Inorganic Chem 1 2 PDF
Inorganic Chem 1 2 PDF
Acholi Felix,0773915983
Introduction
Inorganic chemistry is the study of substances other than carbon compounds through a few of the
latter are, conventionally included in inorganic chemistry
Early studies in inorganic chemistry were directed towards solving analytical and mineralogical
problems. There is ,too, a mass of relatively factual information concerning the preparation,
manufacture, properties factual and uses of inorganic chemicals
Periodic Table
The original form of the periodic table was first put forward by Mendeleef in 1869 when he arranged
the known elements in the order of their relative atomic masses.
The elements fall into 8 vertical groups numbered from I-VIII and horizontal rows of elements are
known as periods which are 7 numbered 1-7.
Those periods containing 8 elements are known as short periods and the others as long periods
The elements in any one vertical group have similar chemical and physical properties
Therefore the properties of elements are periodic function of their atomic number which is periodic
table
Electronic configuration
Describes how the electrons of an atom are arranged in the energy levels, subshells and orbitals. The
term normally applies to an atom in their ground states
The electrons in the ground state occupy orbital’s in order of the orbital energy levels. The lowest
energy orbital’s are always filled first
e.g. for 3 Li
1S 2S
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Rule 2: Pauli Exclusion Principle
This states that an orbital can not contain more than two electrons and then only if they have
opposite spins
e.g. 3 Li
1S 2S
This states that the orbital’s of a subshell must be occupied singly first and with parallel spins before
they can be occupied in pairs
e.g. 7 N
1S 2S 2P
1S22S22P3
Rule 4:
Electrons in degenerate orbital’s which are singly occupied have parallel spins
1S
2S 2P
3S 3P 3d
4P 4d 4f
4S
5P 5d 5f
5S
6d 6f
6S 6P
7S
2
Principal quantum number , n where n= 1,2,3,4 etc
This denotes the principal quantum energy shell in which the electron in an atom is found. Within the
principal quantum energy shell there are shells but the total number of electrons that can occupy any
principal quantum shell is given by 2n2
The inner most orbital i.e. the one nearest to the nucleus has principal quantum number of 1 and the
number of electrons in each energy level is shown as
n 1 2 3 4 5
Max. no. of 2 8 18 32 50
electrons
Within the principal quantum energy shell there are subshells which are denoted as s, p, d and f and
the number of electron that an orbital can accommodate is shown as
orbital S P d f
No. of electron 2 6 10 14
Question
Write the electronic configuration of the following elements with their respective atomic number
(i) Aluminium (Z=13) (ii) Phosphorous (Z=15) (iii) Calcium (Z=20) (iv) Chlorine (Z=17)
(v)Vanadium (Z=23) (vi) Selenium (Z=34) (vii) Nickel (Z=28) (viii) Copper (Z=29)
N.B. Fully filled and half filled orbital’s are regarded as thermodynamically more stable therefore the
electronic configuration of Chromium (Z=24) and Copper (Z=29) follow this.
The block to which an element belongs is determined by the orbital’s which are in the process of
filling up. E.g.
N.B. Electronic configuration can be used to determine the period and group of the element.
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PERIODIC PROPERTIES
Atomic radius is half the internuclear distance between two atoms of the same element joined by the
singly covalent bond.
Nuclear charge. This is the attraction of the positively charged nucleus for the outermost
electron. Increase in nuclear charge, decrease in atomic radius
Screening effect/ shielding effect. This is tendency of inner electrons to shield outer electrons
from nuclear attraction. Increase in screening effect results into increase in atomic radius.
Variation across the period
Atomic radius decreases across the period. This is because the nuclear charge increases due to the
addition of protons to the nucleus. For every proton added, an electron is added to the same energy
level and almost screening effect almost remains constant. The effective nuclear charge increases thus
the electrons become more strongly attracted and closer to the nucleus
Element Na Mg Al Si P S Cl Ar
Atomic 0.156 0.136 0.125 0.117 0.110 0.104 0.09 0.094
radius(nm)
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
At.
Radius 1.44 1.32 1.22 1.17 1.17 1.16 1.16 1.15 1.17 1.25
(oA)
The metallic radius decreases from scandium to nickel and it slightly increases from nickel to Zinc.
As atomic number increases, the nuclear charge increases. However, the electrons are being added to
inner 3d-subshell therefore these electrons are poorly shielded from the nuclear charge hence the
nuclear attraction for the outer for the most electron increases resulting into increase in atomic
radius/ metallic radius.
The slightly increase from nickel to Copper is because the 3d-subenergy level in copper is fully filled
with electrons and this increases the shielding of the outer electrons from the nuclear charge hence
atomic radius increases.
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The decrease in radius coupled with increasing atomic mass causes an increase in the density and
decrease in atomic volume in passing from Scandium to Nickel.
Atomic radius increases down the group. Both nuclear charge and screening effect increases. However
the increase in screening effect outweighs the increase in nuclear charge due to addition of extra
energy level of electrons thus the effective nuclear charge decreases such that the outermost
electrons are less strongly attracted towards the
Element Li Na K Rb Cs
At. Radius (nm) 0.123 0.157 0.203 0.216 0.235
Ionic radius
These are formed by removing one or two electrons from the outer most energy level. The nuclear
attraction for the remaining electrons increases thus the radius of the cation is smaller than that of
the atom from which it is formed.
Examples include
Formed by addition of one or more electrons to a neutral gaseous atom . The effective nuclear
charge is reduced and hence the electron cloud expands. Therefore the anions are larger than
corresponding atoms .e.g.
The first ionization energy is minimum amount of energy required to remove one mole of electrons
from one mole of free gaseous atoms to form one mole of unipostively charged gaseous cations.
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Successive ionization energies refer to loss of a second, third, …………… , nth electron. Thus the second
ionization energy of X is the first ionization energy of X+ and sum of the first n ionization energies gives
the energy change for the formation of the Xn+ ion
Nuclear Charge; ionization energy increases with increasing nuclear charge.
Screening effect: increase in screening effect decreases the magnitude of ionization energy
Nature of orbital: Electrons being removed from fully filled and half filled energy levels
require more energy because such electronic structure are stable.
Type of orbital: S, P, d and f orbital have different shapes. In energy level the S- orbital
penetrate closer to the nucleus therefore the penetrating trend is S>P>d>f hence an orbital of
higher penetrating power requires more energy
Atomic radius: Atoms with small radius the electrons are strongly bound by the nuclear
attraction and thus require more energy to be removed.
Element Li Be B C N O F Ne
I.E (KJmol-1) 520 899 801 1086 1403 1310 1681 2080
Across a period, ionization energy increases with increase in atomic number Electrons are added to
the same main energy level as nuclear charge increases. These electrons shield each other poorly from
the increasing nuclear charge therefore atomic radius decreases resulting into increase in ionization
energy along the period
However, beryllium, neon and nitrogen have abnormally high ionization energy because the electrons
are removed from 2S2,2P6 and 2P3 which are fully filled and half filled respectively and are regarded as
thermodynamically stable
Qn: The table below shows the elements in period 3 of the periodic table
Element Na Mg Al Si P S Cl Ar
Z 11 12 13 14 15 16 17 18
1st I.E 502 745 587 791 1020 1000 1260 1530
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Variation down the group
Ionisation energy decreases down the group. Both nuclear charge and screening effect increase down
the group. Due to extra energy level of electrons being added, the increase in screening effect exceeds
the increase in nuclear charge. Effective nuclear charge decreases such that the outer most electrons
become less strongly attracted hence less energy is required
Atomic number of an element. The number of successive ionization energy indicates the
number of electrons present. E.g. Mg has 12 successive ionization energies.
Arrangement of electrons and distribution of energy levels
Metallic character. Elements which easily lose electrons have low values of ionization energy
and are electropositive. The 1st ionization energy is usually below 800KJmol-1
Qn: The data given below are for the elements A, B, C and D which belong to the same period in the
periodic table
Element A B C D
1st I.E 495 580 790 1255
Melting point of
oxide ………… 2300 1610 -20
(a) Which ones of the elements A,B, C and D is a metal? Explain your answer
(b) State the type of bonding and structure of the oxides of elements A and D
(c) The 2nd, 3rd, and 4th ionization energy of element B are 1500, 7700 and 10500KJmol-1
respectively. To what group in the periodic table does B belong? Give reason for your answer
This is the energy released when an electron is gained by one mole of an isolated neutral gaseous
atom to form a uninegative gaseous ion
Electron affinity values are negative i.e exothermic process even for highly electropositive elements.
The more exothermic the E.A, the easier an atom gains electron hence the more stable the ion is.
The second E.A is accompanied by absorption of energy i.e. endothermic. This is because the incoming
electron experiences greater repulsion from both outermost electron and the negative ion. In
addition, the increased radius of the ion decreases the nuclear attraction for the incoming electron.
E.A. Values are not experimental and thus inaccurate. They are determined directly from Born-haber
cycle
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Variation across the period
Across the period, E.A increases. This is due to decrease in atomic radius and increase ineffective
nuclear charge which increases the nuclear attraction for the incoming electron thus more energy is
evolved.
N.B. E.A. of Beryllium and Magnesium are less exothermic because the electron is added to
completely filled S-orbital which is stable
Down the group, E.A decreases due to decrease in effective nuclear charge caused by addition of an
extra energy level of electrons. The nuclear charge decreases and ability of the nucleus to attract
electrons is reduced hence less energy is given out.
ELECTRONEGATIVITY
This is the tendency of an element to attract bonding electrons towards itself in a covalent compound.
Nuclear charge
Atomic radius
Screening effect
Across the period, electronegativity increases because the atoms become smaller and the effective
nuclear charge increases therefore the electron attractive power increases
Down the group, electronegativity decreases due to increasing atomic radius and decrease in effective
nuclear charge.
Element F Cl Br I
Electronegativity 4.0 3.0 2.8 2.5
ELECTROPOSITIVITY
This is the ability to lose outermost electrons to form a positively charged ion. This is basically a
property of a metallic elements because they have few electrons in the outermost energy level with
low ionization energy.
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Down the group, Electropositivity increases because:
The shielding of outer most electrons from nuclear attraction increases as more
completed energy levels are added.
Atomic radius increases
The most reactive metals are therefore found at the bottom of the group e.g. Lithium in group I reacts
slowly with cold water due to low Electropositivity value
CHARGE DENSITY
High charge. Highly charged positive ions greatly polarize anions with large negative
charge
Small radius of the Cation
Large anions. Anions with large radius are more polarisable
Polarisation affects both the chemical and physical properties of ionic compounds
Examples include:
The melting point of chlorides of Sodium, Magnesium and Aluminium are shown below
DIAGONAL RELATIONSHIP
This is the similarity in chemical properties between elements in period two to their diagonal
neighbours in period three and adjacent groups.
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N.B.The similarity in Chemical properties between the pairs See S- block elements.
ATOMIC STRUCTURE
Hydrogen Spectrum
The hydrogen spectrum consists of a series of lines both in the visible and invisible region of the
electromagnetic spectrum i.e. line spectrum.
In each series, the spacing between the adjacent lines decreases towards the continuum i.e. converge
into continuous spectrum.
For the visible spectrum, each line has a different colour and represents a radiation of definite
wavelength and frequency
I.R U.V
red violet
frequency increases
wavelength increases
When an electric discharge is passed through hydrogen gas at low pressure ,the gas molecules break
down to form gaseous atom. The hydrogen atoms absorb energy in discrete units quanta.
The electron in each hydrogen atom becomes excited and gets promoted from levels of lowest energy
(ground state) to higher energy levels far away from the nucleus.
The electron in higher permissible state is unstable and falls back towards the ground state emitting
light/ radiations with definite frequencies.
When the radiations are resolved by the spectrometer, an emission spectrum develops.
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n=
n=7
n=6
n=5
n=4
n=3
paschen series
n=2
balmer series
n=1
lyman series
Each series represent a transition from a higher energy level to a given level of lower energy.
1 1 1
RH 2 2 Where RH is Reybergs constant
n1 n2
The energy given out when an electron falls back to lower energy level is given by:
c hc
Since f , the expression can be written as E where c is speed of light
When an electron is removed from n ,it is removed from the influence of the nucleus .i.e .ionisation
Qn: The diagram below shows some energy levels in the hydrogen atom
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n
0
-82 n=4
-146 n=3
-329 n=2
-1310 n=1
KJmol-1
(a)If an electron is in ground state, what is the minimum energy for ionisation
(c) If an electron is in energy level 4 what is the frequency of the lowest energy it can emit
(h=3.99X10-13 )
Hydrogen atoms has one electron but produces a spectrum containing a series of lines
The lines in each series have definite frequency and wavelength.
The spacing between the adjacent lines in each series differs and converges into a
continuum.
The number of lines in spectro-series increases with an increase in the resolving
power of the spectrometer prism used. hence atom has got an infinite number of
energy levels
Qn: The atomic spectrum of hydrogen can be divided into a number of series
(c) Explain how ionisation energy of an element can be calculated from spectro-measurement
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BONDING AND STRUCTURE
BONDING
These are bonds formed by equal sharing of two or more electrons between two atoms in a molecule.
Each atom contributes equal numbers of electrons so that the atomic orbital overlap. The shared
electrons must be unpaired with opposite spin.
Covalent bonds are usually formed between non-metal atoms due to their high
electronegativity.e.g.Ammonia, Chlorine, carbondioxide, methane etc
When a covalent bond is formed between atoms of different electronegativity, the more
electronegative atom attracts bonding electrons towards itself leading to slight charge separation.
Examples include:
Carbondioxide and tetrachloromethane have polar bonds due to difference in
electronegativity but the bond polarity cancels out because the molecule is symmetrical
therefore they are called non-polar covalent compounds.
Trichloromethane the bonds are polar but the molecule is unsymmetrical therefore it a polar
covalent compound
They contain simple discrete molecules held by weak vanderwaals forces in simple molecular
structure e.g Sulphur,carbondioxide and giant atomic structure e.g. Silicon (IV)oxide, Diamond
They are soluble in non-polar solvents e.g. benzene
They are non-electrolyte
They have low melting and boiling point
This is weak covalent bond formed between an electron rich atom and electron deficient atom/ion.
The atom with lone pairs of electrons donates an electron pair therefore it is called donor atom and
the atom receiving the electrons is acceptor.
Examples include:
Hydroxonium, ammonium and dimerised AlCl3 and BeCl2 i.e in the vapour phase Aluminium Chloride
and Beryllium chloride exist as
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Cl Cl Cl
Cl
Al Al Cl Be Be Cl
Cl Cl
Cl
Cl
Qn: A compound contains 79.78% chlorine and rest Aluminium. The vapour of this compound has a
density of 2.28X103 gm-3 at 1427K and 1.013X105Pa
(b) State the conditions under which the above structure exists
Ionic bond is bond formed by electron transfer from electropositive element to another
electronegative atom.
The electropositive atom loses electrons to become positively charged while the electronegative atom
gains the electrons to become negatively charged.
There is a total separation of charges held by strong electrostatic forces of attraction which constitute
a large continuous arrangement of oppositely charged ions resulting into a giant ionic lattice.
The strength of the ionic bond depends on the magnitude of the forces which depends on:
Charge of the ion. Electrostatic forces of attraction increases with increase in the
magnitude of the charge on the ions.
Ionic radius. Electrostatic attraction decreases with increase in ionic radius.
This is an electrostatic attraction between the delocalized electrons of the metal atoms and positive
nucleus.
The strength of the metallic bond increases with increase in the number of delocalized electrons
Qn: The melting points of group I metals decreases down the group
Soln: The metallic radius increases therefore the delocalized electrons are held by weak forces
hence decrease in melting point.
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Qn: The table below shows the melting points of elements in period 3
Element Na Mg Al Si P S Cl
At.No. 11 12 13 14 15 16 17
Melting
point(oC) 98 650 660 1410 44 119 -101
It is a permanent bond formed by dipole-dipole attraction between the hydrogen atom and a
highly electronegative atom in a molecule with atleast a lone pair of electron
1. Solubility in water
Organic compounds with polar functional groups such as Alcohols, Amines and Carboxylic acids
are soluble due to association of the molecule with water through hydrogen bond
Hydrogen bonds in molecule elevate the boiling points due to extra energy required to overcome
the bonds before molecule vapourise
Number of hydrogen bond formed
Electronegativity of the atom
Examples include:
Since oxygen is more electronegative than nitrogen, the b.p .t of CH3CH2CH2OH is greater than
CH3CH2CH2OH.
Water molecule forms more hydrogen bond although the electronegativity of Fluorine is higher hence
a higher b.p.
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3. Density and Volume
Hydrogen bonds increases the volume and lowers the density e.g. Ice floats on water
Each oxygen atom is tetrahedrally attached to four hydrogen atoms i.e two are normal covalent
bonds and the other are longer hydrogen bond. This arrangement gives ice a more open structure
hence an increased volume therefore a fixed mass for water, the density decreases and it freezes.
Qn:
(b) State the factors that affect the melting point of:
(i) Metal
(c) Explain the trend in the melting points of the elements in group II and group IV of the periodic
Table
(d) Why are transition metals of period 4 having higher melting point than non-transition metals
of the same period.
(i) The melting point of Aluminium chloride is abnormally low compared to that
Aluminium Oxide
(ii) The melting point of Calcium oxide is higher than of Calcium chloride
The elements in this block have their valence placed in the S-orbital. The outer most configurations
are:
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Group I (Table 1)
Element Li Na K Rb Cs
Ist I.E (KJmol-1) 520 500 420 400 380
2nd I.E(KJmol-1) 7300 4600 3100 2700 2400
Atomic 0.15 0.19 0.23 0.25 0.26
radius(nm)
Melting point 180 98 63 39 29
(oC)
Density(gm-3) 0.53 0.97 0.86 1.53 1.87
Hydration -499 -390 -305 -281 -248
energy(KJmol-1)
Electrode -3.05 -2.71 -2.92 -2.93 -3.02
potential(V)
Group II (Table 2)
Element Be Mg Ca Sr Ba
Ist I.E (KJmol-1) 900 740 590 550 500
2nd I.E(KJmol-1) 1800 1460 1150 1060 970
Atomic 0.11 0.16 0.20 0.21 0.22
radius(nm)
Melting point 1280 650 838 768 714
(oC)
Density(gm-3) 1.86 1.74 1.55 2.60 3.50
Hydration -2385 -1897 -1561 -1414 -1274
energy(KJmol-1)
Electrode -1.85 -2.37 -2.87 -2.89 -2.91
potential(V)
Melting point
Group II elements have higher melting point than group I because they contribute two electrons for
delocalization unlike group I which contributes only one electron. Therefore the metallic radius of
group II elements is smaller than those for group making the metallic bond to be stronger.
Density
The alkali metals are less dense due to larger atomic radius and weaker metallic lattice
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Oxidation state
This is the net charge that can be created on an atom when all other atoms bonded to it have been
removed as ions with a noble gas configuration.
The elements easily lose their valence electron to form positively charged ions therefore the oxidation
state of group I and II is +1 and +2 respectively.
Hydration energy
This is the evolved when one mole of a gaseous ion is completely surrounded by water molecules to
form an infinitely dilute solution.
Ionic charge
Ionic radius
The lower the charge density, the weaker the attraction for the water molecules hence the lower the
hydration energy
Down the group hydration energy decreases due to an increase in ionic radius
The hydration energy of group II elements is more negative than those of group I because of higher
charge and smaller ionic radius.
Electrode potential ( E )
The standard electrode potentials values increase down the group. This is due to decrease ionization
energy and atomization energy (endothermic processes) which is exceeded by hydration energy
(exothermic process) i.e. becomes more negative.
However, the standard electrode potential of lithium is higher than expected due to high hydration
energy caused by high charge density of lithium ions.
The electrode potential of group Ii elements are more negative despite hydration energy because
endothermic processes (atomization and ionization energy) have low value which is exceeded by
exothermic process (hydration energy).
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Hat
M(s) M (g)
I.E
M+ (g)
Eo
Hh
M +(aq)
Qn: Draw the born- harber cycle for relating standard electrode, E , atomization energy, H at ,
ionization energy,I.E and Hydration energy, H h
The standard electrode potential for conversion of each metal to its ion is positive (endothermic) thus
S- block elements are reducing agents.
Group I elements are stronger reducing elements than Group II and the tendency increases as you
move down the group.
Qns: (a) State three energy factors which make group I elements stronger reducing agent than Group
II elements.
(b) Explain briefly why Potassium is a stronger reducing agent than Sodium.
1. HYDROGEN
The hot metals react with dry hydrogen gas to form ionic hydrides i.e.
Since the metals are electropositive, the oxidation state of hydrogen in the hydrides is -1.
2. WATER
All the elements except Beryllium react with water with increasing vigour down the group to
liberate hydrogen gas.
Magnesium reacts slowly with cold water but vigorously with steam
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Mg (s) + H2O (g) MgO (s) + H2 (g)
Calcium, Barium Strontium react readily with water to form the hydroxide and hydrogen gas.
All group I elements readily react with cold water to form strong alkaline solution e.g.
3. ACIDS
Group I elements react violently with dilute mineral acids to form salt and hydrogen gas.
Group II elements react but the reaction becomes more vigorous down the group except with dilute
sulphuric acid. e.g.
Calcium, Strontium and Barium react slowly with dilute sulphuric acid due to formation of sparingly
soluble salt which prevent further reaction e.g.
Magnesium, Calcium and Barium react with very dilute nitric acid to liberate hydrogen gas e.g.
Qn: Compare the reaction of beryllium and barium with sulphuric acid
4. OXYGEN
However barium and Strontium can form peroxides when the normal oxide is heated in more
oxygen .e.g. 2BaO (s) + O2 (g) 2BaO2 (s)
Lithium forms only a normal oxide .i.e. 4 Li (s) + O2 (g) 2 Li2O (s)
Sodium forms a yellow normal peroxide .i.e. 2Na (s) + O2 (g) Na2O2 (s)
Potassium, Caesium and Rubidium form super oxides when burnt in excess in oxygen e.g.
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K (s) + O2 (g) KO2(s)
All the oxides are basic except beryllium oxide which is amphoteric .i.e.
The peroxides form hydroxides and hydrogen peroxides when dissolved in water
The super oxides liberate oxygen gas, hydrogen peroxide and the hydroxide when dissolved in water.
Qn: (a) Be, Mg, Ca and Ba belong to group II of the periodic table. Describe the reactions of the
elements with;
(i) Water
(ii) Air
(b) Explain why Lithium doesn’t form peroxide or superoxide when burn in oxygen.
(c) State what is observed when potassium super oxide is dropped in water. Write the equation
of reaction.
5. CHLORINE (HALOGENS)
The hot metals directly combine with chlorine to form ionic halides except beryllium i.e.
The anhydrous chlorides are ionic except beryllium chloride which is covalent
NOTE: Beryllium behaves differently from the rest of the elements due:
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COMPOUNDS OF S-BLOCK ELEMENTS
Group I compounds are more ionic than the corresponding compounds of group II. This is due to high
charge density.
The salts of group II elements are less soluble in water than group I. Solubility of ionic compounds in
water is affected by lattice energy and hydration energy i.e.
H h Is hydration energy
U Is lattice energy
Soluble salts have negative enthalpy of solution. The more negative the enthalpy of solution the more
soluble the salt.
1. HYDROXIDES
The hydroxides of Group I elements are all white solids and deliquescent except lithium hydroxide.
They dissolve in water exothermically to form strong alkaline solution.
The hydroxides become more soluble down the group due to increasing ionic radius of the cation
which decreases the lattice energy.
At the cathode, Na+ ions are discharged instead of H+ ions because of the high concentration
of the Brine. The sodium thus formed dissolves in the mercury surface to form Sodium
amalgam. The sodium amalgam then flows out and mixes with water to form a mixture of
hydrogen gas, sodium hydroxide and mercury.
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2NaHg (l) + 2 H2O (l) 2NaOH (aq) + H2 (g) + 2Hg (l)
The mixture is then heated and sodium hydroxide is then stable at high temperatures hence it
is formed.
(b) It is deliquescent hence absorbs water to form sodium hydroxide solution which reacts with
carbon dioxide to form sodium carbonate and in excess a white crystal of sodium hydrogen
carbonate is formed . I.e.
Group II hydroxides are sparingly soluble and are prepared by precipitation method. i.e.
They can also be prepared by dissolving a normal oxide of the metal in water. e.g.
The table below shows the solubility of the hydroxides of group II elements
Be(OH)2 0.00
Mg(OH)2 0.01
Ca(OH)2 0.015
Sr(OH)2 0.89
Ba(OH)2 3.32
The solubility generally increases down the group. This is because the radius of the cations increases
while charge remains constant therefore both hydration and lattice energy decrease. However due to
small size of the hydroxide ion, the lattice energy decreases more rapidly than the hydration energy
therefore the enthalpy of solution becomes more negative.
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The table below shows the solubility of sulphates of group II elements
Sulphates Solubility
BeSO4 4095.24
MgSO4 3600
CaSO4 11.0
SrSO4 0.62
BaSO4 0.009
The solubility decreases. Both lattice energy and hydration energy decrease due decrease in ionic
radius of the cation. Since the sulphate ion is large, the hydration energy decreases more rapidly than
the lattice energy therefore the enthalpy of solution become less exothermic.
The carbonates are prepared by bubbling carbon dioxide through the hydroxide solution to precipitate
the less soluble hydrogen carbonate which on heating decomposes to anhydrous carbonate.
Soln: Due to high charge density of lithium ions which greatly polarize the carbonate ion thus
Lithium carbonate is covalent.
Qn: Describe how sodium carbonate is prepared by solvary process on a large scale.
Soln: See A New Certificate of Chemistry, 6th edition (1987), Holderness and Lambert, page331.
Group II carbonates are insoluble in water and undergo thermo decomposition to form oxide and
carbondioxide gas.
The carbonates are prepared by addition of sodium carbonate solution to the solution containing the
metal ion I.e. precipitation e.g.
The stability of the ionic compound depends on the standard lattice energy.
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Ionic charge, the greater the charge on the ion, the greater the stronger the attraction
between the ions thus lattice energy increases with ionic charge.
Ionic radius, Smaller ions closely approach each other in the lattice thus increasing the lattice
energy.
NITRATES:
The nitrates of group II decompose to nitrites and oxygen gas except lithium nitrate I.e.
Soln: Because in Sodium nitrite, the nitrite ion has a smaller relative to the nitrate thus it forms a
stable lattice.
However, for group II nitrates, the oxide ion is smaller and more highly charged than nitrites
therefore the nitrates of groupie elements decompose to metal oxide, nitrogen dioxide and oxygen
gas. e.g.
CARBONATES
The carbonates of Potassium, Sodium, Rubidium and Caesium are stable and do not decompose.
Qn: Explain why Lithium carbonate decomposes while other carbonates of group I do not
Soln: It is because the Lithium ions have a high charge density hence easily polarize the carbonate
ions to form a covalent compound which is held by weak vanderwaals forces which makes it
easily decompose
Qn:
(b) (i) State and Explain what is observed when sodium carbonate solution is added to aluminium
chloride solution
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The table below shows the decomposition temperatures for group II carbonates
BeCO3 100
MgCO3 350
CaCO3 900
SrCO3 1290
BaCO3 1350
The thermal stability increases due to increasing ionic character i.e. Lattice enthalpy. The larger the
metal ion, the less the polarizing power thus the carbonates become ionic and the stronger the
electrostatic forces of attraction.
Group I metal carbonates are more stable than group II metal carbonates. This is because M2+ ions
have higher charge density than M+ ions therefore they polarize the large carbonates more than M+
COMPLEX FORMATION
High charge density of the cations I.e. Small and highly charges cations easily attract
the lone pair of electrons in the ligard ( donor atom )
Presence of suitable vacant orbital to accommodate the lone pairs of electrons from
ligard to form a dative bond
Down the group, the tendency to form complexes decreases due to decrease in charge density.
The Be2+ ion has the highest charge density in the group and thus forms complex ions.
HYDROLYSIS OF SALTS
Hydrolysis is the reaction of salts with water molecules which results in change Ph .
The large group I and II metals are hydrated in solution and their salts don’t undergo hydrolysis.
However the carbonates and hydrogen carbonate of Sodium and potassium undergo hydrolysis to
form alkaline solution.
26
Qn: Explain why sodium carbonate is use in acid-base titration.
Salts containing cations of high charge density undergo hydrolysis e.g. Soluble beryllium alt exist as
Be(H2O)42+ in aqueous solution which hydrolyses to release a proton which causes the solution to be
acidic.
DIAGONAL RELATIONSHIP
This is the similarity in chemical properties between elements in period two to their diagonal
neighbours in period three and adjacent groups.
27
Their hydroxides and carbonates are Form covalent
sparingly soluble in water Both form ionic carbides which hydrolyze to form compounds.
methane.
Be2C (s) + 4H2O(l) CH4(g) + 2Be(OH)2 (aq)
Al4C3(s) + 12H2O(l) 3CH4(g) + 4Al(OH) 3(aq)
Carbonates, hydroxides, peroxide Form borides and
decompose on heating to give an Both are rendered passive concentrated nitric acid. silicides with metals.
oxide.
Nitrates decompose on heating to give
an oxide, nitrogendioxide and oxygen. Both form fluoro complexes.e.g. BeF42-
Halides (except fluorides) and
chlorates (VII) are soluble in organic
solvent.
28
Ammonium Oxalate followed by Ammonia Solution
1. The diatomic molecules have simple molecular structure with molecules held by weak vanderwaals
forces whose magnitude depends on molecular mass of the molecule.
Boiling point increases down the group. This is because the simple molecules are held by weak
vanderwaals forces whose magnitude increases with increase in magnitude molecular mass.
3. Bond Energy
The bond energy decreases from Chlorine down the group. This is due to increase in atomic radius
which decreases the nuclear attraction for the bond pairs thus increasing the bond length.
However, the bond energy of fluorine is lower than expected due to small radius which makes the
lone pairs of electrons easily approach other thus the further repulsion.
29
4. Electron affinity
Down the group, electron affinity decreases from chlorine to iodine due to the reduction in nuclear
attraction for the incoming electron caused by the addition of extra energy levels of electrons
therefore the incoming electron experiences greater repulsion hence less energy is evolved.
However, the electron affinity of fluorine is lower than expected due to small atomic radius which
gives a higher electron density hence extra repulsion of the incoming electron.
5. Electrode Potential
The reduction potential becomes less positive down the group therefore fluorine is the most
powerful oxidizing agent.
The most negative electrode potential represents the strongest reducing agent and the most positive
electrode represents the strongest oxidizing agent.
High electronegativity
Small atomic radius
Low bond energy
High electrode potential
It combines directly with carbon at room temperature to form carbon tetra fluoride.
Hydrogen fluoride has a very high boiling point due to formation hydrogen bonding.
Hydrofluoric acid is the weakest acid compared to other halogen acid.
Silver fluoride is soluble in water while the chloride, bromide and iodide of silver are
insoluble in water. This is because the small fluoride ions have high hydration energy
which exceeds lattice energy hence the enthalpy of solution is negative.
Fluorine has only one oxidation state.
Fluorine does not form oxo-acids.
Calcium fluorine is insoluble in water while the other halides are soluble in water.
30
Qn: Describe briefly how fluorine, Bromine and chlorine can be prepared in the laboratory.
REACTIONS OF HALOGENS
(a) Water
Chlorine and bromine reacts with water to form halic (I) acids
Iodine is sparingly soluble in water but highly soluble in potassium iodide solution due formation of
potassium tri-iodide which is a complex salt I.e.
N.B. In the presence of Sunlight, the halic (I) acid decompose to oxygen.
(b) Alkalis
2F2 (g) + 2OH- (aq) OF2 (g) + 2F- (aq) + H2O (l)
Chlorine, Bromine and Iodine form the halide, halite (I) and water.
Cl2 (g) + 2 OH- (aq) Cl- (aq) + OCl- (aq) + H2O (l)
Br2 (l) + 2OH- (aq) Br- (aq) + OBr- (aq) + H2O (l)
31
Chlorine, Bromine and Iodine forms the Halide, halate (V) and water.
3X2 + 6OH- (aq) X- (aq) + XO3- (aq) + 3 H2O (l), X= Cl, Br and I
(c) Hydrogen
Fluorine explodes in dry hydrogen even in the dark to form hydrogen fluoride.
Chlorine reacts vigorously with hydrogen in presence of sunlight or ultraviolet light to form
hydrogen chlorine.
Pt/ 200oC
Br2 (l) + H2 (g) 2HBr (g)
Iodine reacts with hydrogen at 400oC to hydrogen iodide and the reaction is reversible.
Pt/ 400oC
I2 (s) + H2 (g) 2HI (g)
S2O32- (aq) Cl2 (g) + H2O (l) SO42- (aq) + S (s) + 2 Cl –(aq) + 2 H+ (aq)
S2O32- (aq) + 4Cl2 (g) + 5H2O (l) 2SO42- (aq) + 10H+ (aq) + 8 Cl- (aq) In excess Cl2)
32
Qn: (a) State what is observed when chlorine gas is bubbled through a solution of sodium
thiosulphate solution. Write the equation of reaction.
(b) State what would be observed when chlorine gas is bubbled through a solution of Iron (II)
chloride solution hence write the equation of reaction.
COMPOUNDS OF HALOGENS
HF HCl HBr HI
1. Boiling point
The boiling point increases from HCl to HI. This is because they are simple molecules held by
van der -waals whose magnitude increases with molecular mass.
However, HF has extremely high boiling point because the molecules associate by hydrogen bonding
due small ionic radius of the fluoride ions.
2. Bond energy
3. Acidic Strength
The acid strength depends on the degree of dissociation of the acid thus the concentration of the
hydrogen ion in aqueous solution.
Since electronegativity decreases down the group due to increase in atomic radius therefore the bond
strength is in the order HF> HCl> HBr> HI thus HF is H-F bond is not easily broken hence it does not
easily release a proton in aqueous solution thus it’s a weakest acid. The H-I bond is the weakest bond
therefore in aqueous solution it easily release a proton.
33
HF slightly ionizes in dilute solution as:
N.B. When concentrated, HF is a weaker acid than in dilute solution due to hydrogen bonding which
reduces the concentration of hydrogen ions. I.e.
Qn: Describe how the hydrides of group (VII) elements are prepared in the Laboratory.
2. HF and HCl don’t react with concentrated sulphuric acid. HBr and HI are strong reducing
agents therefore are oxidized to bromine and iodine by conc. Sulphuric acid. I.e.
HBr (aq) + H2SO4 (aq) Br2 (l) + SO2 (g) + H2O (l)
However, Conc. Hydrochloric acid can be oxidized by the stronger oxidizing agents such as
MnO2 , PbO2 and KMnO4
MnO2 (s) + 4HCl (aq) Cl2 (g) + 2H2O (l) + MnCl2 (aq)
PbO2 (s) + 4HCl (aq) Cl2 (g) + 2H2O (l) + PbCl2 (aq)
2MnO4- (aq) + 10 Cl- (aq) + 16H+ (aq) 5Cl2 (g) + 8H2O (l) + 2Mn2+ (aq)
N.B. Hydroiodic acid (acidified Potassium Iodide) is the strongest reducing agent thus it is easily
oxidized.
Hydrofluoric acid reacts with silicon (IV) Oxide to form Hexafluoro silicic acid
(b) A colourless solution of acidified hydrogen peroxide turns brown on addition of acidified
potassium iodide.
34
(b) Oxo- acids / ions
All halogens except fluorine form oxo-ions and oxo-acids e.g. HOCl, HClO2 , HClO3 and HClO4
Qn: Draw and name the structures of the above oxo- acids.
1. Acid Strength
The acidic strength depends on the number of oxygen atoms in the acid molecule. Since
oxygen is more electronegative than chlorine, it pulls the bonding electrons towards itself and this
negative inductive effect is transmitted to the O-H bond weakening it thus hydrogen ions are released
in solution. The greater the number of the oxygen atom, the greater the effect and the weaker the O-
H bond. Thus the strength of the acid is HClO4> HClO3 > HClO2 > HClO.
Chlorate (I) salts are obtained when chlorine gas is bubbled through dilute alkali solution.
Cl2 (g) + 2OH- (aq) OCl- (aq) + Cl- (aq) + H2O (l)
Aqueous solutions of Chlorate (I) disproportionate at about 75oC to form Chlorate (V) and Chloride
However, in presence of an acid chlorate (I) ions act as oxidizing agent e.g. it oxidizes iodide ions to
iodine
With concentrated Hydrochloric acid, Chlorate (I) ions liberate chlorine gas
ClO- (aq) + 2H+ (aq) + Cl- (aq) Cl2 (g) + H2O (l)
N.B. The reaction above is used to determine the percentage of chlorine in bleaching agent.
Qn: (a) 0.6cm3 of jik was dissolved in water and solution made in 250cm3 volumetric flask. 25cm3 of
this solution was acidified and 10cm3 of 0.2M potassium iodide solution added. The iodine
liberated required 5.0cm3 of 0.2M Sodium thiosulphate solution for complete reaction.
Calculate the percentage of Chlorine in Jik
35
(b) Describe an experiment to determine the concentration of Sodium Hypochlorite using
Volumetric analysis.
This is a powerful oxidizing agent that only occurs in aqueous solution. Its salts are more stable and
can be obtained by passing chlorine gas through hot Conc. Alkali.
3Cl2 (g) + 6 OH- (aq) ClO3- (aq) + 5Cl- (aq) + 3H2O (l)
In Acidic medium, Chlorate (V) ions are strong Oxidizing Agents and the reduction half cell equation
It oxidizes Iron (II) to Iron (III), Sulphite ions to Sulphate ions and Iodide ions to Iodine.
6Fe2+ (aq) + 6H+ (aq) + ClO3- (aq) 6 Fe3+ (aq) + Cl- (aq) + 3H2O (l)
ClO3- (aq) + 6H+ (aq) + 6I- (aq) 3I2 (aq) + 3H2O (l) + Cl- (aq)
Qn : (a) A solution of halate (V) ion YO3- contains 2.94g/l. 25cm3 of this solution was added to an
equal volume acidified potassium iodide solution. The iodine liberated required 25.2cm3 of
24.8g/l Na2S2O3.5H2O. Calculate the relative atomic mass of Y hence identify Y.
(b) Give the I.U.P.A.C name for the following oxide and calculate the oxidation number of the
halogen in :
These are compounds formed between halogens with the molecular formula AB, AB3, AB5 and
AB7 where A- is a less electronegative atom with a vacant orbital and a higher oxidation state while B-
is more electronegative.
36
Qn: Explain the shapes of the following interhalogen compounds:
I- Yellow ppte
I- yellow ppte
GROUP IV ELEMENTS
The outer most electronic configuration is nS2 nP2 where n is the principal quantum numbers.
37
1. Existence
Carbon exists as graphite, diamond and amorphous carbon. Silicon occurs as Silica (SiO2). Tin exist
as grey tin and white tin. Lead occurs as a ore in form of galena (PbS)
2. Melting point.
The melting points of group IV elements depend on the structure. Carbon and Silicon have giant
atomic structures which require a lot of energy to break. However the melting point of silicon is lower
than that of carbon since the covalent bonds in silicon atoms are longer thus weaker.
Tin and Lead are weak metals with a metallic structure however lead is more metallic than tin hence
has a higher melting point.
3. Electropositivity
4. Electronegativity
5. Oxidation states
The elements exhibit both +2 and +4 oxidation states. The +4 oxidation state is attained by
promoting one S- electron to an empty P orbital to avail four electrons.
Down the group, the nS2 electrons become more reluctant to participitate in bonding. This is called
inert pair effect. Therefore the stability of +2 oxidation state increases while that of +4 decreases.
Soln: AS the radius of the atoms increase down the group there is increasing tendency for the two
bonding electrons in the S- Sub energy level to resist taking part in bonding.
Carbon forms carbon tetrachloride while lead (IV) chloride readily decomposes to form Lead (II)
chloride and Chlorine
38
Lead (IV) oxide decomposes on heating to form lead (II) oxide and Oxygen
Carbon behaves differently from the rest of the group members due:
Some of the properties in which Carbon differs from the rest of the members include:
It forms a stable multiple bonds with itself and with other non-metals.
Carbon can form a number of hydrocarbons because it can catenate. Catenation is the
ability of the element to form bonds between atoms of the same element.
It forms gaseous oxides unlike other members
The halides are stable to hydrolysis.
1. Water
Hot silicon reacts with steam to form silicon dioxide and hydrogen gas I.e.
Lead reacts slowly with soft water in presence of air (oxygen) to form lead (II) hydroxide
2. Air
The elements burn in air to form dioxides except lead which forms lead (II) oxide
39
2C (s) + O2 (g) 2 CO (g)
3. Acids
The elements do not react with dilute acids except tin which reacts with dilute nitric acid as :
NO3 – (aq) + 4 Sn (s) + 10 H+ (aq) 4 Sn2+ (aq) + NH4+ (aq) + 3 H2O (l)
Silicon reacts with only with conc hydrofluoric acid to form hexafluoro silicic acid and Hydrogen gas
Hot conc nitric acid oxidizes tin, germanium and Carbon to dioxide and itself reduced to oxides of
nitrogen
3Sn (s) + 4HNO3 (aq) 3SnO2 (s) + 4NO (g) + 2H2O (l)
3Pb (s) + 8HNO3 (aq) 3Pb (NO3)2 (aq) + 2NO (g) + 4H2O (l)
Lead and tin react with hot conc. Hydrochloric acid to form dichloride and hydrogen gas.
N.B. lead (II) chloride is sparingly soluble in water but highly soluble in Conc. Acid due formation of a
complex. I.e. PbCl42-
4. Alkalis
All the elements except Carbon react with Conc. Alkali to form complex salts and hydrogen gas.I.e.
40
Pb(s) + 2OH – (aq) + 2H2O (l) Pb(OH)42- (aq) + 2H2 (g)
5. Non- metals
When heated, the elements react with Sulphur, chlorine, fluorine and hydrogen chloride.e.g.
1. Oxides
(a) Monoxides: CO and SiO are covalent compounds with simple molecular structure.
GeO, SnO and PbO are amphoteric oxides with giant ionic structure
Preparation:
Conc.H2SO4
HCOOH (aq) CO (g) + H2O (l)
Conc.H2SO4
H2C2O4(aq) CO2 (g) + CO (g) + H2O (l)
Qn : Explain why Tin (II) Oxalate is used instead of Tin (II) nitrate to prepare Tin (II) Oxide.
41
CO (g) + NaOH (aq) 150oC
HCOONa (aq)
700KPa
With Acids
Qn : (a) 1.5g of impure tin (II) Oxide was dissolved in excess dilute hydrochloric acid and the resultant
solution made to 250cm3 with distilled water. 25cm3 of this solution was titrated with 0.02M
potassium permanganate until the colour turned pink. The volume of Potassium
permanganate solution used was 20cm3. Calculate the percentage impurity of tin (II) oxide
(Sn= 119, O=16)
(b) Write an ionic equation when tin (II) ions are added to :
(b) Dioxides
Lead (IV) is prepared by reacting dilead (II) lead (IV) oxide with dilute nitric acid.
Pb3O4 (s) + 4HNO3 (aq) 2Pb(NO3)2 (aq) + PbO2 (s) + 2H2O (l)
The dioxides are more stable than the monoxides except lead (IV) oxide.i.e.
Lead (IV) oxide oxidizes strong hot concentrated hydrochloric acid to chlorine gas
PbO2 (s) + 4HCl (aq) Cl2 (g) + PbCl2 (s) + H2O (l)
When excess concentrated hydrochloric acid is reacted with lead (IV) oxide at 0oC it forms a complex
ion
42
PbO2 (s) + 4HCl (aq) + 2Cl- (aq) PbCl62- (aq) + 2H2O (l)
Addition of concentrated ammonium chloride to the complex produces a yellow precipitate. i.e.
Soln: If heated lead (IV) Oxide reacts with concentrated sulphuric acid to form lead(II)sulphate,
oxygen and water.
Qn: (a) A compound Q contains 90.65%by mass of lead and the rest Oxygen. Deduce the molecular
formula of Q if its molar mass is 685g.
(b) State what is observed when Q is reacted with the following and in each case write the
equation of reaction.
2. Hydrides
The elements form covalent tetrahydrides whose thermo-stability decreases down the group.
Read on:
Preparation.
Qn : (a) Gaseous hydride of silicon diffuses through a narrow hole for 27.8s. The same volume of
carbondioxide under the same temperature and pressure through the same in 32.6s
43
(b) Write the equation of reaction between the hydride of silicon and sodium hydroxide solution
3. Chlorides
(a) Tetrachlorides
These are covalent liquids with simple molecular structure and become less stable down the group
due to an increase in M-Cl bond length
N.B. Lead (IV) chloride readily decomposes to form chlorine and lead (II) chloride
Carbon tetrachloride does not react with water because of lack of vacant d-orbital.
Other chlorides react with water rapidly to liberate hydrogen chloride. For silicon tetrachloride, the
second product depends on the degree of hydration.
(b) Dichlorides
The stable chlorides in the +2 oxidation state are only formed by tin and lead
Tin (II) chloride reacts with water to form a basic chloride and hydrochloric acid. i.e. it undergoes
hydrolysis
44
However, in excess hot water tin (II) hydroxide is formed.
Lead (II) Chloride is sparingly soluble in water and does not undergo hydrolysis. However it dissolves
on heating since solubility increases with temperature.
N.B. Lead (II) chloride is more soluble in concentrated hydrochloric acid than in water due to
formation of a soluble complex of tetrachloro plumbate (II)
N.B. A solution containing tin (II) ions and lead (II) ions react with hydrogen sulphide gas to precipitate
the metal sulphide (black)
Qn : When a yellow solid A is heated with air at 450oC, a red solid B is formed. B reacts with hot
dilute nitric acid to form a dark brown solid C on precipitation and after filtration and
crystallization of the filtrate; a white solid D is obtained. When C is heated with concentrated
hydrochloric acid, a pale green gas was evolved and when hydrochloric acid is added to
aqueous solution of D at room temperature, a white precipitate E was formed.
(b) Account for your answers in (a) above with aid of equations of reactions.
Qn : The standard enthalpy of formation of tin tetrachloride is -508KJmol-1. The standard enthalpy
of atomization of tin and chlorine are +301 and +121KJmol-1 respectively. The average bond
energy of Si-Cl bond is +383KJmol-1
45
(c) State a reagent that can be used to differentiate between the following ions and in each case
state what would be observed when each is treated with the reagent.
PERIOD 3 ELEMENTS
The period runs from sodium to Argon. The table below shows some physical parameters of the
elements involved.
Elements Na Mg Al Si P S Cl Ar
Melting point 98 651 660 1410 44 114 -101 -189
1. Melting point
This is a constant temperature at which an element in its solid state changes to liquid state under
constant pressure.
46
The abrupt change in melting point is explained as:
From sodium- aluminium, the strong metallic bonds have to be broken down. The strength of
the metallic bond increases due to increase in the number of electrons used per atom and
also due to decrease to metallic radius.
From Aluminium- Silicon, the increase is due to the strong covalent bonds that have to be
broken for a giant atomic structure of Silicon where each silicon atom contributes four
electrons towards covalent bonding.
From Silicon-phosphorous, the decrease is due to change from giant atomic structure to
molecular discrete structure where the molecules are held by weak vanderwaals forces of
attraction
From phosphorous-Sulphur, these are discrete molecules which are as P4 and S8 held by weak
Vander waals force whose magnitude increases with increase in molecular mass. Since the
molar mass of S8 is greater than that of P4 therefore an increase in melting point.
From Sulphur-chlorine, the diatomic molecule has a lower molar mass than sulphur there fore
the magnitude of the vanderwaals forces are weaker hence low melting point.
Qn: Explain the trend of the following parameters across period 3 of the periodic table
(c) Electronegativity
1. Chlorine
Sodium and Magnesium when heated react with chlorine to form ionic chlorides
47
Vaour phase
2AlCl3 (s) Al2Cl6 (g)
Soln: This is because the aluminium ions have a high charge density which greatly polarizes the
chloride ions to form a covalent compound hence reducing the charge separation.
Silicon, phosphorous and Sulphur also react with chlorine to form covalent chlorides with simple
molecular structure.
2. Oxygen
All the elements except chlorine react with oxygen to form oxides.
3. Hydrogen
Sodium and Magnesium react vigorously with hydrogen gas to form ionic hydrides.
48
2Na (s) + H2 (g) 2NaH (s)
Chlorine and Sulphur form the corresponding covalent hydrides. Chlorine reacts in presence of
Sunlight or ultraviolet light.
4. Acids
Sodium, Magnesium and Aluminium react with dilute acids to form salts and hydrogen gas i.e.
hydrochloric acid and sulphuric acid.
Concentrated Nitric acid reacts violently with sodium and magnesium to form the nitrate, water and
nitrogen dioxide
Phosphorous and Sulphur are oxidized to their respective oxides and itself reduced to nitrogen
dioxide.
P4 (s) + 10HNO3 (aq) + H2O (l) 4H3PO4 (aq) + 5NO2 (g) + 5NO (g)
49
COMPOUNDS OF PERIOD 3 ELEMENTS
1. Chlorides
Chlorides NaCl MgCl2 AlCl3 SiCl4 PCl3 , PCl5 S2Cl2, SCl2 Cl2
b.p.t 1465 1418 423 57 74, 164 138 -35
Bond ionic Ionic
Covalent
structure Giant Giant Simple molecular structure
ionic ionic
Sodium chloride and Magnesium chloride dissociate to form neutral aqueous solution
Aluminium chloride undergoes hydrolysis due to high charge density and aluminium ions become
heavily hydrated in solution as Al (H2O)63+
The hydrated ions undergo hydrolysis to release a proton in solution which causes the solution to be
acidic
50
2. Oxides
Silicon (IV) oxide and aluminium oxide do not react with water.
Sodium and Magnesium oxide are basic oxides therefore they do not react with sodium hydroxide
solution
51
Cl2O7 (l) + 2OH- (aq) 2ClO4- (aq) + H2O (l)
3. Hydrides
Bond
Ionic Covalent
Structure Giant ionic Simple molecular
The ionic hydrides react with water to form hydroxide and hydrogen gas
Phosphine does not react with water. Hydride of silicon reacts with water in presence of a strong base.
i.e.
Hydrogen Sulphide and Hydrogen chloride reacts with water to form acidic solution.
EXTRACTION OF ALUMINIUM
Roast bauxite to convert Iron (II) Oxide (impurity) to Iron (III) Oxide and drive off the water of
crystallization.
Crush the roasted ore to powder and heat with concentrated sodium hydroxide sodium hydroxide
solution.
The amphoteric ore and the acidic silicon (IV) Oxide (impurity) dissolves in the alkaline to form
complex salts while the Iron (III) oxide remains undissolved.
The mixture is filtered and the filtrate diluted with water. Carbondioxide gas is passed through the
mixture to precipitate pure aluminium hydroxide.
2Al(OH)4- (aq) + CO2 (g) 2Al(OH)3 (s) + CO32- (aq) + H2O (l)
52
Or. The solution is seeded by adding a little aluminium hydroxide to the aluminate to precipitate
aluminium hydroxide.
The insoluble hydroxide is filtered off, washed and dried. Pure aluminium hydroxide is then heated to
form pure aluminium oxide
The oxide is then dissolved in molten cryolite to increase conductivity. A small amount of Calcium
fluoride is added to lower the melting point of the electrolyte. Also Aluminium fluoride is added to
lower the solubility of the molten aluminium.
The mixture is electrolyzed between the graphite electrodes at 900oC using a low voltage to avoid the
decomposition of Cryolite and high charge density.
Aluminium ions are discharged at the cathode while oxygen is liberated at the anode.
Cathode:
Anode:
Qn: (a) During the extraction of aluminium, the ore is first purified.
(c) Write an equation to show how anhydrous aluminium chloride can be obtained from
aluminium.
Introduction:
Some statistic about types of elements of the periodic table up to atomic number to 103
53
(b) Metalloid = 3
(c) Metals = 81
Electronic Configuration
After the second energy level, an overlap starts occurring between 3d-subshell which is nearer the
nucleus than 4s- subshell but at a higher energy level. Thus after filling 3S and 3P subshells further
electrons after the 4S- subshell (2electrons) later 3d- subshell.
From the electronic configuration, a transition metal is defined as that element having a partially filled
3d-subshell (between 1-9 electrons) therefore Zinc is not regarded as transition metal.
However, anomalous behavior occurs between Chromium (Z=24) and Copper (Z=29) because
configuration giving half filled d-subshell are thermodynamically more stable.
Transition metals form ions by loosing electrons from 4S-subshell rather than the 3d-subshell.
The table below shows the electronic configuration of the short series of the transition metals
54
(i) Fe2+ (ii) Fe3+ (iii) Cr3+
Soln: (a) Because Fe3+ is has 3d5 subshell electrons which is thermodynamically stable compared to
Fe2+ with 3d6 which is unstable.
The physical properties of transition metals do not vary greatly and many of them show a regular
trend. Some of the properties include:
1. Metallic character.
The transition metals are true metals and many of them are widely used industrially. They are hard,
strong and lustrous and have high melting and boiling point and high enthalpies of atomization. These
properties suggest presence of strong metallic bonding.
The strong metallic bonding is due to availability of d-electrons.e.g Sodium with only 3S-electron
available for bonding therefore it has a low melting point compared to iron with two 4S-electrons and
a maximum of six 3d-electrons.
The metallic radius decreases from scandium to nickel and it slightly increases from nickel to Zinc.
As atomic number increases, the nuclear charge increases. However, the electrons are being added to
inner 3d-subshell therefore these electrons are poorly shielded from the nuclear charge hence the
nuclear attraction for the outer for the most electron increases resulting into increase in atomic
radius/ metallic radius.
The slightly increase from nickel to Copper is because the 3d-subenergy level in copper is fully filled
with electrons and this increases the shielding of the outer electrons from the nuclear charge hence
atomic radius increases.
The decrease in radius coupled with increasing atomic mass causes an increase in the density and
decrease in atomic volume in passing from Scandium to Nickel.
3. Ionisation energy
There is a fairly general increase in ionization energy in passing from Scandium to nickel due to
increasing nuclear charge holding the electrons more strongly resulting into decrease in atomic radius.
Qn. The table below shows the electronegativity values for elements in d-block of the periodic table
55
Element Sc Ti V Cr Mn Fe Co Cu Zn
At. No. 21 22 23 24 25 26 27 29 30
Electronegativity 1.3 1.5 1.6 1.6 1.5 1.8 1.8 1.9 1.6
The elements exist in variable oxidation states in variety of the compounds due to availability of
the 3d-electrons which can participate in bond formation by either ionic or covalent
The commonest stable oxidation states are in bold as shown in the table
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+1
+2 +2 +2 +2 +2 +2 +2 +2 +2
+3 +3 +3 +3 +3 +3 +3 +3
+4 +4 +4 +4
+5 +5 +5
+6 +6 +6
+7
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Sc2O3 TiO,TiCl2 VCl2, CrCl2, MnO, FeCl2 CoO,CoCl2, NiO CuO ZnO
ScF3 Ti2O3, V2O3, Cr2O3, MnCl2,MnCl3, FeCl3 Co(NH3)63+ Ni2O3.xH2O Cu2O
TiCl3 VO2 CrCl3 MnO2, CuCl
TiO2, TiCl4 V2O5 CrCl4,CrF5, ,MnO42- CuCl2
CrO3, ,MnO4-
Cr2O72-
The relative stability of these oxidation states is also indicated by the standard reduction electrode
potential.
Since Zinc has one oxidation state for this reason it is regarded non-transition metal.
56
(ii) Oxidising agent
(b) Determine the oxidation state of the transition metal in the following complex
2. Paramagnetism
A substance that can be drawn into a strong magnetic field is known as paramagnetic substance.
Transition metals are paramagnetic due to the presence of unpaired 3d-electrons. Every spinning
electron acts as a tiny magnet. However, in an orbital with 2 paired electrons, the magnetic moment
of one electron cancels out.
The 3d-electrons in isolated metal atom are degenerate.i.e. Energetically alike. However, in presence
of ligards, the orbitals overlap differently and spit in to two levels of different of energy. This excites
electrons from a lower to higher level of energy. The frequency of light absorbed from this energy
transition is from the visible region of the spectrum hence this appears as colour.
N.B. Scandium and Zinc form colourless compounds therefore they are regarded as non-transition
metals.
Qn: (a) State two factors that affect the colour of transition metal compounds
(b) Explain why compounds of S-block elements don’t form coloured compounds
4. Catalytic activity
Transition elements and their compounds act as catalysts with several chemical processes
Homogeneous catalysis (where the catalyst are in the same phase with the reactants), due to variable
oxidation state transition metals/ ions form with the activated complex thus providing an alternative
reaction path way of lower reaction energy e.g.
Fe2+ (aq)
S2O82- (aq) + 2I- (aq) 2SO42- (aq) + I2 (aq)
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Heterogeneous catalysis (where the catalyst and reactants are in different phases), finely divided solid
transition metals/ compound provide an active interface for adsorption of the reactant where they are
bound to the surface by vanderwaals forces.
5. Complex formation
A ligard is anion or molecule with lone pairs of electrons linked to the central metal ion by a dative
bond
Co-ordination number is the number of atoms of ligards molecules that form dative bonds in the
complex ion.
A metal complex or co-ordination compound is a chemical system composed of electron donor and
electron acceptor.
Ligards are classified on basing on the number of atoms directly bonded to the metal centre
(Denticity). i.e.
NCH2CNH
CH2COOH CH2COOH
(EDTA)-Ethylenediamine tetraacetic acid
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Neutral ligard Anionic ligards Cationic ligard
H2O- aqua Cl- -chloro
NH3-ammine Br- -bromo
CO-carbonyl SO42- - Sulphato
NO-nitrosyl OH- -hydroxo
H2NCH2CH2NH2 (en)-ethane-1,2-diamine CN- - cyano
NO2- Nitro
H- -hydrido
Nomenclature of Complexes
(iii) If different ligards exist, list them in order of anion, neutal and cation. If the ligards are
of the same nature, use the alphabetical order
Examples include:
[Cu(NH3)4]2+ Tetraamminecopper(II)ion
[Cr(H2O)4(NH3)2]3+ diamminetetraaquachromium(III)ion
[Pt(NH3)2NO2Cl]2+ chloronitrodiammineplatinum(IV) ion
[Co(NH3)5SO4]Br Sulphatopentaammine cobalt(III)bromide
Name of the central atom ends in –ate or-ic for an acid followed by it oxidation state.
Example include:
[CuCl4]2- tetrachlorocupricate(II)ion
SiF62- Hexafluorosilicate(IV)ion
[Cr(OH)5NH3]3- pentahydroxoamminechromate(II)ion
[CoCl4(H2O)2]- tetrachlorodiaquacobaltate(III)ion
LiAlH4 Lithiumtetrahydridoaluminate(III)
These are formed between the central metal atom and a neutral ligard e.g.
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Ni(CO)4 Tetracarbonylnickel(0)
V(CO)6 hexacarbonylvanadium(0)
ISOMERISM
This occurs when an ion can occupy positions inside and outside complex ion .i.e. acts as a free
ligard
Example
Bromopentaamminecobalt(III)sulphate Sulphatopentaamminecobalt(III)bromide
These isomers can be differentiated by use of acidified barium nitrate solution and the observations
are:
The sulphate ions in bromopentaamminecolbalt(III)sulphate are uncomplexed therefore they are free
to react with barium nitrate solution to precipitate the sparingly soluble barium sulphatei.e.
Qn: Hydrated Chromium(III)chloride forms three isomers which form a white precipitate with
silver nitrate solution.
Soln:
[Cr(H2O)5Cl]Cl2.H2O Chloropentaaquachromium(III)chloride
[Cr(H2O)4Cl2]Cl.2H2O Dichlorotetraaquachromium(III)chloride
(b) Add excess 1M Silver nitrate solution to equimolar solution of each isomer. The number of
moles of silver chloride precipitated by isomer is in the ratio of 3:2:1.
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Conductivity depends on the number of conducting ions present in solution. The isomer with
more ions gives the highest conductivity.
The isomers differ in the spatial arrangement of two ligard molecules in square planar or
octahedral complex giving rise to cis and trans isomers
Linear structure formed by complexes with coordination number 2
Tetrahedral/ square planar formed by complexes with co-ordination no. 4
Octahedral formed by complexes with co-ordination no.6
STABILITY CONSTANT
Consider;
[[ML6 ]n ]
Keq =
[[ L]6 ][M n ] where Keq is the stability constant
A ligard with a higher stability constant substitutes/ displaces others from the complex
Qn: To an aqueous solution of copper (II) sulphate, concentrated hydrochloric acid was added
followed by aqueous ammonia solution
Soln:
(b) In dilute solution of copper(II) sulphate, the blue colour is due to [Cu(H2O)6]2+ . On addition
of concentrated hydrochloric acid the aqua ligard are displaced to form a yellow
tetrachlorocupricate (II) complex.
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On addition of ammonia molecules with a higher stability constant displaces the chloro ligards
to form tetraamminecopper(II)ions which is deep blue.
COPPER
Extraction :
Ores:
The ore is crushed to powder and mixed with water containing a frothing agent such as pine oil. Air
is blown through the mixture to agitate the ore.
High density impurities become wet and sink to the bottom. Particles of the ore rise to the surface and
adhere to the air bubbles. They float on the surface as a froth which is skimmed off, filtered and dried.
(b) Roasting
The concentrated ore is roasted in air to convert pyrites into iron (II)oxide, copper(I)sulphide and
sulphur dioxide gas
2CuFeS2 (s) + 4O2 (g) Cu2S (s) + 2FeO (s) + 3SO2 (g)
(c) Smelting
The mixture is heated in furnace with silicon (IV) oxide in absence of air. Iron (II)oxide reacts to form
a slug of Iron(II)silicate
The molten slug floats on the molten Copper(I)sulphide and can be trapped off.
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The mixture of copper(I)oxide and unchanged copper(I)sulphide is then heated strongly in absence of
air to form blister copper.
Copper (II) sulphate solution is electrolysed using blister copper as the anode and pure copper as
cathode. The pure copper dissolves from the anode into solution and it is deposited at the cathode
The anode loses mass and cathode gains an equal mass of copper.
PROPERTIES OF COPPER
Copper has a low Electropositivity and thus it is an inert and not attacked by dilute mineral acids and
water.
(a) It is oxidized by hot concentrated sulphuric acid to copper (II) sulphate, sulphiurdioxide and water
(b) It is oxidized by cold and hot concentrated nitric acid as shown below respectively
3Cu (s) + 8HNO3 (aq) 3Cu(NO3)2 (aq) + 2CNO (g) + 4H2O (l)
(c) When heated, copper reacts with oxygen and dry chlorine as:
COMPOUNDS OF COPPER
Copper (I) is less stable compared to copper (II) despite the stable electronic configuration of copper
(I) ions. With respect to copper, both copper (I) and Copper (II) ions are unstable i.e.
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Cu+ (aq) + e Cu (s) H 602KJmol 1
The enthalpy of conversion of Cu+ to Cu2+ is -409KJmol-1 and this shows that Cu+ ions are
thermodynamically unstable with respect to both Cu and Cu2+
It is prepared by reduction of copper (II) sulphate with an aldehyde in the presence of an alkali
It is prepared by boiling copper (II) chloride with copper in presence of concentrated hydrochloric
acid.
Qn: 8.0g of a copper ore was leached with dilute sulphuric acid and the resultant solution diluted
to 250cm3. Excess 10% potassium iodide was added to 30cm3 of the solution. The iodine
liberated 23.5cm3 of 0.05M sodium thiosulphate solution for complete reaction.
(c) Describe the application of copper (I) compounds in distinguishing organic compounds and
synthesis
(d) Explain the similarity between silver (I) and copper (I) ions
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Qn: A double salt Cu (NH4)xCly.zH2O where x,y and z are whole numbers. The molar mass of salt is
277.5g. The chloride in 1.388g of the salt is precipitated as silver chloride. After washing and
drying the mass of the precipitate was 2.870g. When 1.388g of the salt is boiled with excess
sodium hydroxide solution, the ammonia liberated neutralizes 10cm3 of 1.0M hydrochloric
acid. Determine the formula of the salt.
This a black basic oxide obtained by the action of heat on copper (II) nitrate, carbonate, sulphate
or copper (II) hydroxide
It reacts with dilute mineral acids to form copper (II) salts and water
This a pale blue precipitate formed when dilute sodium hydroxide solution is added to a solution
of Copper (II) ions
The anhydrous chloride is prepared by reacting dry chlorine gas with heated copper metal
The chloride dissolves in concentrated hydrochloric acid to form a yellow- green solution of
tetrachloro cupricate
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An aqueous solution of copper (II) salts are slightly acidic because the Cu2+ ions have a high charge
density there fore they are heavily hydrated as [ Cu(H2O)6]2+ and this undergoes hydrolysis to release
hydrogen ions in solution which causes the solution to be acidic
IRON
Extraction
Magnetite(Fe3O4)
The mixture of haematite,coke and limestone are fed into the furnace. Air enriched in oxygen is
passed into the bottom of the furnace whose temperature varies from about 2000oC -200oC at the top
The reaction is exothermic and thus increases the temperature of the furnace. Carbonmonoxide
reduces iron (III) oxide to iron
Limestone decomposes to form calcium oxide which removes the major impurity, Silicon (IV) Oxide as
a slug of calcium silicate.
The slug is less dense than the molten iron hence it protects it from re-oxidation. The excess hot gases
pass out of the furnace while the iron and slug are periodically tapped off from the bottom
N.B. The pig iron can be converted to steel by open-hearth process where the carbon is converted to
gaseous oxide by heating and other impurities form oxides which react with limestone to form slag
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PROPERTIES OF IRON
(a) When heated, iron reacts with oxygen to form black solid of triiron tetraoxide
(b) Red hot iron reacts with stream as shown by the equation
Iron slowly reacts with cold water in the presence of oxygen to form hydrated iron (III) oxide
(c) When heated iron reacts with sulphur, chlorine, hydrogen chloride, carbon and carbonmonoxide
(d) It liberate hydrogen gas when reacted with dilute mineral acids
Hot concentrated sulphuric acid oxidizes it to iron (III) sulphate and itself reduced to sulphurdioxide
and water
2Fe (s) + 6H2SO4 (aq) Fe2(SO4)3 (aq) + 3SO2 (g) + 6H2O (l)
Concentrated nitric acid renders iron passive due to the formation of layer of the oxide.
COMPOUNDS OF IRON
This a black basic oxide prepared by thermal decomposition of iron (II) oxalate in absence of air
It reacts with dilute mineral acids to form iron (II) salt and water
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The salts solutions are pale green and are readily oxidized by atmospheric oxygen to the
corresponding iron (III) salts. However, they are stable in presence of an acid.
This a green precipitate formed by action of dilute sodium hydroxide or ammonia solution on a
solution containing Fe2+
On exposure to air, it turns brown due to the formation of Iron (III) hydroxide
An aqueous solution of iron (II) salts contains [Fe(H2O)6]2+ and don’t undergo hydrolysis due to low
charge density
It is prepared by warming Iron with excess dilute sulphuric acid and evaporate the resultant solution
to crystallize pale green crystal. The crystals are efflorescent and oxidized on exposure to air with
formation of brown patches of iron (III) sulphate
A green solution turns yellow with effervescence of a colourless gas which forms brown fumes in air
3Fe2+ (aq) +4H+ (aq) + NO3- (aq) 3Fe3+ (aq) + NO (g) + 2H2O (l)
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(iii) Hydrogen peroxide
H2O2 (aq) + 2H+ (aq) + 2Fe2+ (aq) 2Fe3+ (aq) + 2H2O (l)
6Fe2+ (aq) + Cr2O72- (aq) + 14H+ (aq) 6Fe3+ (aq) + 2Cr3+ (aq) + 7H2O (l)
The iron (III) ions have a high charge density and are heavily hydrated therefore in aqueous solution
they exist as [Fe(H2O)6]3+ hence it undergoes hydrolysis to release protons which cause the solution
to be acidic
The oxide can be reduced by hydrogen, carbon and carbon monoxide to form iron
2FeSO4 (aq) + 2H2SO4 (aq) Fe2(SO4)3 (aq) + SO2 (g) + 2H2O (l)
Qn: Sodium carbonate solution was added to aqueous solution of iron (III) sulphate. Bubbles of a
colourless gas and a brown precipitate were observed. Explain this observation
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Soln: Due to high charge density, the hydrated ion undergoes hydrolysis to form insoluble iron (III)
hydroxide and hydrogen ions which cause the solution to be acidic i.e.
The hydrogen ions react with carbonate ions from sodium carbonate to form carbondioxide
gas which is colourless gas
The brown solution turns pale green and yellow solid is deposited
SO2 (g) + 2Fe3+ (aq) + 2H2O (l) 2Fe2+ (aq) + SO42- (aq) + 4H+ (aq)
N.B. Fe3+ ions are confirmed by use of potassium hexacyanoferrate (II) solution, a dark blue precipitate
is observed.
ZINC
Extraction
-Zincite
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Concentration of ore
Zinc blende is crushed into powder and mixed with water containing a frothing agent. Air is bubbled
through the mixture. The low density ore floats as a froth which is skimmed off.
Roasting
Zinc oxide is then mixed with coke and limestone in a blast furnace. The oxide is reduced to zinc metal
by carbon monoxide
The metal distils off with other blast furnace gases. The mixture of gases is allowed to cool (quenched)
to obtain crude zinc which ix purified by redistillation.
The major impurities are lead (II) sulphide, Cadmium and iron.
Reactions of Zinc
(b) Steam reacts with heated Zinc form Zinc oxide and Hydrogen gas
(c) Warm dilute mineral acids readily react with Zinc to liberate hydrogen gas
(d) It reacts with sodium hydroxide solution in presence of water to form zincate and water
Compound of Zinc
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ZnO (s) + 2OH- (aq) + H2O (l) [Zn (OH)4]2- (aq)
N.B. In aqueous solution salts of Zinc are colourless due to [Zn(H2O)4]2+ and are confirm by use of
disodium hydrogen phosphate where they form a white precipitate soluble in ammonia solution
Question:
(b) (i) Describe briefly how the ore you have named in (a) is concentrated
(ii) What further treatment of the ore is required immediately after concentration?
(c) Outline the process, giving equations for the production of zinc metal from the treated ore
(d) Zinc belongs to d-block in the periodic table yet it is not a transition metal. Explain this
statement.
(e) A piece of zinc metal was suspended in a solution of copper (II) sulphate in water. State what
was observed and write the equation for the change that took place.
MANGANESE
ORES
Pyrolusite-MnO2
Hausmannite-Mn3O4
The extraction is done by reduction of the oxide using aluminium followed by vacuum distillation
Direct reduction of manganese (IV) oxide is explosive thus the oxide is heated in oxygen to be
converted to trimanganese tetraoxide
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2. Manganese reacts with hot water to form sparingly soluble Manganese (II) hydroxide and hydrogen
gas
3. Dilute hydrochloric and sulphuric acid form pink solution of manganese (II) salts and hydrogen gas.
Qn: 4.0g impure manganese was dissolved in 20cm3 of 0.2M sulphuric acid.
Compounds of Manganese
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