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Halogens: Group 7 AQA AS Chemistry
Physical Proper;es Halogens displacing halide ions
Halide ion reduc;on of conc. H2SO4 Tes;ng for halide ions
Halogen reac;ons with water Redox ( H2O2 and S2O3
2-‐ )
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Reac;on of Sodium and Chlorine
hJps://www.youtube.com/watch?v=afRlDab1_e8
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Halogens: F2 Cl2 Br2 I2
pale green orange/brown solu;on black/grey solid (purple fumes)
Halide ions: F-‐ Cl-‐ Br-‐ I-‐ Increasing boiling point as Group descends Decreasing electronega;vity Decreasing oxidising strength of halogen as Group Descends Increasing reducing strength of halide ions as Group Descends
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Explain why Cl2 has a lower boiling point than Br2 ?
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Cl2 molecules are smaller in size and have a smaller Mr than Br2 molecules Hence, the intermolecular forces between Cl2 molecules (van der Waals) tend to be weaker than those present in Br2
As a result, less energy is needed to separate the Cl2 molecules than Br2 molecules
Explain why Cl2 has a lower boiling point than Br2 ?
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F Cl Br I Iden;fy the halogen that is the strongest oxidising agent. Give the formula of the halide ion that is the strongest reducing agent.
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Displacement of halogens by fluorine
hJps://www.youtube.com/watch?v=3Sspgx-‐aOL0
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Halogen/Halide oxida3on (displacement) reac3ons
The stronger halogen oxidising agent will oxidise the halide ion posi2oned below it in the Group.
Strength of oxidising agent, in order of strongest...... to....... weakest:
F2 Cl2 Br2 I2
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Predict which reac;on is feasible or not using the oxidising strength rule
1. F2 + 2Cl− à 2F− + Cl2 2. F2 + 2I− à 2F− + I2 3. Cl2 + 2I− à 2Cl− + I2 4. Br2 + 2Cl− à 2Br− + Cl2 5. Cl2 + 2Br− à 2Cl− + Br2 6. I2 + 2Br− à 2I− + Br2
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Predict which reac;on is feasible or not using the oxidising strength rule
1. F2 + 2Cl− à 2F− + Cl2 2. F2 + 2I− à 2F− + I2 3. Cl2 + 2I− à 2Cl− + I2 4. Br2 + 2Cl− à 2Br− + Cl2 5. Cl2 + 2Br− à 2Cl− + Br2 6. I2 + 2Br− à 2I− + Br2
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Halogen/Halide oxida3on (displacement) reac3ons
F2 oxidises Cl− to Cl2 F2 + 2e− à 2F− 2Cl− à Cl2 + 2e−
F2 + 2Cl− à 2F− + Cl2
F2 oxidises Br− to Br2 F2 + 2e− à 2F− 2Br− à Br2 + 2e−
F2 + 2Br− à 2F− + Br2
F2 oxidises I− to I2 F2 + 2e− à 2F− 2I− à I2 + 2e−
F2 + 2I− à 2F− + I2
The stronger halogen oxidising agent will oxidise the halide of a halogen posi2oned below it in the Group.
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Halogen/Halide oxida3on (displacement) reac3ons
F2 oxidises Cl− to Cl2 F2 + 2e− à 2F− 2Cl− à Cl2 + 2e−
F2 + 2Cl− à 2F− + Cl2
F2 oxidises Br− to Br2 F2 + 2e− à 2F− 2Br− à Br2 + 2e−
F2 + 2Br− à 2F− + Br2
F2 oxidises I− to I2 F2 + 2e− à 2F− 2I− à I2 + 2e−
F2 + 2I− à 2F− + I2
The stronger halogen oxidising agent will oxidise the halide of a halogen posi2oned below it in the Group.
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Halogen/Halide oxida3on (displacement) reac3ons
Cl2 oxidises Br− to Br2 (colourlessàorange solu;on)
Cl2 oxidises I− to I2
The stronger halogen oxidising agent will oxidise the halide of a halogen posi2oned below it in the Group.
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Halogen/Halide oxida3on (displacement) reac3ons
Cl2 oxidises Br− to Br2 (colourlessàorange solu;on)
Cl2 + 2e− à 2Cl− 2Br− à Br2 + 2e− Cl2 + 2Br− à 2Cl− + Br2
Cl2 oxidises I− to I2 Cl2 + 2e− à 2Cl− 2I− à I2 + 2e−
Cl2 + 2I− à 2Cl− + I2
The stronger halogen oxidising agent will oxidise the halide of a halogen posi2oned below it in the Group.
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Halogen/Halide oxida3on (displacement) reac3ons
Br2 oxidises I− to I2
The stronger halogen oxidising agent will oxidise the halide of a halogen posi2oned below it in the Group.
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Halogen/Halide oxida3on (displacement) reac3ons
Br2 oxidises I− to I2 Br2 + 2e− à 2Br− 2I− à I2 + 2e−
Br2 + 2I− à 2Br− + I2
The stronger halogen oxidising agent will oxidise the halide of a halogen posi2oned below it in the Group.
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What other product is missing from reduc;on of H2SO4
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S Ox. state=0
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Halide reac;ons with conc. H2SO4 Concentrated sulfuric acid acts as an oxidising agent, and oxidises: bromide ions AND iodide ions
Concentrated sulphuric acid is not a strong enough oxidising agent to oxidise fluoride or chloride ions
KCl + H2SO4 à KHSO4 + HCl 2KCl + H2SO4 à K2SO4 + 2HCl
HCl misty white fumes
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2Br− + 2H+ + H2SO4 à Br2 + SO2 + 2H2O
Oxida;on (Br− à Br2): Br ox. state: -‐1à0
Reduc;on(H2SO4àSO2): S ox state: +6 à +4
2Br− à Br2 + 2e−
2H+ + H2SO4 + 2e− à SO2 + 2H2O
orange/brown vapour
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Oxida;on (I− à I2): Br ox. state: -‐1à0 Reduc;on(H2SO4àSO2): S ox state: +6 à +4
Reduc;on(H2SO4àS): S ox state: +6 à 0 Reduc;on(H2SO4àH2S): S ox state: +6 à -‐2
2I− à I2 + 2e−
6H+ + H2SO4 + 6e− à S + 4H2O
2H+ + H2SO4 + 2e− à SO2 + 2H2O
8H+ + H2SO4 + 8e− à H2S + 4H2O
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8I− + 8H+ + H2SO4 à 4I2 + H2S + 4H2O
2I− + 2H+ + H2SO4 à I2 + SO2 + 2H2O
Black/grey solid and
purple gas (I2)
Black/grey solid and
purple gas (I2)
6I− + 6H+ + H2SO4 à 3I2 + S + 4H2O
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Reducing ability of halide ions increases as Group 7 descends? [3]
F− , Cl− will not reduce conc H2SO4 Br− will reduce conc H2SO4 to SO2
I− will reduce conc H2SO4 to mixture of SO2, S and H2S
• To be a reducing agent, each halide ion must lose an outer shell electron. • Iodide ions have a larger atomic radius (more electron shells and greater
shielding) than chloride ions. • This results in the outer shell electron, that is to be lost from the iodide
ion, being further from the nucleus and less strongly held by the nucleus compared with the electron that is to be lost from the chloride ion.
• Hence, iodide ions are stronger reducing agents than chloride ions
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In the series, F, Cl, Br, I, it is energe;cally more favourable to convert Iodide ion to Iodine
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In test 3: write the simplest ionic equa;on for the reac;on. Iden;fy the species responsible for the misty white fumes.
In test 4: write the two half-‐equa;ons for I-‐ to I2 and H2SO4 to H2S State the role of the H2SO4 (.........................) and iden;fy the black solid (.........), yellow solid (.................)and the gas that smelled of roJen eggs (.........................).
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In test 3: write the simplest ionic equa;on for the reac;on. H2SO4 + Cl– à HCl + HSO4
– Iden;fy the species responsible for the misty white fumes. HCl
In test 4: write the two half-‐equa;ons for I-‐ to I2 and H2SO4 to H2S 2I− à I2 + 2e− 8H+ + H2SO4 + 8e− à H2S + 4H2O
State the role of the H2SO4 (oxidising agent) and iden;fy the black solid (iodine), yellow solid (sulfur) and the gas that smelled of roJen eggs (hydrogen sulfide).
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Potassium chloride
Potassium bromide
Potassium iodide
Silver nitrate solution
Dilute Aqueous Ammonia
(few drops)
Concentrated Ammonia
(few drops)
!
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F −
Cl − Br −
I −
AgNO3 acidified with dilute HNO3
no ppt; colourless solu;on (AgF is soluble)
white precipitate
cream precipitate
yellow precipitate
add excess dilute NH3 to the ppt.
dissolves precipitate
par;ally soluble
does not dissolve
add excess conc. NH3 to the ppt.
dissolves precipitate
dissolves precipitate
does not dissolve
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Why is AgNO3 acidified when tes;ng for halide ions ?
Remove anions that may interfere with the test (e.g. CO32-‐, OH-‐, SO3
2-‐) and/or prevent the forma;on of other insoluble silver compounds that would invalidate the test
Ideally, why is HNO3 and not HCl, used to acidify AgNO3 ?
A false posi;ve test occurs as a white precipitate will be formed upon addi;on of HCl due to presence of aqueous Cl-‐ , hence invalidate test.
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Indicate a poten3al test tube reac3on test that could be used to dis3nguish between HCl(aq) and HNO3(aq)
TEST: reagent: AgNO3 (or any soluble silver salt) with HCl(aq): white precipitate with HNO3(aq): remains colourless
AgNO3 must be acidified by HNO3 prior to being used as a test for presence of Cl-‐
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Write the simplest ionic equa;on for the reac;on that has taken place in Test 1. State the type of reac;on that has taken place in Test 1.
Write the simplest ionic equa;on for the reac;on that has taken place in Test 2. State what would be observed when excess dilute NH3 (aq) is added to the white precipitate made in Test 2.
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Write the simplest ionic equa;on for the reac;on that has taken place in Test 1. Cl2+ 2I– à 2Cl– + I2 State the type of reac;on that has taken place in Test 1. redox
Write the simplest ionic equa;on for the reac;on that has taken place in Test 2. Ag+ + Cl – à AgCl State what would be observed when excess dilute NH3 (aq) is added to the white precipitate made in Test 2. it dissolves, colourless solu3on
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Indicate two poten3al test tube reac3on tests that could be used to dis3nguish between AgBr(s) and AgI(s)
TEST 1: reagent: conc H2SO4 with AgBr(s): cream solid turns orange AND brown vapour (Br2) with AgI(s): yellow solid turns black, purple vapour (I2), bad egg smell (H2S)
TEST 1: reagent: conc NH3 with AgBr(s): cream solid dissolves, solu;on formed with AgI(s): precipitate remains that does not dissolve
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Indicate two poten3al test tube reac3on tests that could be used to dis3nguish between AgBr(s) and AgI(s)
TEST 1: reagent: concentrated H2SO4 with AgBr(s): cream solid turns orange AND brown vapour (Br2) with AgI(s): black solid/ purple vapour (I2), forma;on of yellow solid (S), bad egg smell (H2S)
TEST 1: reagent: concentrated NH3 with AgBr(s): cream solid dissolves, solu;on formed with AgI(s): solid does not dissolve
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Describe two different tests that dis;nguish AgCl(s) from AgI(s)
NH3 (aq) dilute conc. H2SO4
dissolves white AgCl, colourless solu;on formed
misty white fumes (HCl)
does not dissolve AgI, (even if conc. NH3 used) yellow solid remains
black solid and/or purple vapour(I2) forma;on of yellow solid (S) roJen egg smell gas (H2S)
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Select the correct sodium halide: NaF NaCl NaBr NaI Descrip3on Formula of
sodium halide
1 This sodium halide is a white solid that reacts with concentrated sulfuric acid to give a brown gas.
2 When a solu;on of this sodium halide is mixed with silver nitrate solu;on, no precipitate is formed.
3 When this solid sodium halide reacts with concentrated sulfuric acid, the reac;on mixture remains white and steamy fumes are given off.
4 A colourless aqueous solu;on of this sodium halide reacts with orange bromine water to give a dark brown solu;on.
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Select the correct sodium halide: NaF NaCl NaBr NaI Descrip3on Formula of
sodium halide
1 This sodium halide is a white solid that reacts with concentrated sulfuric acid to give a brown gas.
NaBr
2 When a solu;on of this sodium halide is mixed with silver nitrate solu;on, no precipitate is formed.
NaF
3 When this solid sodium halide reacts with concentrated sulfuric acid, the reac;on mixture remains white and steamy fumes are given off.
NaCl (NaF)
4 A colourless aqueous solu;on of this sodium halide reacts with orange bromine water to give a dark brown solu;on.
NaI
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Halogen reac;ons with H2O
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In bright sunlight: Cl2 + H2O à 2HCl + ½ O2
Cl2 + H2O ⇌ HClO + HCl Cl2 gas and cold water :
Cl2 gas is TOXIC. Why do we use it in our drinking water/swimming pools The (health) benefit outweighs the risk; once reac;on is completed, very liJle remains unreacted; only very low doses of sodium chlorate(I) (NaClO) are formed.
pale green colour due to Cl2 species Is water oxidised ?
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Chlorine + cold dilute NaOH
Cl2 + 2NaOH à NaCl + NaClO + H2O
oxida3on: Cl ox state: 0 à +1 reduc3on: Cl ox state: 0 à -‐1
Sodium Chlorate (I) solu3on used to kill bacteria (e.g. bleach, disinfectants, sterilisers)
Chlorine is both oxidised and reduced
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Br2 + H2O ⇌ HBrO + HBr Br2 liquid and cold water:
Br2 used to kill microbes in swimming pools, but Br2 is toxic?
The (health) benefit outweighs the risk; once reac;on is completed, very liJle remains unreacted; only very low doses are used
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More Redox • Halide ion acts as a reducing agent
• Halogen acts as an oxidising agent
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I2+ 2S2O32–→ 2I– + 2S4O6
2–
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(a) Kills bacteria / prevents bacterial diseases; Chlorine is a toxic substance Cl2+ H2O → HCl + HClO (b) Cl2(aq) to Br–(aq); yellow-‐brown solu;on 2Br– + Cl2 → 2Cl– + Br2
Cl2(aq) to I–(aq); brown/black solu;on 2I– + Cl2 → 2Cl– + I2 c) NaBr, products include: orange/brown vapour Br2 and SO2 (toxic choking colourless gas) NaI, products include: purple vapour/black solid of I2, gas with smell of bad eggs (H2S); SO2 (toxic choking colourless gas) and S (yellow solid) 2Br – → Br2 + 2e– 2I– →I2 + 2e– H2SO4 + 2e– + 2H+ → SO2 + 2H2O H2SO4 + 6e– + 6H+ → S + 4H2O H2SO4 + 8e– + 8H+ → H2S + 4H2O
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(a) Reduc;on involves gain of electrons; a reducing agent loses (donates) electrons (b) (i) Sulphur dioxide, oxida;on state +4;
Sulphur, oxida;on state 0; Hydrogen sulphide, oxida;on state – 2
(ii) Sulphur dioxide is a toxic choking colourless gas Sulphur is a yellow solid Hydrogen sulphide gas has a smell of bad eggs
(iii) H2SO4 + 2H+ + 2e– → SO2 + 2H2O
H2SO4 + 6H+ + 6e-‐ → S + 4H2O H2SO4 + 8H+ + 8e-‐ → H2S + 4H2O
(c) Cl2+ H2O → HCl + HClO Water is not oxidised The oxida;on states of O (–2) and H (+1) remain unchanged