File: 05_KU

05 KU
 Occurrence, extraction
 Isotopes
 Uses
 Physical properties
 Th metals
The l
 Compounds :
◦ Halides
◦ Oxides
◦ Hydroxides
◦ Salts of oxoacids
◦ Complex ions in aqueous solution
◦ Complexes with amido or alkoxy ligands
 Diagonal relationships
British chemist and inventor  French chemist and biologist 
Sir Humphry Davy FRS  Antoine‐Laurent de Lavoisier  Marie Curie (1867‐1934) French physicist Pierre 
(1778 ‐ 1829) (1743 – 1794). Curie (1859 – 1906) 
 Beryllium occurs principally as the silicate mineral beryl,
Be3Al2[Si6O18]
 Magnesium and calcium are the eighth and fifth most
abundant elements, respectively, in the Earth’s crust.
 Mg, the third most abundant in the sea.
 The elements Mg, Ca, Sr and Ba are widely distributed in
minerals and as dissolved salts in seawater; some important
minerals are
◦ dolomite (CaCO3.MgCO3),
◦ Magnesite (MgCO3), )
◦ olivine ((Mg,Fe)2SiO4),
◦ carnallite (KCl.MgCl2.6H2O),
◦ CaCO3 (in the forms of chalk, limestone and marble),
◦ gypsum (C SO4.2H
(CaSO 2H2O)
O),
◦ celestite (SrSO4),
◦ strontianite (SrCO3) and
◦ barytes (BaSO4).
 The natural abundances of Be, Sr and Ba are far less than
those of Mg and Ca
 Be-7 and Be-10 are found as
trace isotopes
 Ca  actually there are 22
isotopes but most of which are
highly radioactive and have
half-lives in the several
millisecond to several day
range. The only notable
exception is barium-133
which has a half-life
f f off 10.51
years.
 Sr-89 is a short-lived artificial
radioisotope that is used in
the treatment of bone cancer
cancer.
 Sr-90 (half-life = 28.9 years)
is a by-product of nuclear
fission and found in nuclear
fallout.
 Ra  All of the 25 isotopes of
radium are radioactive, and
while radium-223, radium-
224, and radium-228 are
found in nature as decay
products of either uranium or
thorium, they are only present
in trace amounts.
 Be & Mg  greyish metals
 Ca & Sr soft and silver-coloured
 Malleable, ductile and quite brittle
 In air the shiny surface of each metal quickly
tarnishes
 Of the group 2 metals, only Mg is
manufactured on a large scale.
◦ Dolomite is thermally decomposed to a mixture of
MgO and CaO, and MgO is reduced by ferrosilicon
in Ni vessels;; Mg
g is removed by
y distillation in vacuo.

◦ B
By electrolysis
l t l i off fused
f d MgCl
M Cl2 : precipitation
i it ti ffrom
dolomite  product : Mg(OH)2, neutralization and
evaporation
 2 ways :
◦ Reduction
R d i off BeF
B F2
(Be is obtained from beryl by first heating with
Na2SiF6  products : BeF2 and Be(OH)2)

◦ Electrolysis
y of BeCl2
reaction?
 Be and Mg are possible to be ontained by
reducing their oxides with the carbon
BeO + C  Be + CO
MgO + C  Mg + CO
 Ca  By electrolysis of fused CaCl2 and CaF2
 Sr and Ba 
◦ by reduction their oxides by Al
◦ By electrolysis of MCl2 (M = Sr
Sr, Ba)
 atomic properties

physical properties
11 4/8/2015
 Atomic size  increasing down the group; smaller than alkali metal
 Ionic size  increasing down the group; smaller than alkali metal
 density
d i property  decreases
d slightly
li h l upto Ca
C after
f which
hi h it
i increases;
i
more denser, heavier and harder than alkali metal
 melting point, boiling point  higher than alkali metals
 Ionization energy  IE1 decreasing down the group; higher than alkali
metals, IE2 decreasing down the group; higher than alkali metals
 Electropositive  increasing down the group; less electropositive
character than alkali metals
 El t
Electronegativity
ti it  decreasing
d i d
down ththe group; hi
higher
h than
th alkali
lk li metals
t l
 Oxidation number/valency  hint : higher degree of hydration ; electron
configuration

 Reducing character  standard oxidation potential increasing down the

group; less
l powerful
f l than
h alkali
lk li metals
l
 Ca = orange-red but pale green when viewed through blue glass
 Sr
S = crimson
i but
b violet
i l through
h h blue
bl glass
l
 Ba = apple green
 Light, strong metal, good
conductor of heat and
electricity
y
 To add strength to other
metals without adding much
weight
 Beryllium copper—used to
make tools which are to be
used in hazardous
environment,- productions
of bullets, precision
measurement devices and in
aerospace
 Very costly, £ 10,000 /kg
 Moderate light stregth to weight ratio
 Good conductor of heat and electricity
 Similar with Be, Mg is used in alloys to
add strength without adding much
weight
i h
 Mg-Al-Cu (duralumin)  used in
aircraft, car, bike frames and small boats
 Alloys with rare earth minerals, it
becomes temperature resistant to build
car engines
 Other Mg alloys are used in the
production of household material
 Mg is used as flares and distress signals
(guess why?)
 Mg bombs were dropped on Germany
during WWII
 MgO  used in refractory lining material
 MgSO4 is used as epson salts (artificial
snow), fertilizers
 Mg(OH)2 as an antacid
 As a constituent od chlorophyll
 Low strength to weight ratio
 Good conductor of heat and electricity
 Most Ca found in CaCO3
 Found in human body (bones, teeth, etc)
 Used in toothpaste, vitamins, antacid, etc
 Gypsum (CaSO4.2H2O)
 CaCO3  in limestone, chalk,
 marble is very important in the construction
industry (as decorative stone)
 Lime is used in paper making, food,
cosmetic, pharmaceutical, toothpaste,
chewing gum, and vitamins. It is also used
for treating industrial waste.
 CaH2  used as irreversible drying agent
 Other drying agents  MgSO4, CaCO4,
CaCl2, Na2SO4, K2CO3
 CaCl2  de-icer
 Good conductor of
heat and electricity
 Used in fireworks
and flares
 Used as a glas
additive
 BaSO4  as lubricating mud in drilling
operations
 Alloys : Ba-Ca-Pb
 B i
Barium meall  relatively
l i l opaque to X X-rays
and shows particulary well on X-ray
photographs
 Used in medical field
 as cancer treatment, and as a tracer for
medical imaging, although because safer
radioactive elements have been discovered it
is rarely used any more.
 Reactivity 
increases

Size of the atom 
increases
 The metals reduce O2 to form oxides:
∆
◦ 2M(s) + O2(g) → 2MO(s) (M = Be, Mg or Ca)
◦ 2M + O2  MO2 (M = Sr, Ba)
 The larger metals reduce water to form H2 gas:
◦ 2M(s) + H2O(l) → 2M2+(aq) + 2OH-(aq) + H2(g) (M = Ca, Sr, Ba)
 The metals reduce halogens to form ionic halides:
∆
◦ M(s) + X2 → MX2(s) [X = F (not with Be), Cl, Br, I]
 Most of the elements reduce H2 to form ionic hydrides:
◦ M(s) + H2(g) → MH2 (s) (M = all except Be)

 The elements reduce nitrogen to form ionic nitrides:

◦ 3M(s) + N2(g) ∆
→ M3N2(s)

 Except for BeO,

BeO the element oxides are basic:
◦ MO(s) + H2O(l) → M2+(aq) + 2OH-(aq)
 Except for BeO, the element oxides are basic:
◦ MO(s) + H2O(l) → M2+(aq) + 2OH-(aq)
◦ Be is the only alkaline earth metal that does not react with
water. This is due to its small size and high ionization
energy in relation to the other elements in the group.
 All carbonates undergo thermal decomposition:
∆
MCO3(s) MO(s) + CO2(g)
 Reacting with sulfur ∆
8M + S8 8MS
 Reacting with C
∆
◦ 2Be(s) + C(s) → Be2C(s)
∆
◦ M(s) + 2C(s) → MC2(s) (contains )
 Mg2C3contains the linear [C3]4-, isoelectronic
with
i h CO2 formed
f dbby h
heating
i M
MgC C2 or by
b
reaction of Mg dust with pentane vapour at
950 K

 Reaction of Mg2C with water produces

MeC≡CH
 Halides
 Oxides
 Hydroxides
 Salts of oxoacids
 Complex ions in aqueous solution
 C
Complexes
l with
ith amido
id or alkoxy
lk li
ligands
d
 Metal of group IIA react with halogens directly, on heating, to
form alides having general formula MX2
M+X2  MX2 (X=(X F,F Cl,
Cl Br,
Br I)
 These halides can also be obtaines by the action of halogens
acids on metals, their oxides, carbonates and hydroxides
M 2HX  MX2 +H
M+2HX H2
MO+2HX  MX2 +H2O
MCO3+2HX  MX2+H2O+CO2
M(OH)2+2HX  MX2+2H2O
 BeF2 can be prepared by thermal decomposition
(NH
( 4)2BeF4  BeF2 +2NH4F
 BeCl2 is prepared indirectly from its oxide as follows (at 600-
800 K):
BeO+C+Cl2  BeCl2+CO
 Beryllium halides  covalent; others are ionic
 BeF2  very soluble in water
 BeX2  colourless, deliquescent crystals
 BeCl2
But…
……

Linear  dimer  polymer

Planar  ….  ….
Explain why?
 Beryllium halides  covalent; others are ionic
 BeF2  very soluble in water
 BeX2  colourless, deliquescent crystals
 BeCl2
But…
……

Linear  dimer  polymer

g
Planar  trigonal planar  tetrahedral
p
Explain why?
 A deliquescent substance absorbs water from
the surrounding air and eventually forms a
liquid.

 A hygroscopic solid absorbs water from the

surrounding air but does not become a liquid
liquid.
 MgF2, CaF2, SrF2 and BaF2  ionic, high
melting points,
points sparingly soluble in water,
water the
solubility increasing slightly with increasing
cation size

Inverse polarization

Quasilinear  a species for which the calculated energy difference

between linear and bent structures (with a change in angle of >208) is
less than 4 kJ mol-1.
 Inverse polarization
 Participation of d atomic orbitals
 MgX2 (X = Cl, Br, I)
◦ its hydrate salts will partially hydrolyzed when
heated
◦ Its anhydrous salts can be prepared by
dehydration of hydrated salts  hygroscopic
 CaCl2  by-product of solvay process

Crystalline complexes in
pyridenine, THF 
 Have general formula MO and are basic
 BeO  insoluble white solid;
 prepared by thermal decomposition of corresponding
carbonate or hydroxides releasing CO2 gas
 They have high lattice
energies
g and meltingg
points
 MgO is suitable as a
refractoryy material 
why?
 Refractory materials are
suitable for use in furnace
linings; such a material
has a high melting point,
low electrical conductivity
and high thermal
conductivity, and is
chemically inert at the
high operating
temperatures of the
furnace.
 The action of water on MgO slowly converts it to
Mg(OH)2 which is sparingly soluble.
 Oxides of Ca, Sr and Ba react rapidly and exothermically
with water, and absorb CO2 from the atmosphere.

 The conversion of CaO to calcium carbide and its

subsequent hydrolysis is industrially important

 BeO and MgO insoluble and sparingly soluble in water

 why?
 BeO dissolves in acid and alkali g
give salts
 MO2  M = Mg, Ca, Sr and Ba; the stability (decomposition
reaction)) increases with the size of M2+ ion. r+ increases 
∆latticeHo (MO,s) is always more negative than ∆latticeHo
(MO2,s)

 BeO2  failed to be prepared

 strong oxidizing agents
 MgO2  prepared by reacting MgCO3 or MgO with H2O2
 CaO2  prepared by dehydration of CaO2.8H2O which
prepared from

 SrO2 and BaO2  SrO (or BaO) + O2

 Reactions peroxides with acids  products: hydrogen
peroxides
 The lattice energies of SrO and SrO2 are -3220 and
-3037
3037 kJ/mol
kJ/ l
 Why does SrO2 have less negative lattice energy
tthan
a SSrO?
O (est
(estimate
ate from
o : Kapustinskii
apust s equat
equation)
o )
Radius O22- = 126 pm
Radius [O2]2- = 180 pm
 The stabilities of M(OH)2 (M = Mg, Ca, Sr, Ba)
increase down the group

 Mg(OH)2  weak base

 Ca(OH)2, Sr(OH)2, Ba(OH)2  strong base
 An oxoacid is an acid that
◦ contains oxygen
◦ contains at least one
other element
◦ has at least one hydrogen
atom bound to oxygen
◦ forms an ion byy the loss
of one or more protons.
 BeCO3+H2O  [Be(H2O)4]2+
 Basic beryllium acetate
 Rainwater is not chemically pure water.
◦ Contains dissolved atmospheric gases.
◦ Once on the ground it may pick up a few to about
1000 ppm of dissolved substances.
◦ If the water contains ions capable of forming a
precipitate we say that the water is hard.

 Hardness may be permanent or temporary.

 Contains HCO3- ion.
◦ When heated g gives CO32-,
CO2 and H2O.
◦ The CO32- reacts with
multivalent ions to form
precipitates.
(for example CaCO3,
MgCO3)
 Soften water by
precipitating the multivalent
ions using slaked lime
lime.
 Contains significant concentrations of anions
other than carbonate.
◦ For example SO422-, HSO4-.
◦ Usually soften by precipitating the Ca2+ and
Mg2+ using sodium carbonate leaving sodium
salts in solution.
solution

 Bathtub ring is caused by

salts off Mg2+
2 and Ca2+
2 of
f
palmitic acid
(a common soluble soap).
  Ion exchange.
◦ Undesirable cations,
Mg2+ Ca2+ and Fe3+
are changed for ions
that are not as
undesirable, ex. Na+.
◦ Resins or zeolites
zeolites.

Prentice-Hall © 2002
 Contains Mg2+ and Ca2+
 Temporary hardness
◦ The presence of hydrogencarbonate salts and can be
overcome by boiling or by adding appropriate amount
of Ca(OH)2

 Permanent hardness
◦ Caused by other Mg2+ and Ca2+ salts (e.g. sulfates)
 Water softening  by passing the hard water through a
ti h
cation-exchange i zeolite,
resin, lit etct
 A hydrate X.nH2O in which n =1/2 is called a
hemihydrate; if n = 1 1/2, it is a sesquihydrate. (e.g.
CaSO4.½H2O)
 Solutions of beryllium
salts
lt are acidic
idi
 Aqua species of Mg2+,
Ca2+, Sr2+ and Ba2+
◦ [Mg (H2O)6]2+
◦ [Ca (H2O)6]2+
 With ligands : [EDTA]4- and [P3O10]5-
 Macroligands : crown ethers and cryptands, form
stable complexes with Mg2+, Ca2+, Sr2+ and Ba2+
 the stability constants for complexation with
cryptand-222 (cavity radius 140 pm) in water
follow the sequence Ba2+ > Sr2+ >> Ca2+ > Mg2+
 Group 1 - Alkali metals
Group 2 - Alkaline earth metals
The s-block
s block metals are used as reducing agents for an immense number of different
types of compounds.
Reactions of the elements with water:

( ) + H2O(l)  M (aq)
Group 1: M(s) ( ) + (OH) (aq)
( ) + ½ H2(g)
+ -
2( )

Group 2: M(s) + 2 H2O(l)  M+2(aq) + 2 (OH)-(aq) + H2(g)

These reactions are very exothermic and increase in violence from the lightest to the
heaviest elements in the group (enough to ignite the H2 for the heavier elements).
The non-reversible nature of this reaction means that such metals are very useful for
drying many kinds of solvents
solvents. More generally:

Group 1: M(s) + HOR  M+ + (OR)- + ½ H2(g)

Group 2: M(s) + 2 HOR  M+2 + 2 (OR)- + H2(g)
These reactions make metal alkoxides that are very useful for the synthesis of other
products using metathesis reactions. Metathesis indicates that the reagents
exchange ligands with one another. Such reactions are especially favourable when it
produces a metal halide because of the large exothermicity provided by the lattice or
hydration energies.
e.g.’s MOR + ClPR’2  MCl + R’2POR
MNR2 + ClSiR’3  MCl + R’3SiNR2
 Group 1 - Alkali metals
Group 2 - Alkaline earth metals
One of the most important discoveries in synthetic chemistry
was made by Victor Grignard (Nobel Prize 1912) following the
initial work of others. He showed that the reaction of Mg with
organic iodides (RI, later applied to other halides) results in the
insertion of the Mg into the R-I bond. This provides a reagent of
the form R-Mg-I that can be used in nucleophilic or metathesis
reactions to make new carbon-carbon bonds.
M R I  R-Mg-I
Mg(s) + R-I RM I
R-Mg-I + I-R  R-R + MgI2
O O
B + C
M Br
Mg C + MgBr
M B
O O Cp*2Mg
Analogous and more reactive reagents can be made with Li and Na.
2 Li(s) + R X R
R-X Li + Li
R-Li X (X = h
Li-X lid )
halide)
R-Li + X-R’  R-R’ + Li-X
Such compounds were among the first that were recognized to
contain bonds between metals and carbon
carbon. These were thus
some of the initial examples of organometallic chemistry (one of
the most studied branches of inorganic chemistry today). (Cp*Na•THF)
 Group 1 - Alkali metals
Group 2 - Alkaline earth metals
y
The s-block metal hydrides are also very
y useful compounds
p that can usually
y
be made by the reaction of the metal with H2(g); this does not work for BeH2 -
you can use a Born-Haber cycle to figure out why. The H atoms are hydrides
(H-), which gives them a totally different kind of chemistry than protons (H+).
All of the ss-block
block hydrides are ionic except for LiH
LiH, BeH2 and MgH2, which
have significant covalent character.

H Be H

Group 1: M(s) + ½ H2(g)  MH (s)

Group 2: M(s) + H2(g)  MH2(s) Gas phase

The coordination polymer solid state structure of BeH2 is similar

to that of BeCl2

These reagents also react with water in a very exothermic fashion to make gaseous
H2. The non-reversible nature of this reaction means that such metal hydrides
(especially CaH2) are also very useful for drying many kinds of solvents
solvents.

More importantly, the group 1 and 2 metal hydrides are excellent reagents for putting
H atoms onto other elements by metathesis reactions:
e.g.’s 3 LiH + PCl3  PH3 + 3 LiCl
2 LiH + BeCl2  BeH2 + 2 LiCl
4 LiH + AlCl3  Li[AlH4] + 3 LiCl
 Group 1 - Alkali metals
Group 2 - Alkaline earth metals
g , most of the s-block metal halide or
Because of their low electronegativities,
chalcogenide compounds are salts with ionic structures. The lattice (or hydration)
energies of such compounds are often used to drive reactions to completion.
The alkali earth metal ions resemble the alkali
metal
t l ions
i in
i having
h i a low
l electronegativity,
l t ti it andd
being very hard in the HSAB classification. The big
difference, though, is their charge, which makes
them stronger Lewis acids.
acids The effect of charge on
log K1 for hard metal ions with EDTA, all having an
ionic radius of about 1.0 Å, makes this point (see
next slide for Ca EDTA complex):
p )

Metal ion: Na+ Ca2+ La3+

Th4+
Ionic radius (Å): 1.02 1.00 1.03
0.94
l
log K1 (EDTA):
( ) 1.86 10.65 15.36
23.2
 We thus find that the metal ions in Group 2 are
much better at complexing with ligands than are
those in Group 1. Being hard, complexing of Group
2 cations is confined largely to oxygen donors, and
to nitrogens, more so where the nitrogen donors
are part of a ligand that also has some oxygen
donors such as in EDTA.
donors,

H2O OH2
O O
O O
O O
Ca
O O
N N

[Ca(EDTA)(H 2O)2]2-
2

EDTA
The alkali earth metal ions Ca2+, and particularly
Sr2+, and Ba2+ are large enough to fit well into the
cavities of crown ethers and cryptands, and
actually form more stable complexes than large
alkali metal ions. Thus we can compare log K1
ions Thus,
values with some crown ethers and cryptands for
Ba2+ and K+, which are almost identical in size:

Ligand: 18-crown-6 15-crown-5 cryptand-

222

log K1(K+): 2.05 0.75 5.5

log K1(Ba2+): 3.89 1.71 9.6

Thus, even with these ligands,

Thus ligands the charge on the
metal ion has an effect on complex stability.
 Others… will be dicussed in elements of
group
g p 13