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Lecture Outline
1.
Introduction
2.
3.
4.
5.
Diagonal Relationship
6.
Learning
Outcomes
References
Chemistry for Advanced level, Peter Cann & Peter Hughes, 1st Edition, John McMurray (Publishers) Ltd
Chemistry, 3rd Edition, McGraw Hill
Useful Websites
http://www.chemguide.co.uk/inorganic/group2menu.html
http://sockkhim.edu.glogster.com/properties-of-grp-ii-compounds/
http://sockkhim.edu.glogster.com/group-ii-physical-properties/
http://sockkhim.edu.glogster.com/chemistry-properties-of-group-ii-metals/
Group II Elements
1.
INTRODUCTION
The Group II elements are also known as the alkaline earth metals for two reasons:
a)
Their oxides (white solids) form alkaline solutions when dissolved in water.
CaO(s)
lime
H2O(l)
Ca(OH)2(s)
slaked lime
Ca(OH)2(s)
slaked lime
H2O(l)
Ca(OH)2(aq)
limewater (alkali)
b)
In ancient times, alchemists attempted to obtain pure metals from their ores by heating.
They often encountered the Group II oxides in their furnaces. As these Group II oxides
melt at very high temperatures, they remained as solids in these alchemists fires.
Hence, these solids were referred to as earth which to the alchemists were materials
which did not melt just like the sand and soil due to their extremely high melting points.
Electronic Configuration
Element
Electronic Configuration
Short
Form
1st IE
2nd IE
3rd IE
Be
1s2 2s2
[He] 2s2
900
1760
14800
Mg
[Ne] 3s2
736
1450
7740
Ca
[Ar] 4s2
590
1150
4940
Sr
[Kr] 5s2
548
1060
4120
Ba
1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d105s2 5p6 6s2
[Xe] 6s2
502
966
3390
These elements form ions with +2 charge by losing their 2 outermost electrons.
M
Eg.
M2+
+ 2e
Be
Be2+ +
2e
Mg
Mg2+ +
2e
Group II Elements
Why should the Group II metals have a fixed oxidation state of +2?
Question:
The outermost 2 electrons in the ns shell are easily removed as they are shielded from
the nucleus by the inner core electrons. Hence +2 oxidation state is easily and mainly
formed.
MX2
q q
r r
M
), MX2 compounds are more stable
than MX compounds.
The +3 oxidation state:
The +3 oxidation state is not possible as the 3rd IE is significantly greater than either 1st
or 2nd IE. As the 3rd electron would be removed from an inner quantum shell, this
process requires too much energy which cannot be compensated by the higher lattice
energy of MX3 compounds.
2.
Boiling
Point/ OC
Melting
Point/ OC
Atomic
Radius/ nm
Ionic
Radius/ nm
Density/
g cm3
Be
Mg
Ca
Sr
Ba
2477
1100
1487
1380
1640
1280
650
850
768
714
0.112
0.160
0.197
0.215
0.217
0.031
0.065
0.099
0.113
0.135
1.84
1.73
1.55
2.63
3.51
Mg
Ca
Sr
Ba
0.16
0.065
0.20
0.099
0.21
0.11
0.22
0.14
2.1
Atomic radius/nm
0.11
Ionic radius/nm
0.031
Trend:
Group II Elements
2.2
Ionisation Energies
Trend:
Group II Elements
2.3
Electronegativity
It is the ability of an atom in a molecule to attract electrons to itself.
Electronegativity:
Trend:
Be
1.5
Mg
1.2
Ca
1.0
Sr
1.0
Ba
0.9
higher
level shell.
Quickcheck 1:
State and explain why the atomic radius of Ba is greater than Mg.
Group II Elements
2.4
(Also see Table 2 on page 3 for melting and boiling points values).
a) Trend:
Reason:
b) Trend:
Group II Elements
c) Trend:
Melting point of Group II elements are lower than those of transition elements
Fe
Co
Ni
Cu
1550
1492
1453
1083
Atomic Radius/nm:
0.116
0.116
0.115
0.117
Group II Elements:
Be
Mg
Ca
Sr
1280
650
850
768
0.112
0.160
0.197
0.215
Transition Elements:
Melting Point/oC:
Melting Point / C:
Atomic Radius/nm:
Reason:
Group II elements:
Contribute only 2 valence electrons per atom for metallic bonding
Bigger ionic radii
Transition Elements:
Contribute more than 2 valence electrons (4s and 3d electrons)
per atom for metallic bonding
Smaller ionic radii
Relatively weaker electrostatic attraction between cations and sea of delocalised
electrons in Group II elements.
Hence, weaker metallic bond strength in Group II elements.
(Also to be discussed in The Introduction to the Chemistry of Transition Elements)
2.5
Group II Elements
3.
3.1
Reactivity
Trend:
3.2
a)
The E [standard redox potential] value is a measure of the tendency of the species
to undergo reduction.
2+
Be (aq)
Mg2+ (aq)
Ca2+ (aq)
Sr2+ (aq)
Ba2+ (aq)
Mn+ + ne
Element
+
2e
+
2e
+
2e
+
2e
+
2e
Be(s)
Mg(s)
Ca(s)
Sr(s)
Ba(s)
The more negative the E value, the greater the tendency for oxidation
(backward reaction) to occur.
The E values of Group II elements are very negative indicating that they are
easily oxidised
b) Trend:
Group II Elements
3.3
General equation:
2M (s)
O2 (g)
2MO (s)
Reactivity of metals with oxygen increases on going down the group, a consequence
of the increase in reducing strength of the metals.
All the oxides are white solids, basic and ionic in nature and have extremely high
melting points (except for BeO). BeO is amphoteric.
Examples:
Note:
2Be(s)
O2(g)
2BeO(s)
2Mg(s)
O2(g)
2MgO(s)
2Ca(s)
O2(g)
2CaO(s)
2Sr(s)
O2(g)
2SrO(s)
2Ba(s)
O2(g)
2BaO(s)
O2 (g)
BaO2 (s)
Group II Elements
3.4
Important!
Group II elements (except Be and Mg) reduces water to produce hydroxides and H2
General Equation:
M (s)
2H2O (l)
M(OH)2
H2 (g)
Reactivity
Be
Nil
Mg
Ca,
Sr,
Ba
hydrogen gas.
(steam)
The Group II hydroxides are not very soluble, but they get more soluble down the
group. Calcium hydroxide (also known as slaked lime) is present mainly as a white
precipitate (although some does dissolve to form limewater).
All the hydroxides are basic except for Be(OH)2 which is amphoteric.
Quickcheck 2:
2, 3 are correct.
10
Group II Elements
Important!
4.
Nature of oxides:
The oxides of Group II elements are all basic except for BeO which is amphoteric.
Ionic oxides are basic while covalent oxides are acidic. The
amphoteric oxides possess both the ionic and covalent character.
BeO is amphoteric because the small Be2+ ion has high charge density and it
polarises the O2 anion and result in some degree of covalent character in the
bonding of BeO.
[Compare this with what you know about Al2O3. Are they similar?]
Yes.
4.1
All Group II oxides (except BeO) react with water to form hydroxides.
General Equation:
MO (s)
H2O (l)
M(OH)2 (aq)
Reaction of group II oxides with water increases with vigor down the group:
Reactivity
Oxides
Nil
MgO
Mg(OH)2(s)
Quickcheck 3:
Group II metal, X, reacts only very slowly with cold water but
vigorously with steam. Group II metal, Y, readily reacts with cold water. Suggest the identity
of X and Y, and give a reason for your choice.
Answer:
X = Mg; Y = Ca, Sr or Ba.
Reactivity increases down the group.
11
Group II Elements
4.2
The nitrates and carbonates of Group II elements are thermally unstable; they
decompose on heating to form stable oxides.
Nitrates decompose on heating to give oxides, nitrogen dioxide and oxygen:
General Equation:
2M(NO3)2 (s)
2MO (s)
4NO2 (g)
O2 (g)
brown gas
MCO3 (s)
MO (s)
CO2 (g)
O
M
2+
C
O
2+
Charge Density
q
r
High cationic
charge (q+), small
cationic radius (r+)
high charge
density
Polarising Power refers to the ability of cation M2+ to distort the electron cloud of
the anion
In general, the higher the charge density of M2+, the greater the polarising power of
the cation.
Note :
Group II salts are less stable than Group I salts because of the
greater polarising power of the M2+ cation, which distorts the anion
more.
12
Group II Elements
NO bond in the NO3 anion is polarised and weakened by the cation such that the
NO bond break and MO, NO2 and O2 are formed.
O-
M2+
N O
2MO
4NO2
O2
O
Cleavage of the NO bond lead to decomposition
4.3
Compound
Mg
Ca
Sr
Ba
Very Important!
DECOMPOSITION TEMPERATURE/ 0C
Nitrates
Carbonates
129
540
560
900
570
1290
592
1350
Group II nitrates and carbonates have to be heated more and more strongly down
the group before they will decompose.
Recall:
Charge Density
Note:
q
r
Group II Elements
Quickcheck 4:
Route 1
Route 2
5.
(A)
C. Q S U
D. Q S T
DIAGONAL RELATIONSHIP
GROUP I
GROUP II
GROUP III
Li
Be
Na
Mg
Al
Ca
Ga
Both Mg2+ and Li+ have similar charge density and polarising power.
Both Be2+ and Al3+ have similar charge density and polarising power.
Beryllium shows quite different chemical behaviour when compared to the rest of
Group II metals. In fact, it is closer to aluminum in its chemical properties.
o
o
o
o
o
14
Group II Elements
6.
Barium sulfate (BaSO4) is used in barium meal test in Xray diagnostic work.
15
1.
The element strontium is placed below calcium and above barium in Group II.
(a)
Rubidium (Rb) is next to strontium in the same period. Account for the difference in the
ionic radius Rb+ and Sr2+.
Ion
Rb+
Sr2+
Ionic radius
0.148 nm
0.113 nm
(b)
How should the ionisation energy of strontium compare with that of:
(i)
rubidium
(ii)
calcium
Explain your answer.
2.
(a)
The alkaline earth metals (beryllium, magnesium, calcium, strontium and barium) all
have a fixed oxidation number in their compounds.
(b)
The group II elements are strong reducing agents (E values are negative and the
magnitude increases on going down the group). Give an explanation for this property
and the trend in this property on going down the group.
3(a)
(b)
(i)
Suggest reasons why magnesium gives the nitride, Mg3N2, in addition to its
oxide when burned in air.
(ii)
A 1.00 g sample of the powder obtained from burning magnesium in air was
boiled with water. The ammonia that was evolved neutralised 12.0 cm3 of 0.5
moldm3 hydrochloric acid.
Construct balanced equations for the production of magnesium nitride and its
reaction
with water. Calculate the percentage of magnesium nitride in the
1.00 g sample.
[Ans: 30.3%]
II
*4
(a)
(b)
(c)
Group II Elements
(a)
Beryllium chloride (boiling point 547C) is much more volatile than magnesium chloride
(boiling point 1418C).
(b)
Beryllium oxide is amphoteric, but the oxides of all the other alkaline earth metals are
basic.
*6
Heating barium oxide with oxygen under pressure causes barium peroxide to be formed
in the following equilibrium reaction:
2BaO + O2
2BaO2
When 1.00 g of the mixture of oxides (BaO and Ba2O) was treated with dilute sulfuric
acid, 1.49 g of a white solid was precipitated and a solution of hydrogen peroxide was
produced. On the addition of an excess of acidified potassium iodide to the solution,
0.00118 mol of iodine, I2, was produced.
Suggest an identity for the white solid and write an equation for the reaction of each of
the oxides with dilute sulfuric acid. Use the above data to calculate the mass of each
oxide present in the mixture.
[Ans: BaO2 = 0.199 g ,BaO = 0.801 g]
7(a)
State and explain the relative thermal stability of calcium nitrate and strontium nitrate.
(b)
(i)
When a 1.01 g sample of potassium nitrate is heated above its melting point, a
colourless gas is evolved and the mass of the sample decreases by 0.16 g.
Suggests an identity for the gas and for the resulting solid, and hence construct
an equation for the decomposition.
*(c)
(ii)
Unlike all other Group I nitrates, lithium nitrate decomposes on heating in the
same
way as Group II nitrates. Suggest a reason for this difference in
behaviour and give an equation for its decomposition.
(i)
When water is added to the solid remaining after barium nitrate has been
heated, an alkaline solution is produced. The addition of sulfuric acid to this
solution produces a white precipitate. Identify the products of these two
reactions, and write equations for them.
(ii)
When the procedure described in (a) is repeated using the solid remaining after
magnesium nitrate has been heated, several differences are observed. Describe
clearly what these differences are, and explain why they occur.
The following table lists the melting points of the oxides of the Group II elements.
oxide
MgO
CaO
SrO
BaO
melting point/ C
2852
2614
2430
1918
(a)
(b)
Suggest a use for one of these oxides, based on its melting point.
17
Group II Elements
(c)
The mineral dolomite is a double carbonate of magnesium and calcium, with the
formulae CaMg(CO3)2. When 1.000 g of an impure sample of dolomite was completely
dissolved in an excess of hydrochloric acid, 0.450 g of carbon dioxide was given off.
Write a balanced equation for the reaction and calculate the purity of the dolomite.
[Ans: 94.3%]
*9 (a) Explain the following observation as fully as you can. Include any relevant equations.
Magnesium nitrate produces a brown gas on gentle heating whereas barium nitrate
gives a brown gas only on prolonged heating.
(b)
(a)
(b)
Magnesium reacts with ammonia to form a yellow binary salt, X, and hydrogen. In
another experiment, 0.198g of compound X upon complete reaction with water gives a
white solid Y. Upon filtering to remove the white solid Y, the resultant solution which
contains ammonia requires 20.0 cm3 of 0.1 mol dm3 sulfuric acid for reaction.
Construct balanced equations for the two reactions.
(c)
(d)
The solubility products of some Group II compounds are shown in the following table:
Ba(OH)2
Ca(OH)2
Mg(OH)2
BaCO3
2.60 x 109
7.88 x 106
CaCO3
4.95 x 109
12
5.66 x 10
MgCO3
1.15 x 105
(i)
With reference to data given above, suggest a reason why when small quantities
of carbon dioxide are to be detected, barium hydroxide solution is occasionally
used instead of limewater.
(ii)
18
Group II Elements
2. On strong heating, CaSO4 decomposes into CaO and SO3. The compound CaCO3
decomposes at a lower temperature than CaSO4. Which factor best explains the greater
thermal stability of CaSO4?
[J99/P3/Q14]
A.
B.
C.
D.
MO (s)
CO2 (g)
Mg
+101
Ca
+178
Sr
+235
[N00/P3/Q14]
Ba
+269
4. A student made up a 0.10 mol dm3 solution of Ba(OH)2.8H2O which she found in the
laboratory cupboard and left the solution in an open beaker. A week later, she returned to
the laboratory, used the solution for titration with 0.10 mol dm3 HCl and was surprised to
discover her titres were lower than expected.
What explains why the values were low?
[N08/P1/Q15]
A. Some of the barium hydroxide had reacted with carbon dioxide in the air to form solid
barium carbonate.
B. Some of the water had evaporated from the barium hydroxide solution.
C. The concentration of HCl was less than the stated 0.10 mol dm3.
D. The crystals had less water of crystallisation than stated.
19
Group II Elements
For Qns 59, choose from any of the following combination of statements.
A
1, 2 & 3 are
correct
B
1 and 2 only are
correct
C
2 and 3 only are
correct
D
1 only is correct
E
3 only is correct
5. Which of the following statements concerning the Group II elements, magnesium, calcium
and barium are correct?
[N89/P3/Q35]
1. Their reactivity increases with increasing relative atomic mass.
2. The only oxidation number exhibited in their stable compounds is +2.
3. On strong heating their nitrates give off oxygen only.
6. Anhydrous barium nitrate and anhydrous magnesium nitrate both decompose on heating,
evolving nitrogen dioxide and oxygen and forming an oxide. Which of the following
statements concerning these decompositions are correct?
[J93/P4/Q36]
1. Nitrogen dioxide is evolved at a lower temperature from magnesium nitrate than from
barium nitrate.
2. For both nitrates the volume of nitrogen dioxide evolved is four times greater than the
volume of oxygen.
3. The numerical value of the lattice energy of magnesium nitrate is greater than that of
barium nitrate.
7. Soluble barium compounds are highly toxic. In hospitals, barium sulfate in suspension is
safe for use in taking Xray photographs of the alimentary canal. It is mixed with food and
eaten by the patient prior to the photographs being taken.
Why is sulfate used rather than other compounds of barium?
[N93/P4/Q35 modified]
1. Barium sulfate is not poisonous because it is insoluble in water.
2. Barium sulfate reacts with organic materials in the body.
3. Barium sulfate forms sulfuric acid with the acid in the stomach.
8. Which of the following statements about beryllium are true?
[J85/P3/Q36]
20