7.1.

Introduction to Group 1 Alkali Metals and Groooooooooooooooooooooooooooooooooup 2

Alkaline Earth Metals

The first two vertical columns of the Periodic Table, i.e. Groups 1 and 2, are called the s
block metals, because they only have 1 or 2 electrons in their outer shell.

These outer electrons are of an sorbital type (s subshell or subquantum level) and the
chemistry of the metals, with their relatively low ionisation energies, is dominated by the
loss of these s electrons to form a cation and also accounts for their generally high
chemical reactivity ...

o the outer s1 electron loss by the Group 1 Alkali Metals gives the M+ ion, and,

o the outer s2 electrons lost by the Group 2 Alkaline Earth Metals forms the M2+ ion,

o and in each case the cation has a residual very stable noble gas core of electrons.

The only chemically stable oxidation states are +1 for Group 1 metals and +2 for Group 2
elements, governed by the relative ease of loss of the outer s electrons and the subsequent very
high ionisation energies required to remove a 2nd (for group 1) or 3rd electron (for group 2) from
the inner noble gas core of electrons left (i.e. from the next principal quantum level or shell).

The relative ease of delocalising the outer 1/2 electrons in the metal lattice makes them
good conductors of heat and electricity (bonding model for metals).

The low ionisation energies and low electronegativity means that when combined with
nonmetals, most compounds of the Group 12 elements tend to be ionic in nature.

Group 1and Group 2 ions are their compounds are important in the natural world of living systems
and geology.

o Calcium carbonate and phosphate minerals are important components of skeletons, teeth
as well as bone!

o For marine organisms the skeletal remains form sedimentary rocks like limestone and
chalk which mainly consist of calcium carbonate and magnesium carbonate.

o In biochemistry, at the heart of the chlorophyll molecules involved with photosynthesis is

magnesium ion (Mg2+).

o Sodium and potassium ions (Na+ and K+) are important components of a balanced
electrolyte solutions in living systems and in nerve impulse transmission systems.

some other LINKS

o For introductionrevision GCSE notes on Alkali Metals and GCSE Quiz on Alkali
Metals

o and an ASA2 A level Quiz on the basics of sblock metal chemistry.

7.2. Information and Data Table GROUP 1 ALKALI METALS (from left to right is
down the group!)

property\Z symbol, 11Na 19K 37Rb 55Cs

3Li Lithium 87 Fr Francium
name Sodium Potassium Rubidium Caesium
melting point/oC 181 98 64 39 29 27
o
boiling point/ C 1347 883 774 688 679 677
3
density/gcm 0.53 0.97 0.86 1.48 1.87 >1.87
1
1st IE/kJmol 513 496 419 403 376 400
1
2nd IE/kJmol 7298 4562 3051 2632 2420 2100
atomic metallic
152 186 231 244 262 270
radius/pm
M+ ionic radius/pm 78 98 133 149 165 180
electronegativity 0.98 0.93 0.82 0.82 0.79 0.70
electron
2,1 2,8,1 2,8,8,1 2,8,18,8,1 2,8,18,18,8,1 2,8,18,32,18,8,1
configuration
electron
[He]2s1 [Ne]3s1 [Ar]4s1 [Kr]5s1 [Xe]6s1 [Rn]7s1
configuration
Electrode potential
3.04V 2.71V 2.92V 2.92V 2.92V 2.92V
M/M+
Symbol flame Li Na K
Rb red Cs blue Fr na
colour red/crimson yellow lilac/purple

Typical metals in some ways e.g. silvery grey lustrous solids*, very good conductors of heat
and electricity, relatively high boiling points.

o * When freshly cut they are quite shiny, but they rapidly tarnish by reaction with oxygen to
form an oxide layer, which is why they are stored under oil. Ask your teacher to show you
the bottle from which we extract the lumps for doing our demonstrations not a pretty
sight if its a bit old!
 o The 1st ionisation energies are the lowest of any group of elements, but note the jump up
to a very high 2nd ionisation energy.

Equations for the 1st and 2nd ionization energies.

M(g) ==> M+(g) + e (very low 1st IE, M = Li, Na, K, Rb, Cs, Fr)

M+(g) ==> M2+(g) + e (much higher 2nd IE)

The very high 2nd ionization energy is due to removing an electron from
an electronically very stable noble gas inner core of electrons.

Untypical in other ways e.g. relatively soft, low density (Li, Na and K float on water before
reacting ...), and very low melting points.

o The reasons for the low melting points, densities and physical hardness lies in looking at
the bonding model for metals.

o The more electrons that can be delocalised and the closer the atoms (actually ions in a
metallic lattice) can approach each other the stronger the bond, thereby raising melting
points, densities and tensile strength.

o However, Group 1 metals can only release one electron per atom to contribute towards
the pool of bonding delocalised electrons. Group 2, 3 and transition metals etc. can
contribute more electrons for metallic bonding. This why the Group 2 elements have
higher melting points, densities and are harder metals.

o Also, being the first element on a given period, they have the highest relative atomic/ionic
radii because you have the minimum nuclear attractive force on the outer electrons.

Any metal flamecolour is due to electronic transitions in the atom or cation.

o Electrons are promoted to higher quantum levels via collisions of the high thermal kinetic
energy particles in the hot flame. When the promoted electron 'relaxes' or 'falls' back to
its more stable electronic level, energy is emitted (this is the basis of an emission
spectrum). If the frequency/wavelength/energy of the photons emitted is in the visible
region of the electromagnetic spectrum, a 'flame colour' results e.g. as observed in
fireworks.

The set of quantum levels and associated energies are unique for each atom
which means the quantum level differences varies from atom to atom, therefore
the frequency/energy of emitted photons is different, hence you see different
flame colours in the visible region of light from each Group 1/2 metal each
element has a 'finger print' emission spectrum.

The sblock groups 1/2 have the lowest ionisation energies of all the elements in
the periodic table, so the high temperature of the flame (>1000 oC) means that the
kinetic energy of the flame particles is quite sufficient to promote electrons to a
higher quantum level when the metal atoms collide with other high KE atoms or
molecules.

Planck's Equation: E = h, where

 E = E2 E1, the energy difference between e.g. the outer s level E 1 and
a higher level E2,

h = Planck's constant and = frequency of light of the emitted photons.

For more examplesdetails see electronic structure and

emission/absorption spectra notes.

Oxidation state or oxidation number is always +1 in Group 1 Alkali Metal compounds.

o Only the single outer selectron is easily lost, the 2nd, and subsequent ionisation
energies are far too high to form chemically stable cations of 2+ etc. i.e. the energy
required will not be compensated by ionic bond formation.

Detailed notes on oxidation state and redox reaction theory.

o The stable Group 1 cation has the electron configuration of a noble gas,

e.g. the sodium atom, Na, is 2,8,1 or 1s22s22p63s1 or [Ne]3s1

so the sodium ion, Na+, is 2,8 or 1s22s22p6 or [Ne]

See also section 4. on Group trends and comparison with Group 2 metals.

o and for help notes on data, see the inorganic data page. (opens in new window)

PLEASE NOTE that Francium is highly radioactive and therefore difficult and
dangerous to study BUT all its known physical and chemical properties fit in with it being
at the foot of Group 1 and other properties could be inferred from the properties and group
trends of Li to Cs.

Z = 3 lithium Li in Group 1 Alkali Metals

The structure of the element:

o Giant lattice metallic structure of immobile positive metal ions surrounded by a 'sea' of
freely moving mobile electrons (so-called delocalised electrons).

Physical properties:

o Relatively soft silvery solid, less dense than water; mpt 181 oC; bpt 1347oC; good
conductor of heat/electricity.

Group, electron configuration (and oxidation states):

o Gp1 Alkali Metal; e.c. 2,1 or 1s22s1; (+1 only) e.g. LiCl, Li2O etc.

Reaction of element with oxygen:

 o Burns when heated in air to form the ionic white solid, lithium oxide, (Li+)2O2-.

4Li(s) + O2(g)==> 2Li2O(s)

Reaction of oxide with water:

o It is a basic oxide, readily dissolving/reacting to form an alkaline solution of lithium

hydroxide of pH 13-14.

Li2O(s) + H2O(l)==> 2LiOH(aq)

Reaction of oxide or hydroxide with common mineral acids:

o Li2O behaves as a basic oxide dissolving to form the chloride, sulphate and nitrate salt
in the relevant dilute acid.

o The hydroxide MOH is a strong base and alkali (since a soluble base) and similarly forms
salts.

o Li2O(s) + 2HCl(aq) ==>2LiCl(aq) + H2O(l)

LiOH(aq) + HCl(aq) ==>LiCl(aq) + H2O(l)

o Li2O(s) + H2SO4(aq) ==>Li2SO4(aq) + H2O(l)

2LiOH(aq) + H2SO4(aq) ==>Li2SO4(aq) + 2H2O(l)

o Li2O(s) + 2HNO3(aq) ==>2LiNO3(aq) + H2O(l)

LiOH(aq) + HNO3(aq) ==>LiNO3(aq) + H2O(l)

o In all cases the ionic equations are

for M2O: Li2O(s) + 2H+(aq)==> 2Li+(aq) + H2O(l)

for MOH: OH-(aq) + 2H+(aq)==> H2O(l)

Reaction of oxide with strong bases/alkalis:

o None, lithium oxide is ONLY basic.

Reaction of element with chlorine:

o Burns when heated in chlorine to form white powder/colourless crystals of ionic lithium
chloride, Li+Cl-.

2Li(s) + Cl2(g)==> 2LiCl(s)

Reaction of chloride with water:

 o The salt readily dissolves forming a neutral solution of hydrated lithium and chloride ions
(~pH 7).

LiCl(s) + aq==> Li+(aq) + Cl-(aq)

or LiCl(s) + 4H2O(l)==> [Li(H2O)4]+(aq) + Cl-(aq)

The chloride ion is such a weak base it shows no chemical interaction with water
and the lithium ion shows virtually no acidic character, so lithium chloride solution
is neutral ~pH 7.

Reaction of element with water:

o The metal reacts quite quickly forming hydrogen gas and alkaline lithium hydroxide,
pH 13-14.

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

Other comments:

o -

7.3. Information and Data Table GROUP 2 ALKALINE EARTH METALS (from left to right
is down the group!)

property\Zsymbol, 4Be 12Mg 20Ca 38Sr

Ba Barium
56 Ra Radium
88
name Beryllium Magnesium Calcium Strontium
 melting pt./oC 1278 649 839 769 729 700
o
boiling pt./ C 2487 1090 1484 1384 1637 1140
3
density/ gcm 1.85 1.74 1.55 2.54 3.51 5.0
1
1st IE/ kJmol 900 738 590 550 503 509?
1
2nd IE/kJmol 1757 1451 1145 1064 965 979
1
3rd IE/kJmol 14848 7733 4910 4210 3600 3300
atomic radius/ pm 111 160 197 215 217 223
2+
M ionic radius/ pm 34 78 106 127 143 152
electronegativity 1.57 1.31 1.00 0.95 0.89 0.89
electronconfig. 2,2 2,8,2 2,8,8,2 2,8,18,8,2 2,8,18,18,8,2 2,8,18,32,18,8,2
2 2 2
electronconfig. [He]2s [Ne]3s [Ar]4s [Kr]5s2 [Xe]6s2 [Rn]7s2
Electrode pot'ial
1.97V 2.36V 2.84V 2.89V 2.92V 2.92V
M/M2+
Symbol flame
colour (see Ca brick Sr Ba apple
Be na Mg na Ra na
chemical tests new red crimson green
window)

Very typical metals, silvery grey lustrous solids, relatively high melting and boiling points, good
conductors of heat and electricity.

o The first two ionisation energies are relatively low but there is quite a jump to the 3rd
ionisation energy.

Equations for the 1st, 2nd ionization energies.

M(g) ==> M+(g) + e (very low 1st, M = Be, Mg, Ca, Sr, Ba, Ra)

M+(g) ==> M2+(g) + e (2nd higher IE)

M2+(g) ==> M3+(g) + e (much higher 3rd IE)

The very high 3rd ionization energy is due to removing an electron from an
electronically very stable noble gas inner core of electrons.

Compared to adjacent Group 1 metal on same period:

o The melting and boiling points are higher, and they are harder, stronger and more dense
than the adjacent Group 1 metal on the same period. This is because their are two
delocalised electrons per ion in the crystal lattice giving an overall stronger electrical
attraction with the more highly charged M2+ ions.

o Chemically very similar e.g. form mainly ionic compounds but different formulae and less
reactive because the 1st ionisation energies are higher (due to extra nuclear charge) and
a 2nd ionisation energy input to form the stable M 2+ ion.

Oxidation state or oxidation number is always +2 in Group 2 Alkaline Earth Metal

compounds.
 o The two outer selectrons are readily lost. The 3rd, and subsequent ionisation energies
are far too high to form chemically stable cations of 3+ etc. i.e. the energy required will
not be compensated by ionic bond formation.

o The stable Group 2 cation has electron configuration of noble gas,

e.g. the calcium atom, Ca, is 2,8,8,2 or 1s22s22p63s23p64s2 or [Ar]4s2

so the calcium ion, Ca2+, is 2,8,8 or 1s22s22p63s23p6 or [Ar]

See also section 7.4 below on Group trends and comparison with Group 1 metals.

o and for help notes on data, see the inorganic data page (opens in new window)

PLEASE NOTE that Radium is highly radioactive and therefore difficult and dangerous to
study BUT all its known physical and chemical properties fit in with it being at the foot of
Group 2 and other properties could be inferred from the properties of Mg to Ba.

7.4. General Trends down groups 1 & 2 with increasing atomic number and formula patterns

The 1st ionisation energy (IE) or 2nd etc. decrease: (important to link to reactivity trend)

o because as you go down

the group from one
element down to the next,
on the next period, the
atomic radius gets bigger
due to an extra filled
electron shell.

o The outer electrons are

further and further from the
nucleus and are also
shielded by the extra full
electron shell of negative
charge. Therefore the
outer electrons are less
and less strongly held by the positive nucleus and so less and less energy is needed to
remove them.

o Note (probably not needed for exams, but a Q students might raise):
 Despite the significant increase in atomic number i.e. positive nuclear charge
down the group, this effect is outweighed by 'shielding effects' of inner full
electron shells and also the nuclear charge is spread over an increasingly larger
surface as the atomic radius increases.

The effective nuclear charge is NOT what it seems as given by the atomic
number and is more related to the number of outer electrons and the size of the
atom.

IONISATION ENERGY
PATTERNS

Successive ionisation energies always increase e.g. ... 3rd > 2nd > 1st ...

o because the same nuclear charge is attracting fewer electrons and on average closer to
the nucleus.

o The negative electrons are being successively removed from an increasingly more
positive ion, so, not surprisingly, more energy is required.

o BUT note the 2nd IE for Group 1 (e.g. for potassium in the right graph above), and the
3rd IE for Group 2 (e.g. magnesium in the left graph above), show a particularly
significant increase in IE compared to the previous ionisation energy or energies.

o This is due to removing an electron from an electronically highly stable full inner shell and
puts an upper limit on the chemically stable oxidation state.

o These abrupt changes in the successive ionisation energy graphs are clear
evidence of principal quantum levels that the electrons occupy.

Atomic and ionic radius increases:

 o

o Because from one element to the next, an extra shell of electrons is added, increasing
the electron 'bulk' and the outer electrons are increasingly less strongly
held (see above).

o The radii of the adjacent Gp 2 atom is smaller than Gp 1 atom on the same period,
because the nuclear charge has increased by one unit (L to R in PT), but is attracting
electrons in the same shell.

o Similarly the radii of a Gp 2 M2+ ion is smaller than the adjacent Gp 1 M+ ion on the same
period, because the nuclear charge has increased by one unit (L to R in PT), but is
attracting the same number of electrons in the same shells. (see data tables in section
7.2 and section 7.3)

REACTIVITY TREND THEORY relate to atomic radius and ionisation energy

o The metal gets more reactive down the group because ...

o When an alkali metal atom reacts, it loses an electron to form a singly positively charged
ion e.g. Na ==> Na+ + e (in terms of electrons 2.8.1 ==> 2.8 and so forming a stable ion
with a noble gas electron arrangement).

o As you go down the group from one element down to the next the atomic radius gets
bigger due to an extra filled electron shell.

o The outer electron is further and further from the nucleus and is also shielded by the
extra full electron shell of negative charge.

o Therefore the outer electron is less and less strongly held by the positive nucleus.

o This combination of factors means the outer electron is more easily lost, the M + ion more
easily formed, and so the element is more reactive as you go down the group best seen
in the laboratory with their reaction with water.

o The reactivity argument mainly comes down to increasingly lower ionisation energy down
the group and a similar argument applies to the Gp 2 metals, but two electrons are
removed to form the cation.
 o The reaction of a group 1/2 metal with oxygen, water or halogens gets more vigorous as
you descend the group.

Generally (but not always), the melting and boiling points fall steadily:

o This is because the ionic radii increase down the group increasing charge separation
between the metal cations of the lattice and the free delocalised electrons.

o This weakens the electrical attractive bonding force and so less thermal KE is needed to
weaken the lattice to the 'collapse point' i.e. melting.

o BUT the situation is not as simple as might be expected, e.g. the metal ions do not
always have the same crystal lattice packing arrangement.

The electronegativity tends to decrease:

o
 o The electronegativity values are the lowest of the elements, but there is still a group
trend.

o They get lower because the effective nuclear attractive force on the outer electron charge
decreases down the group.

o You can explain it along the lines of the decreasing 1st IE argument (above), by
merely changing the last part of the argument from 'easier to lose electron' to 'weaker
attraction of electron charge'.

Formula patterns:

o The general formulae are written in the summary tables in two ways

'simple' formatM2O or ionic formulae (M+)2O2 where M represents Li to Fr or

Be to Ra.

o Since all compounds can be considered ionic, most formulae needed are readily derived
in principle by knowing the formula and charge of 10 ions!

o All formulae are readily derived from equating the total positive charge of the cation with
the total negative charge of the anion, and expressing the formula as the simplest whole
number ratio.

o The Group 7 halide ion, X, can be fluoride F, chloride Cl, bromide Br and iodide I.

o The ethanoate ion is included as an illustration of carboxylic acid salts (RCOOH acid ==>
RCOO in salt).

o The oxides, hydroxides and carbonates and hydrogencarbonates are usually white
ionic solids and the Gp1/2 salts listed in the 2nd table are usually white/colourless
crystalline ionic solids.

The Group 2 hydrogencarbonates do not exist as stable solids and are only
modestly stable in aqueous solution at room temperature.

o All relevant equations showing their formation and reactions are in subsequent sections.

oxide hydroxide carbonate hydrogencarbonate

sblock cation \ anion

O2 OH CO32 HCO3
formula derived from M2O MOH M2CO3 MHCO3
Group1 cation M+ +
(M )2O 2 +
M OH +
(M )2CO 3
2
M+HCO3
formula derived from MO M(OH)2 MCO3 M(HCO3)2
Group 2 cation M2+ 2+
M O 2 2+
M (OH )2 2+
M CO3 2
M2+(HCO3)2

There are also Group 1 hydrogen sulphates (hydrogensulfates/hydrogensulphates) of formula

MHSO4, i.e. half neutralisedsulphuric acid which are rarely encountered but can be crystallised.
 The oxidation numbersstates in the compounds listed in the two tables above and below:

o +1 for metal cation of group 1, +2 for metal cation of group 2

o oxygen 2, hydrogen +1, carbon +4 in table above and below

(exceptethanoate, carbon oxidation numbers are awkward in organic

compounds, leave em' in AS is my advice!)

o halogens e.g. Cl 1, nitrogen +5, sulphur +6

o you need to be able to analyse an anion to understand the relationship between the
constituent oxidation states and the charge on the anion, sum of oxidation states =
overall charge on ion e.g.

carbonate, CO32, C is +4, 3 O's at 2, sum of ox. states = +4 and 6 = 2 =

charge on anion

hydrogencarbonate, HCO3, H is +1, C is +4, 3 O's at 2, sum of ox. states = +1

and +4 and 6 = 1 = charge on anion

nitrate(V), NO3, N is +5, 3 O's at 2, sum of ox. states = +5 and 6 = 1 =

charge on anion

sulphate(VI), SO42, S is +6, 4 O's at 2, sum of ox. states = +6 and 8 = 2 =

charge on anion

halide nitrate(V) sulphate(VI) ethanoate

\anion
cation
2
X NO3 SO 4 CH3COO
formula derived from MX MNO3 M2SO42 CH3COOM
Group1 cation M+ MX +
M NO +
3
+
(M )2SO4 2
CH3COOM+
formula derived from MX2 M(NO3)2 MSO4 (CH3COO)2M
Group 2 cation M2+ 2+
M (X )2 2+
M (NO )
3 2
2+
M SO 4
2
(CH3COO)2M2+

The three strong acids mentioned in reactions in sections 5. to 9. are ...

o hydrochloric acid, HCl==> chloride salts

o nitric acid, HNO3==> nitrate salts

o sulphuric (or sulfuric) acid ==>sulphate salts (or sulfates)

o and the 4th acid is the weak organic carboxylic acid ethanoic acid*, CH3COOH
==>ethanoates

*old name 'acetic acid', and the salts were called 'acetates'
 7.5. The reaction of sblock metals and oxygen & their oxide (O 2) chemistry

The oxides and hydroxides are white ionic solids.

The reaction of Group 1 metals with oxygen (a redox reaction)

Group 1 metals: 4M(s) + O2(g)==> 2M2O(s) (M = Li, Na, K, Rb, Cs)

o shows the formation of the 'simple' oxide expected from their position in the periodic
table when the element is heated or burned in air.

o Oxidation state changes: M is 0 to +1, Oxygen is 0 to 2 in the oxide ion O 2.

ionically: 4M(s) + O2(g)==> 2(M+)2O2(s)

the metal is oxidised (0 to +1), electron loss, increase in oxidation state

oxygen molecules are reduced (0 to 2), electron gain, decrease in

oxidation state

o The oxides are soluble in water forming the strongly alkaline hydroxide:

M2O(s) + H2O(l)==> 2MOH(aq)

ionically: (M+)2O2(s) + H2O(l)==> 2M+(aq) + 2OH(aq)(not a redox change)

This is an acidbase reaction, the O2 ion is a strong BronstedLowry

base and accepts a proton from water (acting as the BronstedLowry
acid).

o Unfortunately, except for lithium (an anomaly), 'higher' oxides can be formed e.g.

o 2M(s) + O2(g)==> M2O2(s) [redox change, M (0 to +1), O (0 to 1)]

shows the formation of the yelloworange peroxide by Na, K, Rb and Cs

each oxygen is in the 1 oxidation state in the peroxide ion O22

 they readily hydrolyse with water forming hydrogen peroxide

M2O2(s) + 2H2O(l)==> 2MOH(aq) + H2O2(aq) (not a redox change)

o M(s) + O2(g)==> MO2(s) shows the formation of the 'superoxide' by K, Rb and Cs

oxidation number changes are M from 0 to +1 as expected, but on average each

oxygen changes from 0 to 1/2 in the superoxide ion O2

2MO2(s) + 2H2O(l)==> 2MOH(aq) + H2O2(aq) + O2(g) (redox change)

oxidation state changes: M and H no change (+1), four O's change from 1/2 in
superoxide ions to two of 1 in the peroxide molecule and two at zero in the
oxygen molecule.

This is a case of disproportionation where the oxidation state of an

element gives a higher and lower state product from the same 'original
species'.

The simple oxides readily dissolve in acids and are neutralised to form salts.

o M2O(s) + 2HCl(aq)==> 2MCl(aq) + H2O(l) (M = Li, Na, K, Rb, Cs)

to give the soluble chloride salt

ionically: (M+)2O2(s) + 2H+(aq)==> 2M+(aq) + H2O(l) (not a redox change)

Acidbase reaction, acid donates proton the oxide ion base, applies to all
four examples.

The chloride Cl, nitrate NO3 and sulphate SO42 are spectator ions.

o M2O(s) + 2HNO3(aq)==> 2MNO3(aq) + H2O(l)to give the soluble nitrate salt

o M2O(s) + H2SO4(aq)==> M2SO4(aq) + H2O(l)to give the soluble sulphate salt

o M2O(s) + 2CH3COOH(aq)==> 2CH3COOM(aq) + H2O(l)to give the soluble ethanoate salt

The reaction of Group 2 metals with oxygen (a redox reaction)

Group 2 metals: 2M(s) + O2(g)==> 2MO(s) (M = Be, Mg, Ca, Sr, Ba)

o shows the formation of the oxide expected from their position in the periodic table when
the element is heated or burned in air. Oxidation state changes: M from 0 to +2, and
oxygen from 0 to 2.

o The oxide, apart from beryllium, is slightly soluble in water forming the alkaline hydroxide,
which increases in strength of basic character down the group.

MO(s) + H2O(l)==> M(OH)2(s/aq) (not a redox change, M = Be, Mg, Ca, Sr, Ba)
 ionically: M2+O2(s) + H2O(l)==> M(OH)2(s/aq)

if the hydroxide is soluble: M2+O2(s) + H2O(l)==> M2+(aq) + 2OH(aq)

BronstedLowry acidbase reaction, the oxide base accepts

proton from the water.

The mixture of magnesium hydroxide and water is sometimes

called milk of magnesia.

The formation of calcium hydroxide (slaked lime) when water is

added to calcium oxide (quicklime) is very exothermic!

The pH of the resulting solution ranges from ~pH 10 to ~pH 13

for Mg(OH)2 to Ba(OH)2

All the oxides are basic and readily neutralised by acids (not a redox change).

MO(s) + 2HCl(aq)==> MCl2(aq) + H2O(l) (M = Be, Mg, Ca, Sr, Ba)

to give the soluble chloride salt

ionically: M2+O2(s) + 2H+(aq)==> M2+(aq) + H2O(l)

This applies to all four acid reactions examples in this section,

acid proton donation to the oxide ion base.

In each case the chloride Cl, nitrate NO3 and sulphate SO42
are spectator ions.

MO(s) + 2HNO3(aq)==> M(NO3)2(aq) + H2O(l) (M = Be, Mg, Ca, Sr, Ba)

to give the soluble nitrate salt

MO(s) + H2SO4(aq)==> MSO4(aq/s) + H2O(l) (M = Be, Mg, Ca, Sr, Ba)

to form the sulphate salt (soluble => insoluble)

but reaction increasingly slower for calcium oxide ==> barium oxide as
the sulphate becomes less insoluble.

MO(s) + 2CH3COOH(aq)==> (CH3COO)2M(aq) + H2O(l) (M = Be, Mg, Ca, Sr, Ba)

to give the ethanoate salt

Beryllium oxide BeO is amphoteric (another Be Gp 2 anomaly) and dissolves

in strong bases like sodium hydroxide.

The equation below shows the formation of a hydroxoberyllate complex

ion (not a redox change).
 BeO(s) + 2NaOH(aq) + H2O(l)==> Na2[Be(OH)4](aq) (beryllate salt)

ionically: Be2+O2(s) + 2OH(aq) + H2O(l)==> [Be(OH)4]2(aq)

7.6. Reaction of sblock metals and water & their hydroxide (OH ) chemistry

The oxides and hydroxides are usually white ionic solids.

The reaction of group 1 metals with water (a redox reaction)

Group 1 metal hydroxide formation

o 2M(s) + 2H2O(l)==> 2M+OH(aq) + H2(g) (M = Li, Na, K, Rb, Cs)

o shows the formation of the alkaline metal hydroxide and hydrogen.

Oxidation state changes: M from 0 to +1, one H per water remains unchanged in
oxidation number and one changes from +1 to 0 in H2.

o M = Li (slow at first), Na (fast), K (faster may ignite hydrogen to give a lilac coloured
flame* from hot potassium atoms), Rb, Cs, Fr (very explosive) i.e. the reactivity
increases down the group.

The reactivity trend is explained in section 7.4

*2H2(g) + O2(g)==> 2H2O(l) i.e. the chemistry of the lit splint pop!

o The hydroxides, MOH, are white ionic solids, all very soluble (except LiOH), strong
bases, getting stronger down the group.

All Group 1 hydroxides are soluble in water giving strongly alkaline

solutions,

and their aqueous solutions readily neutralised by acids (not a redox change)
e.g.

MOH(aq) + HCl(aq)==>MCl(aq) + H2O(l) (M = Li, Na, K, Rb, Cs)

to give the soluble chloride salt*

ionically: OH(aq) + H+(aq) ==> H2O(l)

an acidbase reaction, same for all four examples in this section

 MOH(aq) + HNO3(aq)==> MNO3(aq) + H2O(l) (M = Li, Na, K, Rb, Cs)

to give the soluble nitrate salt

2MOH(aq) + H2SO4(aq)==> M2SO4(aq) + 2H2O(l) (M = Li, Na, K, Rb, Cs)

to give the soluble sulphate salt

MOH(aq) + CH3COOH(aq)==> CH3COOM(aq) + H2O(l) (M = Li, Na, K, Rb, Cs)

to give the soluble ethanoate salt CH3COOM+

* The hydroxide solutions are readily titrated with standardised

hydrochloric acid (burette) using phenolphthalein indicator, the colour
change is from pink to colourless.

The reaction of group 1 metals with water (a redox reaction)

Group 2 metal hydroxide formation

o M(s) + 2H2O(l)==> M(OH)2(aq/s) + H2(g) (M = Mg, Ca, Sr, Ba)

o shows the formation of the hydroxide and hydrogen with cold water.

o ionically: M(s) + 2H2O(l)==> M2+(aq) + 2OH(aq) + H2(g)

o oxidation number changes, M is 0 to +2, for one H per water it changes from +1 to 0 in
H2.

o M = Be (no reaction, anomalous), Mg (very slow reaction), Ca, Sr, Ba (fast to very fast).

i.e. the reactivity increases down the group.

The reactivity trend for Group 2, and its explanation, are similar to that above for
the Group 1 Alkali Metals.

The reactivity trend for sblock metals is explained below

Magnesium hydroxide and calcium hydroxide (limewater) are sparingly

soluble, but the solubility increases down the group, so barium hydroxide is
moderately soluble.

As previously mentioned, a mixture of magnesium oxide/hydroxide and water is

sometimes called milk of magnesia and the saturated aqueous solution of
calcium hydroxide is called limewater.

If the metal is heated in steam the oxide is formed:

o e.g. Mg(s) + H2O(g)==>MgO(s) + H2(g)

 NOT an experiment you would do with Alkali Metals! but beryllium gives little
reaction.

o The oxide is formed because the hydroxide is thermally unstable at higher temperatures

M(OH)2(s)==> MO(s) + H2O(g) (M = Be, Mg, Ca, Sr, Ba)

REACTIVITY TREND THEORY: The Group 1/2 metal gets more reactive down the group
because ...

o When an alkali metal atom reacts, it loses an electron to form a singly positively charged
ion.

e.g. Na ==> Na+ + e

in terms of electrons 2.8.1 ==> 2.8 and so forming a stable ion with a noble gas
electron arrangement.

o As you go down the group from one element down to the next the atomic radius gets
bigger due to an extra filled electron shell as you go down from one period to the next
one.

o This means the outer electron is further and further from the nucleus.

o This also means the outer electron is also shielded by the extra full electron shell of
negative charge.

o Due to this shielding the effective nuclear charge on the external electron is ~ +1 (~
proton number number of noble gas inner core electrons).

o Further more, the effective nuclear charge of ~+1 is acting over a larger 'surface area' as
the atomic radius increases.

o Therefore both of these factors combine to make the outer electron less and less strongly
held by the positive nucleus as the atomic number increases (down the group).

o So, the outer electron is more easily lost, and the M+ ion more easily formed, and so the
element is more reactive as you go down the group best seen in the laboratory with
their reaction with water.

o The reactivity argument mainly comes down to increasingly lower ionisation energy down
the group (i.e. ease of ion formation) and a similar argument applies to the Group 2
metals, but two electrons are removed to form the cation.

o The enthalpy change in forming the hydrated cation from the solid metal does not appear
to be as important here.

At a more advanced and detailed level, this change can be theoretically split into
the

enthalpies of (i) atomisation, (ii) ionisation, (iii) hydration of gaseous ion ... (BUT
not here!).
 o The reactivity trend is also paralleled by the increasingly negative halfcell potential
(EM/M+ and EM/M2+) down groups, 1 and 2 i.e. increasing potential to acts as a reducing
agent an electron donor.

o As with water, the reaction of a group 1/2 metal with oxygen or halogens gets more
vigorous as you descend the group.

All the hydroxides are basic with increasing strength down the group and readily neutralised by
acids (not redox reactions). Magnesium hydroxide is sparingly soluble in water but the solubility
increases down the group.

o M(OH)2(aq/s) + 2HCl(aq)==> MCl2(aq) + 2H2O(l) (M = Be, Mg, Ca, Sr, Ba)

to give the soluble chloride salt*

all base (OH) ... acid (H+) reactions

ionically if soluble the reaction is: OH(aq) + H+(aq)==> H2O(l)

ionically if insoluble: M2+(OH)2(s) + 2H+(aq)==> M2+(aq) + 2H2O(l)

o M(OH)2(aq/s) + 2HNO3(aq)==> M(NO3)2(aq) + 2H2O(l) (M = Be, Mg, Ca, Sr, Ba)

to give the soluble nitrate salt

o M(OH)2(aq/s) + H2SO4(aq)==> M2SO4(aq/s) + 2H2O(l) (M = Be, Mg, Ca, Sr, Ba)

to give the sulphate salt

o M(OH)2(aq/s) + 2CH3COOH(aq)==> (CH3COO)2M(aq) + 2H2O(l) (M = Be, Mg, Ca, Sr, Ba)

to give the ethanoate salt

o *Saturated calcium hydroxide solution (limewater) can be titrated with

standardised hydrochloric acid (burette, low molarity) to determine its solubility.
You normally use phenolphthalein indicator and the endpoint colour change is
from pink to colourless.

The Group 2 hydroxides, M(OH)2, get more soluble down the group:

o If the hydroxide more or less insoluble (e.g. for Be and Mg), they can be made by adding
excess sodium/potassium hydroxide solution to a solution of a soluble salt of a Group 2
metal e.g. three 'double decompositions' are shown below ...

(i) calcium chloride + sodium hydroxide ==> sodium chloride + calcium hydroxide

CaCl2(aq) + 2NaOH(aq)==> 2NaCl(aq) + Ca(OH)2(s)

(ii) magnesium sulphate + potassium hydroxide ==> potassium sulphate +

magnesium hydroxide
 MgSO4(aq) + 2KOH(aq)==> K2SO4(aq) + Mg(OH)2(s)

(iii) beryllium nitrate + sodium hydroxide ==> sodium nitrate + beryllium hydroxide

Be(NO3)2(aq) + 2NaOH(aq)==> 2NaNO3(aq) + Be(OH)2(s)

or ionically: M2+(aq) + 2OH(aq)==> M(OH)2(s) for any Group 2 metal M

All the hydroxides are white powders or white gelatinous precipitates.

Beryllium hydroxide is amphoteric (an anomaly in the group), because apart from the
reactions above, it dissolves in strong alkalis like sodium hydroxide to form a hydroxocomplex
ion salts called 'beryllates' e.g.

o Be(OH)2(s) + 2NaOH(aq)==> Na2[Be(OH)4](aq) (not a redox change)

o ionically: Be(OH)2(s) + 2OH(aq)==> [Be(OH)4]2(aq)showing formation of a complex ion

For the reaction of Group 1 and 2 hydroxides with carbon dioxide to form the carbonates
and hydrogen carbonates, see section 7.9

For the thermal decomposition of nitrates see section 7.11

See also VOLUMETRIC TITRATION QUESTIONS involving acids and group1 /2 alkaline
hydroxides

7.7. The reaction of sblock metals with acids

Group 1 metals are far too reactive to contemplate adding them to acids in a school
laboratory!

Group 2 metals, apart from beryllium (another anomaly), readily react with acids, with
increasing vigour down the group (explanation in section 7.4). A redox reaction to form the
soluble chloride salt.

o M(s) + 2HCl(aq)==> MCl2(aq) + H2(g) (M = Mg, Ca, Sr, Ba)

ionically for all four examples: M(s) + 2H+(aq)==> M2+(aq) + H2(g)

oxidation state changes: one M at (0) and two H's at (+1) ==> one M (+2) and
two H's at (0)

the metal is oxidised, electron loss, increase in oxidation state

 hydrogen ions are reduced, electron gain, decrease in oxidation state

o M(s) + 2HNO3(aq)==> M(NO3)2(aq) + H2(g)

to form the soluble nitrate salt

Looks ok in principle, and does this with Mg and very dilute nitric acid, but rarely
this simple, the nitrate(V) ion can get reduced to nasty brown nitrogen(IV) oxide
gas (nitrogen dioxide, NO2) and other products, NO gas?, NO2 ion?

o M(s) + H2SO4(aq)==> MSO4(aq/ s) + H2(g)

to form soluble ==> insoluble sulphate salt

The reaction from magnesium to barium becomes increasingly slower as the

sulphate becomes less soluble, it coats the metal, inhibiting the reaction.

o M(s) + 2CH3COOH(aq)==> (CH3COO)2M(aq) + H2(g) to form soluble ethanoate salt

This reaction is much slower than the previous three because ethanoic acid is a
weak acid (about 2% ionised, so the fizzing appears a lot less vigorous than the
other three acids using solutions of similar molarity).

In aqueous solutions the metal cations formed are hydrated to aqacomplex

ions.

o not quite the simple isolated ions Mn+(aq)which we use in most equations
for brevity.

o e.g. [M(H2O)6]n+(aq) where n=1 for Gp 1 and n=2 for group 2.

There may be several layers of water molecules around the ion, so the six is not
the whole story, but is typical for the number of 'nearest neighbours', albeit
weakly dative covalently bonded water molecules in this case.

The six is called the coordination number and each water molecule (or
anything else attached to the central metal ion) is called a ligand.

The shape of such an ion is 'octahedral' and its simplified structure is shown
above on the right. The middle 'blob' is the metal ion and the six outer 'blobs' are
the water molecules.

(I will replace with proper diagrams later)

However lithium and beryllium are anomalous (M = Li n = 1, or Be n = 2),

because of electronic quantum level restrictions, they can have a maximum co
ordination number of four, so their aqueous cations should be written as
[M(H2O)4]n+(aq) which has a tetrahedral shape (shown on the left).

As described above, The soluble groups 1/2 salt solutions contain the hydrated cations derived
from the metal:
 o tetraaqua cations[Li(H2O)4]+(aq) and [Be(H2O)4]2+(aq)

o or the hexaaqua ions [M(H2O)6]+(aq) M = Na, K etc. for Group 1

o and [M(H2O)6]2+(aq) where M = Mg, Ca etc. for Group 2

o The tetraaqua beryllium ion and the hexaaqua magnesium ions generate a slight acidity
in their salt solutions due to the significant polarising power of the ions (Be 2+ very small
and double charged, Mg2+ double charged) e.g.

o for beryllium: [Be(H2O)4]2+(aq) + H2O(l) [Be(H2O)3(OH)]+(aq) + H3O+(aq)

o or magnesium: [Mg(H2O)6]2+(aq) + H2O(l) [Mg(H2O)5(OH)]+(aq) + H3O+(aq)

7.8. The reaction of sblock metals with chlorine & halide (X ) salts

The salts are white or colourless crystalline solids

Group 1 metals readily react with halogens (a redox reaction)

o e.g. heating the metal in chlorine will cause it to burn forming the chloride

o 2M(s) + Cl2(g)==> 2MCl(s) (redox reaction, M = Li, Na, K, Rb, Cs)

Oxidation state changes: M from 0 to +1, X = F, Cl, Br & I from 0 to 1

The salt products, M+X, are whitecolourless crystalline ionic solids that
dissolve in water to give neutral solutions of about pH 7. The crystalline solids
have high melting and boiling points.

The solids do not conduct electricity (no mobile ions or electrons) but will conduct
and undergo electrolysis when molten or dissolved in water when ions are free to
move to electrodes.

o The halogen is in the 1 oxidation state in the halide ion X

o The halides of groups 12 are important raw materials e.g.

sodium chloride ==> sodium hydroxide from rock salt by electrolysis of

aqueous solution

potassium bromide/iodide ==> elemental bromine/iodine from seawater by

oxidation

calcium chloride ==>calcium metal by electrolysis of molten chloride

 Group 2 metals (except Be) readily react on heating with halogens (a redox reaction)

o e.g. heating in chlorine the chloride is formed

o M(s) + Cl2(g)==> MCl2(s) (M = Mg, Ca, Sr, Ba)

Oxidation state changes: M from 0 to +2, X = F, Cl, Br & I from 0 to 1

The salt products, M2+(X)2, are similar in properties to the Group 1 M +X

compounds.

However, beryllium chloride has a polymeric covalent structure, due to the high
polarising influence of beryllium in its +2 oxidation state and the smaller
difference in electronegativity between BeCl compared to chlorine and the other
group 1 and 2 metals.