviour comparable to that of the alkali metals. All the alkali metals
react with water, with the heavier alkali metals reacting more vigorously than the lighter ones.

Group 1 of the Periodic Table

Name Sym. No. Atomic Melting Boiling Phase Density Valence Oxidation
Weight Point Point Electrons States

180.54 1342 0.534 +1 (strongly

Lithium Li 3 6.941 Solid 2s1
°C °C g/cm3 basic oxide)

0.968 +1 (strongly
Sodium Na 11 22.98976928 97.72 °C 883 °C Solid 3s1
g/cm3 basic oxide)

0.89 +1 (strongly
Potassium K 19 39.0983 63.38 °C 759 °C Solid 4s1
g/cm3 basic oxide)
 1.532 +1 (strongly
Rubidium Rb 37 85.4678 39.31 °C 688 °C Solid 5s1
g/cm3 basic oxide)

1.93 +1 (strongly
Cesium Cs 55 132.9054519 28.44 °C 671 °C Solid 6s1
g/cm3 basic oxide)

1.87 +1 (strongly
Francium Fr 87 223 27 °C 677 °C Solid 7s1
g/cm3 basic oxide)

How do the Alkali Metals React with Water?

The alkali metals lithium, sodium and potassium all react with
cold water forming a soluble alkaline hydroxide and hydrogen gas.
You must know how to test for hydrogen gas!
All three metals are less dense than water and so they float.

How does Sodium React with Water?

Sodium melts and forms a floating ball of metal which fizzes

as it moves over the surface of the water giving off hydrogen gas.

sodium + water sodium hydroxide + hydrogen.

2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g)

How does Lithium React with Water?

Lithium is less reactive than sodium and does not melt but
does react quickly with cold water giving off hydrogen gas.

lithium + water lithium hydroxide + hydrogen.

2Li(s) + 2H2O(l) 2LiOH(aq) + H2(g)

How does Potassium React with Water?

Potassium is the most reactive. It melts, reacts vigorously and burns

with a lilac flame as it gives off hydrogen gas. Potassium is
dangerous and can explode when it comes into contact with water.
potassium + water potassium hydroxide + hydrogen.
2K(s) + 2H2O(l) 2KOH(aq) + H2(g)
All the hydroxides are strongly alkaline. Note the state symbol
(aq) after the hydroxide, showing that it is dissolved in water.

The alkali metals are so named because they form

alkaline hydroxides in water. The metals
themselves are not alkalis, they are just metals (neutral

The Reactions with Air or Oxygen

General

These are all very reactive metals and have to be stored out of contact with
air to prevent their oxidation. Reactivity increases as you go down the
Group.

Lithium, sodium and potassium are stored in oil. (Lithium in fact floats on
the oil, but there will be enough oil coating it to give it some protection. It is,
anyway, less reactive than the rest of the Group.)
Rubidium and caesium are normally stored in sealed glass tubes to prevent
air getting at them. They are stored either in a vacuum or in an inert
atmosphere of, say, argon. The tubes are broken open when the metal is
used.

Depending on how far down the Group you are, different kinds of oxide are
formed when the metals burn (details below). Reaction with oxygen is just a
more dramatic version of the reaction with air.

Lithium is unique in the Group because it also reacts with the nitrogen in the
air to form lithium nitride (again, see below).

Details for the individual metals

Lithium

Lithium burns with a strongly red-tinged flame if heated in air. It reacts with
oxygen in the air to give white lithium oxide. With pure oxygen, the flame
would simply be more intense.

For the record, it also reacts with the nitrogen in the air to give lithium
nitride. Lithium is the only element in this Group to form a nitride in this
way.
 Note: You will find the reason why lithium forms a nitride
on the page about reactions of Group 2 elements with air
or oxygen. You will find what you want about 3/4 of the
way down that page.
Lithium's reactions are often rather like those of the Group
2 metals. There is a diagonal relationship between lithium
and magnesium. You will find this discussed on the page
about electronegativity.

Use the BACK button on your browser to return to this page

from either of these links.

Sodium

Small pieces of sodium burn in air with often little more than an orange
glow. Using larger amounts of sodium or burning it in oxygen gives a strong
orange flame. You get a white solid mixture of sodium oxide and sodium
peroxide.
The equation for the formation of the simple oxide is just like the lithium
one.

The peroxide equation is:

Potassium
Small pieces of potassium heated in air tend to just melt and turn instantly
into a mixture of potassium peroxide and potassium superoxide without any
flame being seen. Larger pieces of potassium burn with a lilac flame.

The equation for the formation of the peroxide is just like the sodium one
above:

. . . and for the superoxide:

Note: Potassium peroxide and superoxide are described as

being somewhere between yellow and orange depending
 on what source you look at. I have a bit of a problem with
this, because over my teaching career I have heated
potassium in air many times and, if memory serves
correctly, it always leaves a greyish white film on the bit of
porcelain you are heating it on. I don't recall ever seeing it
yellow or orange!
The formula for a peroxide doesn't look too stange,
because most people are familiar with the similar formula
for hydrogen peroxide. The formula for a superoxide always
looks wrong! There is more about these oxides later on.

Rubidium and caesium

Both metals catch fire in air and produce superoxides, RbO2 and CsO2. The
equations are the same as the equivalent potassium one.

There is a bit of video from the Royal Society of Chemistry showing the two
metals burning on exposure to air. The rubidium doesn't show a clear flame
colour in this video, although the caesium does show traces of blue-violet.

Both superoxides are described in most sources as being either orange or

yellow. One major web source describes rubidium superoxide as being dark
brown on one page and orange on another!

In the video both look black! - I have no idea what is going on here!

Why are different oxides formed as you go down the Group?

 Lithium (and to some extent sodium) form simple oxides, X2O, which
contain the common O2- ion.

 Sodium (and to some extent potassium) form peroxides, X2O2,

containing the more complicated O22- ion (discussed below).

 Potassium, rubidium and caesium form superoxides, XO2. The

structure of the superoxide ion, O2-, is too difficult to discuss at this
level, needing a good knowledge of molecular orbital theory to
make sense of it.

The more complicated ions aren't stable in the presence of a small positive
ion. Consider the peroxide ion, for example.

The peroxide ion, O22- looks like this:

The covalent bond between the two oxygen atoms is relatively weak.

Now imagine bringing a small positive ion close to the peroxide ion.
Electrons in the peroxide ion will be strongly attracted towards the positive
ion. This is then well on the way to forming a simple oxide ion if the right-
hand oxygen atom (as drawn below) breaks off.

We say that the positive ion polarises the negative ion. This works best if the
positive ion is small and highly charged - if it has a high charge density.

Note: A high charge density simply means that you have a

lot of charge packed into a small volume.

Even though it only has one charge, the lithium ion at the top of the Group is
so small and has such a high charge density that any peroxide ion near it falls
to pieces to give an oxide and oxygen. As you go down the Group to sodium
and potassium the positive ions get bigger and they don't have so much
effect on the peroxide ion.
The superoxide ions are even more easily pulled apart, and these are only
stable in the presence of the big ions towards the bottom of the Group.

So why do any of the metals form the more complicated oxides? It is a

matter of energetics.

In the presence of sufficient oxygen, they produce the compound whose

formation gives out most energy. That gives the most stable compound.
 The amount of heat evolved per mole of rubidium in forming its various
oxides is:

enthalpy change (kJ / mol of Rb)

Rb2O -169.5

Rb2O2 -236

RbO2 -278.7

Uses of Lithium
Lithium is used in heat resistive ceramics and glasses.
Alloy of Lithium is used in aircraft building.
Lithium Deuteride is used as fusion fuel in thermonuclear weapons.
Lithium batteries are packed with lot of energy as compared to other metals. Revolutionized devices like
cell phones, computers use lithium batteries.
Lithium salts are used as mood stabilizing drug.
Lithium-6 is a main source for tritium production.
Lithium is used in deoxidizing copper and copper alloys.
Lithium compounds are used as pyrotechnic colorants in fireworks that produces red luminance.
Lubricating greases are produced from Lithium.
Sodium

Sodium is a chemical substance which we consume everyday in our food in the form of sodium chloride
(common salt). Sodium is produced by electrolysis of sodium chloride. Sodium element is highly
reactive. In 1806, Sir Humphry Davy, a chemist, obtained sodium by passing electric current through
molten sodium hydroxide. Sodium was first produced through nuclear fusion in stars, by fusion of two
carbon atoms. It can also be produced in stars when neon atoms gain a proton.

Uses of Sodium
Sodium is used as luster in metals.
Liquid Sodium is used as coolant in Nuclear reactors.
Sodium salt of fatty acids are used in soap.
NaK, an alloy of sodium and potassium, is an important heat transfer agent.
Sodium compounds are used in paper, textile, petroleum and chemical industries.
Sodium Iodide is used to treat extensive ringworm.
Sodium is used in street lights and sodium vapor lamps as it can give yellow glow with bright luminance.
Sodium hydroxide is used as oven cleaner.
Potassium
Potassium is the 19th element in the periodic table. Potassium plays a vital role in the proper
functioning of our body. It is an essential mineral that should be maintained in organisms. If potassium
level is not balanced it may lead to hyperkalemia or hypokalemia. Potassium turns gray on exposure to
air. To prevent oxidation and to keep out moisture, potassium is stored in petroleum.

Uses of Potassium
Potassium chloride is essential for the growth of plants. It is used in fertilizers.
Potash improves water retention, yield, nutrient value, taste, color, texture and disease resistance of
food crops.
Potassium chlorate and potassium nitrate are used in explosives and fireworks.
Potassium nitrate is used as a food preservative.
Potassium maintains blood pressure and acidity levels in our body.
Potassium chromate is used in the tanning of leather and in the manufacture of inks, gun powder, dyes,
safety matches etc.,
Potassium is essential for normal cell respiration and electrolyte function as 95% of our cells are made of
potassium.
Potassium hydroxide is used to make detergents.
Potassium helps to pump fluids inside the heart and the nerves.
Rubidium

Rubidium is a radioactive element. It is derived from a latin word rubius meaning deepest red.

Uses of Rubidium
Rubidium 82 is used in myocardial perfusion.
Rubidium is used in the manufacture of atomic clocks, electronic tubes, photocells.
Rubidium is used as working fluid in vapor turbines.
It is used as a component in the engines of space vehicles.
Rubidium vapor is used in laser cooling.
Rubidium chloride is used to induce cells to take up DNA.
It is used in thermoelectric generators.
Rubidium Carbonate is used in making optical glasses.
Due to hyperfine structure of rubidium's energy levels, it is used in atomic clocks.
A compound made up of rubidium, silver and iodine, has certain electrical characteristics and is used in
making thin film batteries.
Cesium

Cesium is an active metal. Chemically, cesium is the most electropositive element and combines with
anions to form compounds. It is a highly toxic element. Cesium hydroxide is the strongest base
discovered yet. It has many isotopes of which cesium-133 is a stable isotope and the most important
standard for measurement of time (Cesium clocks or atomic clocks). Cesium is liquid at or near room
temperature.

Uses of Cesium
Cesium-134 is used in nuclear power industry.
Used in photoelectric cells due to its quick electron emission.
Cesium is used as catalyst for hydrogenation of certain organic compounds.
It is used in propulsion systems.
It removes air traces from vacuum tubes.
Cesium is used in photovoltaic cells, television image devices, night-vision equipment.
Cesium vapor is used in magnetometer.
Cesium-137 is used in brachytherapy to treat cancers. (Brachytherapy is a cancer treatment method
using radioactive elements)
Cesium chloride solution is used in molecular biology for density gradient ultracentrifugation, primarily
for the isolation of viral particles, subcellular organelles and fractions, and nucleic acids from biological
samples.
Cesium is used as a standard in spectrophotometry
It is used in military aircraft.
Francium

Francium has the lowest electronegativity among all the known elements. It is a highly radioactive metal
and heaviest of these metals. Francium is produced by bombarding thorium with protons or by
bombarding radium with neutrons. This element is rare and is not used much. It is mainly used for
scientific research in laboratory. It decays quickly as it has short half life.

Alkali metals are of great use to us but should not be used without expert guidance as they get violent
during reactions and should be handled cautiously as they are toxic.