Topic 8: Redox Chemistry AS and Groups 1, 2 and 7
- Syllabus
- 2017
- Topic
- —
- Level
- AS
Oxidation number is the charge an atom would have if every bond were treated as fully ionic and bonding electrons were assigned to the more electronegative atom. It is an electron-accounting model, not always a real charge.
| Rule | Oxidation number |
|---|---|
| uncombined element | 0 |
| monatomic ion | its ionic charge |
| sum in a neutral compound | 0 |
| sum in a polyatomic ion | overall ion charge |
| Group 1 / Group 2 in compounds | +1 / +2 |
| fluorine in compounds | −1 |
| oxygen usually | −2; −1 in peroxides |
| hydrogen usually | +1; −1 in metal hydrides |
Assign the fixed values first, multiply each oxidation number by its atom count, set the total equal to the species charge, and solve for the unknown.
Oxidation number belongs to each atom in the accounting model. It is not automatically the measured charge on that atom or the charge of the whole molecule.
| Species | Charge equation | Result |
|---|---|---|
| KMnO4 | +1+x+4(−2)=0 | Mn = +7 |
| Cr2O72− | 2x+7(−2)=−2 | Cr = +6 |
| H2O2 | 2(+1)+2x=0 | O = −1 because it is a peroxide |
| NaH | +1+x=0 | H = −1 because it is a metal hydride |
| NH4+ | x+4(+1)=+1 | N = −3 |
Write one unknown for the requested element, include every subscript and coefficient, and make the weighted total equal to 0 for a neutral compound or to the ion charge for a polyatomic ion.
Apply peroxide and metal-hydride exceptions before using the usual O = −2 and H = +1 rules. Reinsert the result and verify the total charge.
Do not divide by the number of atoms until every known contribution and the overall charge have been included.
A Roman numeral in a chemical name states the oxidation number of the named element in that compound or ion.
| Name | Roman numeral meaning | Formula check |
|---|---|---|
| iron(III) chloride | Fe is +3 | FeCl3 |
| copper(I) oxide | Cu is +1 | Cu2O |
| chlorate(V), ClO3− | Cl is +5 | x+3(−2)=−1 |
| chlorate(VII), ClO4− | Cl is +7 | x+4(−2)=−1 |
Write the numeral immediately after the relevant element name in parentheses. Use I, II, III, IV, V, VI or VII—not an Arabic numeral or a signed ionic charge.
In chlorate(V), V is the oxidation number of chlorine, not the charge on the chlorate ion, which is −1.
Treat the given oxidation numbers as signed contributions. Choose the smallest whole-number ratio that makes their total zero, then write the electropositive element first and simplify the subscripts.
| Name/oxidation numbers | Balance | Formula |
|---|---|---|
| iron(III) oxide: Fe +3, O −2 | 2(+3)+3(−2)=0 | Fe2O3 |
| sulfur(VI) oxide: S +6, O −2 | +6+3(−2)=0 | SO3 |
| copper(I) sulfide: Cu +1, S −2 | 2(+1)+(−2)=0 | Cu2S |
| chromium(III) sulfate | 2 Cr3+ balance 3 SO42− | Cr2(SO4)3 |
Keep a polyatomic ion intact and use brackets when more than one is required. Confirm both overall neutrality and the lowest ratio.
The criss-cross shortcut can leave unsimplified or chemically mis-grouped subscripts. Always verify the signed total and preserve polyatomic ions.
| Process | Electron transfer | Oxidation-number change |
|---|---|---|
| oxidation | loss of electrons | increases |
| reduction | gain of electrons | decreases |
For Mg + 2H+$\rightarrowMg^{2+}+H_2$, magnesium changes 0 to +2 and loses two electrons, so it is oxidised. Hydrogen changes +1 to 0 and gains electrons, so it is reduced.
In s- and p-block reactions, assign oxidation numbers before and after, identify each change, then use the electron count to confirm that total electron loss equals total electron gain.
Adding oxygen often signals oxidation, but electron transfer and oxidation-number change are the general definitions and also work when oxygen is absent.
| Agent | What it does to another species | What happens to the agent |
|---|---|---|
| oxidising agent | accepts electrons from it / oxidises it | gains electrons and is reduced |
| reducing agent | donates electrons to it / reduces it | loses electrons and is oxidised |
In Mg + 2H+$\rightarrowMg^{2+}+H_2,H^+$ gains electrons and is the oxidising agent; Mg loses electrons and is the reducing agent.
Identify the species containing the atom whose oxidation number decreases: that whole reactant species is the oxidising agent. The reactant whose oxidation number increases is the reducing agent.
An oxidising agent is not oxidised. It causes oxidation by accepting electrons and is itself reduced.
In disproportionation, the same element in one reactant species is simultaneously oxidised and reduced, forming products in higher and lower oxidation states.
In Cl2 + H2O ⇌ HCl + HClO, chlorine starts at 0. It becomes −1 in HCl and +1 in HClO, so the same Cl2 is both reduced and oxidised.
Confirm one starting oxidation number, at least two products containing that element, one increase and one decrease. Then check the balanced equation.
A reaction containing both oxidation and reduction is redox, but it is disproportionation only when both changes begin from the same element in the same reactant species.
| Before/after pattern | Classification |
|---|---|
| at least one oxidation number rises and another falls | redox |
| no oxidation number changes | not redox |
| the same reactant element both rises and falls | disproportionation, and therefore redox |
Cr2O72−$\rightleftharpoons2CrO_4^{2-}changescolourwithconditions,butchromiumremains+6inbothions.Itisnotredox.ChlorinereactingwithcoldalkaligivesCl^-andClO^-$, so Cl changes 0 to −1 and +1: disproportionation.
Assign only the oxidation numbers needed to test change, but compare the same element in reactants and products and cite the numerical changes.
A visible colour change, gas or precipitate does not prove redox. Classification depends on oxidation-number change.
Metals generally form positive ions by losing valence electrons. Their oxidation number increases from 0 in the element to a positive value: Na→Na++e− and Mg→Mg2++2e−.
Non-metals generally form negative ions by gaining electrons. Their oxidation number decreases from 0: Cl2+2e−$\rightarrow2Cl^-andO_2+4e^-$\rightarrow2O^{2-}$.
These opposite electron changes allow metals to act as reducing agents and non-metal molecules such as halogens to act as oxidising agents in many s- and p-block reactions.
This is a useful general trend, not a claim that non-metals always have negative oxidation numbers. Oxygen and halogens can appear in positive oxidation states in suitable compounds.
Write the changing species, balance its atoms, then add electrons to the more positive side until total charge is equal. For a full ionic equation, multiply half-equations so electron numbers match, add them and cancel electrons and any identical species.
| Change | Half-equation |
|---|---|
| iron oxidation | Fe2+$\rightarrowFe^{3+}+e^-$ |
| chlorine reduction | Cl2+2e−$\rightarrow2Cl^-$ |
| iron metal with iron(III) | Fe→Fe2++2e−; 2Fe3++2e−$\rightarrow2Fe^{2+}$ |
Adding the last pair gives Fe(s)+2Fe3+(aq)→3Fe2+(aq). Atoms and total charge are both balanced and no electron remains in the overall equation.
Electrons appear in half-equations to balance charge but must cancel from the final ionic equation. Do not balance charge by changing ionic formulae.
First ionisation energy generally decreases down both Groups 1 and 2.
| Change down the group | Effect on the outer electron |
|---|---|
| an extra occupied shell | greater distance from nucleus |
| more inner electrons | greater shielding |
| greater nuclear charge | increases attraction, but is outweighed by distance and shielding |
The outer electron feels weaker effective attraction and requires less energy to remove. Group 2 values remain generally higher than neighbouring Group 1 values because a Group 2 atom has a greater nuclear charge with a similar shell pattern.
Do not explain the decrease by nuclear charge falling—it increases. Increased radius and shielding outweigh that increase.
Reactivity increases from Li to K in Group 1 and from Mg to Ba in Group 2 because their characteristic reactions require electron loss.
Down the group, an extra shell increases distance and shielding, effective nuclear attraction for the outer electron falls, ionisation energy decreases, and forming M+ or M2+ becomes easier. Reactions with water or oxygen therefore become faster and more vigorous.
Group 2 atoms must lose two electrons rather than one, but the down-group trend is governed by the decreasing energies required to remove their outer electrons.
Metal reactivity down these groups increases even though electronegativity and ionisation energy decrease. Easier electron loss is the relevant direction.
| Reagent | Group 1, Li to K | Group 2, Mg to Ba |
|---|---|---|
| oxygen | Li forms Li2O; Na forms Na2O and Na2O2; K favours the more oxygen-rich superoxide KO2 in excess O2 | 2M+O2→2MO |
| chlorine | 2M+Cl2→2MCl | M+Cl2→MCl2 |
| cold water | 2M+2H2O→2MOH+H2; vigour increases Li to K | M+2H2O→M(OH)2+H2; Mg is very slow, Ca to Ba increasingly vigorous |
Magnesium reacts much more readily with steam: Mg(s)+H2O(g)→MgO(s)+H2(g). Calcium, strontium and barium form increasingly alkaline hydroxide solutions or suspensions with cold water.
Typical evidence includes metal burning in oxygen/chlorine, hydrogen effervescence with water, and an alkaline indicator colour when hydroxide forms.
Do not write one oxygen product for every Group 1 metal. Under the specified trend conditions, lithium favours oxide, sodium peroxide and potassium superoxide.
| Reactant | With water | With dilute acid |
|---|---|---|
| Group 1 oxide M2O | M2O+H2O→2MOH | M2O+2H+$\rightarrow2M^++H_2$O |
| Group 2 oxide MO | MO+H2O→M(OH)2 | MO+2H+$\rightarrowM^{2+}+H_2$O |
| hydroxide | already provides OH− in water | OH−+H+$\rightarrowH_2$O |
Soluble products give alkaline solutions. With acid, the basic oxide or hydroxide is neutralised to a salt and water; a solid may dissolve and the mixture may warm.
Reaction with water depends on accessibility and solubility: MgO reacts slowly, while heavier Group 2 oxides react more readily. Acid neutralisation is the common chemical pattern.
Do not describe gas bubbles for simple oxide/hydroxide neutralisation. Carbon dioxide is associated with carbonate plus acid, not oxide plus acid.
| Compound family down Mg to Ba | Trend | Useful endpoints |
|---|---|---|
| M(OH)2 | solubility increases | Mg(OH)2 is sparingly soluble; Ba(OH)2 is much more soluble |
| MSO4 | solubility decreases | MgSO4 is soluble; BaSO4 is insoluble |
Increasing hydroxide solubility makes saturated solutions more alkaline down the group. Decreasing sulfate solubility means adding sulfate ions increasingly gives a white precipitate, with BaSO4 especially useful for sulfate testing.
When comparing observations, separate solubility from reaction rate and use the correct anion. A cloudy mixture or precipitate indicates limited solubility, not absence of ions.
The two trends run in opposite directions. Do not transfer the hydroxide trend to sulfates.
A small and/or highly charged cation has high charge density and strongly polarises the electron cloud of NO3− or CO32−. This weakens bonds within the anion and makes thermal decomposition easier. Down a group, cation radius increases, polarising power falls and thermal stability rises.
| Family | Thermal decomposition pattern |
|---|---|
| Group 1 carbonates | generally stable; Li2CO3$\rightarrowLi_2O+CO_2$ |
| Group 2 carbonates | MCO3$\rightarrowMO+CO_2$ |
| Group 1 nitrates | 2MNO3$\rightarrow2MNO_2+O_2$ except Li |
| Li and Group 2 nitrates | 4LiNO3$\rightarrow2Li_2O+4NO_2+O_2;2M(NO_3)_2$\rightarrow2MO+4NO_2+O_2$ |
For similarly sized cations, a 2+ ion polarises more strongly than a 1+ ion. Lithium resembles magnesium because Li+ is unusually small, so both have appreciable polarising power.
Greater stability down the group means a higher temperature is needed; it does not mean decomposition becomes more exothermic or faster at the same temperature without qualification.
Heat excites electrons in atoms or ions to higher energy levels. When they fall to lower levels, they emit photons whose energies match the level differences. Characteristic wavelengths combine to give a diagnostic flame colour.
| Cation | Flame colour |
|---|---|
| Li+ | crimson red |
| Na+ | yellow |
| K+ | lilac |
| Ca2+ | brick/orange-red |
| Sr2+ | crimson red |
| Ba2+ | apple green |
| Mg2+ | no characteristic visible flame colour |
The observed colour identifies the metal ion because its allowed energy-level separations are characteristic. Sodium contamination can mask other colours because its yellow emission is intense.
Heating does not permanently colour the electrons. The colour is light emitted during downward transitions, not the colour of the solid compound itself.
| Procedure/evidence | Interpretation |
|---|---|
| heat comparable nitrate or carbonate samples in hard-glass tubes under comparable conditions | onset and vigour compare thermal stability |
| bubble gas through limewater | milkiness confirms CO2 from carbonate |
| insert a glowing splint | relighting confirms O2 from nitrate |
| observe brown gas and test damp indicator | brown, acidic NO2 accompanies nitrate decomposition to oxide |
Clean a nichrome/platinum wire loop with concentrated HCl and heat until no colour remains. Moisten it with HCl, pick up the sample, place it in a non-luminous blue flame, record the colour, and clean between samples.
Use similar sample amounts, particle sizes, heating positions and flame conditions. Record both the temperature/heating needed and verified gases rather than inferring decomposition from appearance alone.
A glowing splint tests oxygen; a lighted splint pop tests hydrogen. Use the test matched to the expected decomposition gas.
| Ion | Reagent and condition | Positive result | Ionic equation |
|---|---|---|---|
| CO32− / HCO3− | add dilute acid; pass gas into limewater | effervescence; limewater turns milky | CO32−+2H+$\rightarrowCO_2+H_2O;HCO_3^- +H^+\rightarrow$CO$_2$+H$_2$O | | SO$_4^{2-}$ | acidify, then add BaCl$_2$(aq) | white BaSO$_4$ precipitate | Ba$^{2+}$+SO$_4^{2-}\rightarrowBaSO_4$(s) |
| NH4+ | add NaOH(aq) and warm | NH3 turns damp red litmus blue and forms white fumes with HCl | NH4++OH−$\rightarrowNH_3+H_2$O |
CO2 is confirmed by Ca(OH)2+CO2$\rightarrowCaCO_3+H_2O.AcidifyingthesulfatetestremovescarbonateinterferencebeforeBa^{2+}$ is added.
A gas or white precipitate alone is not a complete identification. State the reagent, condition, observation and confirmatory test or ionic equation.
c(mol dm−3)=n/V(dm3), so convert cm3 to dm3 by dividing by 1000. Mass concentration = molar concentration ×Mr in g dm−3.
| Step | Calculation |
|---|---|
| 1 | moles of known solution = concentration × titre/pipette volume in dm3 |
| 2 | use the balanced acid–base equation to convert to moles of unknown in the aliquot |
| 3 | concentration of unknown = moles ÷ aliquot volume in dm3 |
| 4 | multiply by Mr only if g dm−3 is required |
Methyl orange changes red in acid through orange at the endpoint to yellow in alkali. Phenolphthalein is colourless in acid and pink in alkali; detect the first permanent very pale endpoint colour appropriate to titration direction.
Titre and aliquot volumes play different roles. Do not put both into c=n/V without first applying the balanced mole ratio.
| Stage | Action |
|---|---|
| burette | rinse with HCl, fill, remove funnel/air bubble and record initial reading |
| flask | rinse pipette with standard sodium carbonate, transfer a fixed aliquot to a conical flask and add methyl orange |
| rough titre | add HCl while swirling to locate the endpoint |
| accurate titres | run quickly to near endpoint, then add dropwise while swirling over a white tile; repeat to obtain concordant titres |
| calculate | use Na2CO3+2HCl→2NaCl+H2O+CO2 and the mean concordant titre |
With carbonate in the flask and HCl in the burette, methyl orange changes from yellow towards the first permanent orange endpoint. Read the burette at eye level to the nearest calibrated precision.
Use a volumetric pipette and filler, do not rinse the conical flask with analyte, and wash flask walls down with distilled water without changing moles present.
Concordant titres are close repeated values, not simply every recorded titre. Exclude the rough result from the calculated mean.
| Source | Control | Uncertainty treatment |
|---|---|---|
| two burette readings | eye level, no funnel/bubble, dropwise endpoint | add reading uncertainties for the titre |
| pipette delivery | condition with solution, allow to drain, touch tip to flask; do not blow out | use stated pipette tolerance |
| endpoint judgement | white tile, suitable indicator, repeat from both sides if needed | reflected in titre scatter |
| standard-solution volume/mass | quantitative transfer, make meniscus to mark, stopper and invert | use balance and flask tolerances |
For quantities multiplied or divided, add percentage uncertainties. For a burette with ±0.05 cm3 per reading, a titre has ±0.10 cm3; percentage uncertainty is 0.10/titre×100%. A larger sensible titre reduces this percentage.
Obtain concordant titres and average them to improve precision. Report a result to precision supported by the apparatus and include dominant systematic limitations separately.
Do not double every apparatus uncertainty automatically. The burette is doubled because a titre is the difference of two readings; a single pipette delivery uses one tolerance.
| Step | Quantitative action |
|---|---|
| calculate | required moles = target concentration × flask volume in dm3; mass = moles × molar mass of the hydrated solid acid |
| weigh/dissolve | accurately weigh the pure solid acid, dissolve it in distilled water in a beaker |
| transfer | pour through a funnel into a volumetric flask; rinse beaker, rod and funnel into the flask |
| make to volume | add water near the mark, use a dropping pipette to place the meniscus on the line, stopper and invert repeatedly |
Pipette a known aliquot of standard acid into a conical flask, add the suitable indicator (commonly phenolphthalein for ethanedioic acid/NaOH), titrate with NaOH to concordant endpoints, and use the balanced equation to find NaOH concentration.
For 100.0 cm3 of 0.0500 mol dm−3 H2C2O4$\cdot2H_2$O, moles required = 0.00500 mol; multiply by the hydrate's molar mass when calculating the solid mass.
Use the molar mass of the actual hydrated crystals, not anhydrous acid. Quantitative transfer requires all rinsings to reach the volumetric flask.
| Property down F2 to I2 | Trend | Explanation |
|---|---|---|
| melting/boiling temperature | increases | more electrons and greater polarisability strengthen London forces |
| room-temperature state | gases F2/Cl2, liquid Br2, solid I2 | stronger attractions require more energy to separate molecules |
| electronegativity | decreases | radius and shielding increase, weakening attraction for a bonding pair |
| reactivity as oxidising halogen | decreases | attraction for an incoming electron becomes weaker |
The elements also darken down the group: fluorine pale yellow, chlorine pale green, bromine red-brown and iodine grey-black in standard states.
The boiling trend is not caused by stronger X–X covalent bonds. Phase change overcomes intermolecular London forces between X2 molecules.
| Added halogen | Cl− | Br− | I− |
|---|---|---|---|
| Cl2 | no reaction | Br2 forms | I2 forms |
| Br2 | no reaction | no reaction | I2 forms |
| I2 | no reaction | no reaction | no reaction |
A more reactive halogen oxidises a less reactive halide: X2+2Y−$\rightarrow2X^-+Y_2.X_2gainselectronsandisreduced;Y^-$ loses electrons and is oxidised.
| Halogen | Standard state | Aqueous | Non-polar organic solvent |
|---|---|---|---|
| Cl2 | pale-green gas | pale green | pale green/yellow-green |
| Br2 | red-brown liquid | orange/red-brown | orange/red-brown |
| I2 | grey-black solid | brown | violet/purple |
Identify the displaced halogen from the final layer and solvent. Iodine is brown in water but violet/purple in a non-polar organic solvent.
| Reaction | Equation | Chlorine changes |
|---|---|---|
| with metal | 2Na+Cl2$\rightarrow$2NaCl | 0 to −1; chlorine is reduced |
| with water | Cl2+H2O⇌HCl+HClO | 0 to −1 and +1 |
| cold dilute NaOH | Cl2+2NaOH→NaCl+NaClO+H2O | 0 to −1 and +1; bleach |
| hot concentrated NaOH | 3Cl2+6NaOH→5NaCl+NaClO3+3H2O | 0 to −1 and +5 |
HClO/chlorate(I) produced in water is an oxidising disinfectant that kills microorganisms, so chlorine is used in water treatment. Dose must be controlled because chlorine chemistry can also be hazardous.
Bromine and iodine can undergo analogous reactions, with the same need to balance atoms and track the halogen from 0 into lower and higher oxidation states.
Chlorine with alkali is not simple neutralisation. It is disproportionation because chlorine is simultaneously reduced and oxidised.
| Solid halide + concentrated H2SO4 | Main evidence | Redox meaning |
|---|---|---|
| Cl− | steamy HCl fumes; acid–base reaction only | HCl is not a sufficient reducing agent |
| Br− | HBr then red-brown Br2 and SO2 | HBr reduces H2SO4 to SO2 |
| I− | HI then I2; SO2, sulfur and/or H2S may form | HI is strongest and reduces sulfur to lower oxidation states |
Reducing ability increases HCl < HBr < HI because the H–X bond weakens and X− is increasingly easy to oxidise down the group.
| Halide test after acidifying with HNO3 | Precipitate | With NH3(aq) |
|---|---|---|
| Cl− | AgCl white | dissolves in dilute NH3 |
| Br− | AgBr cream | dissolves in concentrated NH3 |
| I− | AgI yellow | insoluble |
Ag++X−$\rightarrowAgX(s).Hydrogenhalidesformwhiteammoniumhalidesmokewithammonia,HX(g)+NH_3(g)\rightarrowNH_4X(s),andformacidicsolutionsinwater,HX+H_2O\rightarrowH_3O^++X^-$.
Use nitric acid before silver nitrate; sulfuric acid would add sulfate and hydrochloric acid would add chloride, creating interfering precipitates or ions.
| Property | Fluorine end | Astatine end |
|---|---|---|
| state/colour at room temperature | pale-yellow gas | dark grey/black solid |
| melting/boiling temperature | lowest | highest, by stronger London forces |
| electronegativity/reactivity as halogen | highest; strongest oxidising tendency | lowest; weakest oxidising tendency |
| halide reducing ability | F− weakest | At− predicted strongest |
F2 should displace every lower halide, while At2 should displace none of Cl−, Br− or I−. Compounds and displacement behaviour are predicted by continuing the same electron-gain, shielding and polarisability trends.
State the observed trend, identify its cause, place F or At beyond the known sequence, and give a directional prediction. Keep state, colour, electronegativity and redox strength as separate claims.
Astatine is rare and radioactive, so many properties are predictions with limited direct evidence. Trend extrapolation should be stated as a prediction, not an exact measured value.