F321 Redox & Oxidation Numbers

Redox and Oxidation Numbers

Candidates should be able to: (a) apply rules for assigning oxidation number to atoms in elements, compounds and ions; (b) describe the terms oxidation and reduction in terms of: (i) electron transfer, (ii) changes in oxidation number; (c) use a Roman numeral to indicate the magnitude of the oxidation state of an element, when a name may be ambiguous, eg nitrate(III) and nitrate(V); (d) write formulae using oxidation numbers; (e) explain that: (i) metals generally form ions by losing electrons with an increase in oxidation number to form positive ions, (ii) non-metals generally react by gaining electrons with a decrease in oxidation number to form negative ions; (f) describe the redox reactions of metals with dilute hydrochloric and dilute sulfuric acids; (g) interpretand make predictions from redox equations in terms of oxidation numbers and electron loss/gain.

Many reactions involve oxidation and reduction and it is not always easy to tell exactly what has been oxidized and what has been reduced. A "simple" definition of oxygen being added or removed isn't adequate since many redox reactions don't involve oxygen. Recall from electrolysis the idea that: O xidation I s L oss of electrons R eduction I s G ain of electrons

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. 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 choose the right oxidation numbers (in priority order): 1) Uncombined elements have oxidation number 0 e.g. H2, Cl2 etc. 2) Group 1 element in a compound: oxidation number = +1, Group 2 element in a compound: oxidation number = +2 Group 3 element in a compound: oxidation number = +3 The oxidation number of fluorine in a compound is always -1 The oxidation number of hydrogen is usually +1 (*exceptions not required for AS) e.g. in NaH it is -1

3) 4)

Page 1

F321 Redox & Oxidation Numbers 5) The oxidation number of oxygen is usually -2 (*exceptions not required at AS) e.g. in F2O it is +2 e.g. in H2O2 it is -1 The oxidation number of chlorine is usually -1 unless one of the rules above means that it needs to be otherwise e.g. in sodium chlorate NaClO where it is +1

6)

Given these rules, we can assign some of the oxidation numbers for the atoms in a substance, and with some further rules we can work out the other oxidation numbers. Rules to work out the remaining oxidation numbers: 7) The oxidation numbers in any compound add up to 0 e.g. in KI K has oxidation number +1 so I has oxidation number -1 8) Oxidation numbers in any compound ion add up to the charge on the ion e.g. in NH4+ H has oxidation number +1 and the sum of the oxidation numbers must be +1 (the charge on the ion) so N must have oxidation number -3. Using these rules we can work out any oxidation numbers: NaCl MgCl2 CO2 S2Cl2 KClO +1 -1 +2 -1 +4 -2 +1 -1 +1 +1 -2 -1 -2 +1 -1 ClO3+5 -2 -2 -2 = -1 ICl3 +3 -1 -1 -1 MnO4+7 -2 -2 -2 -2 = -1 Cr2O72+6 -2 +6 -2 -2 -2 -2 -2 -2 = -2

Now we can apply this idea to redox reactions: We write a balanced symbol equation, indicate the oxidation numbers of each element present, and then draw arrows to show what has been oxidized and what has been reduced, remembering that when something is oxidized its oxidation number increases and when something is reduced its oxidation number decreases. e.g. Mg + 2 HCl MgCl2 + H2 0 +1 -1 +2 -1 0 oxidation reduction

Page 2

F321 Redox & Oxidation Numbers Use of oxidation numbers in names When an atom can have more than one oxidation number in its compounds, we often need a number in roman numerals to indicate what the oxidation number is. We've seen this before where we saw roman numerals in the formulae of transition metal compounds: iron(II) sulphate - oxidation number of iron is +2 iron(III) chloride oxidation number of iron is +3 but we also use them when the name of a negative ion alone could be ambiguous: e.g. potassium chlorate could be KClO3 or KClO4. Both are real compounds. We use the oxidation number of the chlorine to distinguish their names K Cl O4 +1 +7 -2 -2 -2 -2

K Cl O3 +1 +5 -2 -2 -2 potassium chlorate(V) Check your understanding: i) Name these two compounds: NaNO2

potassium chlorate(VII)

NaNO3

Work out if these reactions are redox, and if so what has been oxidized and what has been reduced: ii) 2 Fe(s) + 3 Cl2(g) 2 FeCl3(s) (iron III chloride) iii) CuO(s) + H2(g) Cu(s) + H2O(g) iv) 2 Br-(aq) + Cl2(g) Br2(aq) + 2Cl-(aq) v) HCl (aq) + NaOH(aq) NaCl(aq) + H2O(l) Note that not every reaction shows a change in oxidation state, or involves oxidation or reduction ! Oxidising Agents and Reducing Agents A substance which gains electrons readily may remove an electron from another substance, causing it to be oxidized. We call a substance which does this an oxidizing agent. (Note that by gaining the electron it gets reduced itself in the reaction). Conversely a substance which loses electrons readily can reduce something else it is a reducing agent. (It will get oxidized in the reaction) Note: the oxidizing or reducing agent is the WHOLE SUBSTANCE not just one atom in a substance. Page 3

F321 Redox & Oxidation Numbers e.g. Fe(s) + Cl2(g) FeCl3(s)

Iron is OXIDISED from 0 to +3 So the OXIDISING AGENT is the Cl2 Practical example: Zinc metal is a good reducing agent, and can cause other substances to be reduced while it is oxidized to zinc ions: Zn(s) 0 (grey) 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 VO2+(aq) VO2+(aq) V3+(aq) V2+(aq) Oxidation number of V +5 +4 +3 +2 Colour yellow blue green mauve

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 needed 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 vi) 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).

Page 4

F321 Redox & Oxidation Numbers Answers to "Check your understanding" questions: i) sodium nitrate(III) sodium nitrate(V)

Work out if these reactions are redox, and if so what has been oxidized and what has been reduced: ii) 2 Fe(s) + 3 Cl2(g) 0 0 2 FeCl3(s) +3 -1 -1 -1 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

iii)

CuO(s) + H2(g) Cu(s) + H2O(g) +2 -2 0 0 +1 -2 +1

iv)

2 Br-(aq) + Cl2(g) Br2(aq) + 2Cl-(aq) REDOX -1 0 0 -1 bromide ions are oxidized to bromine chlorine is reduced to chloride ions HCl (aq) + NaOH(aq) NaCl(aq) + H2O(l) +1 -1 +1 -2 +1 +1 -1 +1 -2 +1 NOT REDOX

v)

"nitrate" could mean NO3- or NO2- ions "chlorate" could mean ClO2- or ClO3- or ClO4- ions vi) 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)

Page 5