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In general, when we refer to a chemical formula we mean the symbols for the atoms
present, along with the number of each type of atom. Strictly this is a molecular formula, or
empirical formula (depending on whether the structure is simple molecular or a giant
structure), and we should be aware that there are more detailed types of formula
(structural, displayed, skeletal etc.) that we may also encounter.
We need a chemical formula for:
- any compound
- any diatomic element e.g. H F Br O N I Cl
Otherwise we use just the element symbol (e.g. for metals, noble gases, and often for
sulphur or phosphorus which are really polyatomic molecules)
Valency of atoms
We can use the idea of valency to help figure out the formulae of substances.
Definition: Valency is the number of electrons an atom involves in bonding.
In simple terms, the valency can be thought of as the number of bonds an atom (or group
of atoms) forms.
It doesnt matter what type of bonding the atoms use just the number of electrons
involved: e.g. Na loses 1 outer shell electron to form ionic bonds so its valency is 1. O
gains 2 electrons whether bonding covalently or forming oxide ions, so its valency is 2.
Carbon shares 4 electrons in covalent bonding, so it valency is 4. There is a simple
correlation between Group in the periodic table and valency, at least for the more common
elements, but there are many exceptions:
Group 1
Valency = 1
Group 5 (15) Valency = 3
Group 2
Valency = 2
Group 6 (16) Valency = 2
Group 3
Valency = 3
Group 7 (17) Valency = 1
Group 4
Valency = 4
Group 8 (18) Valency = 0
Valency of Ions
The charge on a simple ion can be predicted from its position in the periodic table, and the
charge corresponds to the valency. Metal atoms in Groups 1-3 lose their outer shell
electrons to form ions, so their valency is the same as the Group number, and the charge
on these ions is positive.
e.g. sodium atom [valency 1] loses 1 electron to make sodium ion Na +
aluminium atom [valency = 3] loses 3 electrons to make an Al3+ ion
Non-metal atoms gain electrons to complete their outer shells. The valency is the same as
the number of electrons they gain, and the charge on these ions is negative.
e.g. oxygen atom [valency 2] gains 2 electrons to make oxide ion O2chlorine atom [valency 1] gains 1 electron to make chloride ion Cl-
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Elements in the d-block do not have easily predicted valencies, and some have more than
one valency. You should know the charges (and hence valencies) of the following):
Zinc ions, Zn2+
Silver ions, Ag+
Valency = 2
Valency = 1
Compound ions
Valency can also be applied to compound ions (ions containing more than one atom).
These have to be learnt!
hydroxide
OH- valency = 1
nitrate
NO3- valency = 1
carbonate
CO32 valency = 2
sulphate
SO42 valency = 2
ammonium NH4+ valency = 1
Using valency to write formulae
Write the valency under each element or ion, then swap and simplify if the numbers if they
will divide down. (The absence of a number implies 1.)
Application
Calcium chloride
Hydrogen sulphide
Aluminium oxide
Calcium oxide
Silicon dioxide
Ca = 2 Cl = 1 so CaCl2
H = 1 S = 2 so H2S
Al = 3 O = 2 so Al2O3
Ca = 2 O = 2 so Ca2O2 simplifies to CaO
Si = 4 O = 2 so Si2O4 simplifies to SiO2
The same rules apply to compound ions. Brackets are used if there is more than one of the
compound ion:
Application
Sodium sulphate
Magnesium nitrate
Aluminium hydroxide
Ammonium sulphate
Na = 1 sulphate = 2 so Na2SO4
Mg = 2 nitrate = 1 so Mg(NO3)2
Al = 3 hydroxide = 1 so Al(OH)3
ammonium = 1 sulphate = 2 so (NH4)2SO4
Note: Al(OH)3 is NOT the same as AlOH3 which would imply 1 Al, 1 O and 3 H
bonded together, not 3 x hydroxide !
Check your understanding:
Use valency to work out the formulae of the three most common lab acids;
i) hydrochloric acid,
ii) sulphuric acid
iii) nitric acid.
These are compounds of hydrogen, with chloride, sulphate and nitrate respectively.
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HNO3 + Mg Mg(NO3)2 + H2
Write balanced equations for the following reactions (including state symbols)
xvi) Solutions of sodium sulphate and barium nitrate react to form a barium sulphate
precipitate and a sodium sulphate solution
xvii)
Zinc carbonate thermally decomposes when heated to produce zinc oxide and
carbon dioxide
Page 3
xviii)
As a final check, remember that equations have to be balanced so that the same number of
atoms of each element appear on each side, but charges also have to be balanced. The
same total charge must appear on each side of the equation.
e.g. potassium iodide solution reacts with lead(II) nitrate solution to produce a yellow
precipitate of lead iodide, and leaving a solution of potassium nitrate.
Full equation:
Split into ions:
Note how the ionic equation deals with the two drawbacks. The spectator ions have been
removed showing just the reaction that actually takes place: that between the lead ions and
the iodide ions. Moreover while the original equation only told us that lead nitrate reacts
with potassium iodide, the ionic equation tells us that any solution containing lead ions will
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react with any solution containing iodide ions (e.g. lead ethanoate solution will react with
sodium iodide) in the same way it is a more general equation.
Application
Sodium hydroxide is neutralized by dilute nitric acid. Use the method above to construct the
ionic equation for this reaction, and use it to explain why any acid can be neutralized by any
alkali.
Full equation:
Find spectators:
Ionic equation:
So any acid (source of H+ ions in solution) reacts with any alkali (source of OH- ions in
solution) to make water, neutralizing the acid/alkali.
xx)
xxi)
Structure:
ionic
ionic
simple mol
Empirical formula:
NaCl
Li2O
CH
Molecular formula:
C6H6
Page 5
% by mass
Ar
moles
ratio
C
85.7
12
7.14
1
H
14.3
1
14.3
2
Page 6
We can use the loss or gain of electrons to tell us what is being oxidized and what is being
reduced in a reaction. We use a concept called OXIDATION NUMBER to help us do this.
Oxidation numbers also can help us to work out chemical formulae correctly.
Changes in oxidation number tell us what has been oxidized or reduced:
OXIDATION is an INCREASE in oxidation number, by LOSING ELECTRONS
REDUCTION is a DECREASE in oxidation number, by GAINING ELECTRONS
Rules to assign oxidation numbers (in priority order):
1)
Uncombined elements have oxidation number 0 e.g. H2, Cl2 etc.
2)
3)
4)
The oxidation number of hydrogen is usually +1, except where a previous rule
applies, e.g. in metal hydrides such as NaH the oxidation number of H is -1 because
the Na has to be +1 according to Rule 2).
5)
The oxidation number of oxygen is usually -2, except where a previous rule applies,
e.g. in F2O it is +2 because the F must be -1 according to rule 3. In peroxides such
as H2O2 the O must be -1 because the H is +1 according to Rule 4.
6)
The oxidation number of chlorine is usually -1 except where previous rule applies
e.g. in sodium chlorate(I) NaClO where Cl must be +1 because Na is +1 and O is -2
according to the earlier rules.
Stock Notation
In the previous example we saw the use of a roman numeral in brackets. This is used to
specify the oxidation number for an element that can have multiple oxidation numbers.
Sodium chlorate(I)
Sodium chorate(III)
Sodium chromate(VI)
Iron(II) hydroxide
Given these rules, we can assign oxidation numbers to some of the atoms in a chemical
formula, and with some further rules we can work out the other oxidation numbers:
Page 7
ICl3
+3 -1
-1
-1
CO2
+4 -2
-2
S2Cl2
+1 -1
+1 -1
MnO4+7 -2
-2
-2
-2
= -1
Cr2O72+6 -2
+6 -2
-2
-2
-2
-2
-2
= -2
KClO
+1 +1 -2
NaNO2
NaNO3
Mg + 2 HCl MgCl2 + H2
0
+1 -1
+2 -1
0
oxidation
reduction
Note that not every reaction shows a change in oxidation state, or involves oxidation or
reduction !
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Fe(s) + Cl2(g)
0
0
FeCl3(s)
+3 -1(x3)
Zn2+(aq)
+2 (colourless)
Being a transition metal, vanadium has variable oxidation number. It forms a variety of ions
with different oxidation states and different colours. Starting with the highest oxidation
number ion we can reduce these using metallic zinc, and see the progressive colour
changes:
Vanadium ion in solution Oxidation number of V
VO2+(aq)
+5
+
2+
mixture of VO2 (aq) and VO (aq)
VO2+(aq)
+4
3+
V (aq)
+3
V2+(aq)
+2
Colour
yellow
green
blue
green
violet
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The manganate(VII) - also called permanganate - ion is a good oxidising agent and can
reverse these changes. The intense colour of the permanganate disappears because the
permanganate ion is being reduced to Mn3+(aq). The vanadium ions are progressively
oxidized, reversing the colour changes above.
MnO4-(aq)
+7 (intense purple)
Mn3+(aq)
+3 (pale pink)
The manganate(VII) ion is a good example of where an oxidation number is used because
the name "manganate" is ambiguous. How many oxygen atoms does the ion contain ?
What is its charge ? We can work it out if we know that oxidation state of the Mn is +7 in
this case.
Check your understanding:
"nitrate" could mean NO3- or NO2- ions
"chlorate" could mean ClO2- or ClO3- or ClO4- ions
xxviii) Assign oxidation numbers to the elements in each of these five ions, and use these
to give the ions their full names (including roman numerals).
Hydrated and anhydrous crystals
Crystals of hydrated ionic substances contain water as part of the crystal structure. For
example, green iron(II) sulphate crystals contain seven water molecules for each formula
unit of iron sulphate. We call this water of crystallization, denoting it in the formula as
shown: FeSO4.7H2O
It is important that we take this into account when weighing or calculating the relative
formula mass for any hydrated substance. We need to add the mass of the water into M r !
Look at the bottles when you are weighing out salts, and check the formula and M r given on
the bottle.
e.g. iron(II) sulphate crystals, FeSO4.7H2O
Mr = 55.8 + 32.1 + (4x16) + (7 x 18) = 277.9
Check your understanding:
xxix) Work out the relative formula mass of:
sodium carbonate crystals, Na2CO3.10H2O
manganese(II) chloride crystals, MnCl2.4H2O
xxx)
When hydrated crystals are heated, some or all of the water is driven off. If all the water is
driven off, they become anhydrous. This is often accompanied by a colour change
anhydrous iron(II) sulphate is grey.
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We may be asked to work out the formula for hydrated crystals given % composition data.
We do this by converting the % to a mole ratio (divide by the A r or Mr for each % given), just
like we did with percentage composition calculations already:
Application
A sample of sodium sulphate contains 14.28% sodium ions, 29.84% sulphate ions and
55.88% of water, by mass. Determine the formula of the crystals.
%
Mr
moles
ratio
Na+
14.28
23.0
0.62
2
SO4229.84
96.1
0.31
1
H2O
55.88
18
3.10
10
(dividing all by 0.31)
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mass (g)
Mr
moles
mole ratio
XCl2
2.73
?
0.1261/6 = 0.02102
1
:
H2O
5.00 2.73 = 2.27
18
0.1261
moles = mass/Mr
6
from formula of hydrated salt
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HCl
H2SO4
HNO3
AlBr3
Li2SO4
K2O
CuO
MgI2
BaCO3
Ca(HCO3)2
Fe(OH)2,
Fe(OH)3
(NH4)2CO3
Al2S3
xiv)
xv)
xvi)
xvii)
xviii)
ixx)
xx)
xxi)
xxii)
xxiii)
Cr2O3
sodium nitrate(III)
xxv)
2 FeCl3(s)
+3 -1
-1
-1
Cu2O
sodium nitrate(V)
REDOX
iron has been oxidized to iron III
chlorine has been reduced to chloride
REDOX
copper II has been reduced to copper
hydrogen has been oxidised
REDOX
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-1
-1
xxviii) Assign oxidation numbers to the elements in each of these five ions, and use these
to give the ions their full names (including roman numerals).
NO3NO2ClO2ClO3ClO4-
+5 -2 -2 -2
+3 -2 -2
+3 -2 -2
+5 -2 -2 -2
+7 -2 -2 -2 -2
nitrate(V)
nitrate(III)
chlorate(III)
chlorate(V)
chlorate(VII)
Mr =
Mr =
286.0
197.9
Page 14