Predict the products of electrolysis in each of the following:
(i) An aqueous solution of AgNO3 with silver electrodes
(ii) An aqueous solution AgNO3 with platinum electrodes
(iii) A dilute solution of H2SO4 with platinum electrodes
(iv) An aqueous solution of CuCl2 with platinum electrodes.
(i) AgNO3 ionizes in aqueous solutions to form Ag+ and NO-3 ions.
On electrolysis, either Ag+ ions or H2O molecules can be reduced at the cathode. But the reduction potential of Ag+ ions is higher than that of H2O.
Ag+(aq) + e- → Ag(s) ; E° = +0.80V
2H2O(l) + 2e- → H2(g) + 2OH-(aq) ; E° = -0.83V
Hence, Ag+ ions are reduced at the cathode. Similarly, Ag metal or H2O molecules can be oxidized at the anode. But the oxidation potential of Ag is higher than that of H2O molecules.
Ag(s) → Ag+(aq) + e- ; E° = -0.80V
2H2O(l) → O2(g) + 4 H+(aq) + 4e- ; E° = -1.23V
Therefore, Ag metal gets oxidized at the anode.
(ii) Pt cannot be oxidized easily. Hence, at the anode, oxidation of water occurs to liberate O2. At the cathode, Ag+ ions are reduced and get deposited.
(iii) H2SO4 ionizes in aqueous solutions to give H+ and SO2-4 ions.
H2SO4(aq) → 2H+(aq) + SO2-4(aq)
On electrolysis, either of H+ ions or H2O molecules can get reduced at the cathode. But the reduction potential of H+ ions is higher than that of H2O molecules.
2H+(aq) + 2e- → H2(g) ; E° = 0.0V
2H2O(aq) + 2e- → H2g + 2OH-(aq) ; E° = -0.83V
Hence, at the cathode, H+ ions are reduced to liberate H2 gas.
On the other hand, at the anode, either of SO2-4 ions or H2O molecules can get oxidized. But the oxidation of SO2-4 involves breaking of more bonds than that of H2O molecules.Hence, ions have a lower oxidation potential than H2O. Thus, H2O is oxidized at the anode to liberate O2 molecules.
(iv) In aqueous solutions, CuCl2 ionizes to give Cu2+ and Cl- ions as:
CuCl2(aq) → Cu2+(aq) + 2Cl-(aq)
On electrolysis, either of Cu2+ ions or H2O molecules can get reduced at the cathode. But the reduction potential of Cu2+ is more than that of H2O molecules.
Cu2+(aq) + 2e- → Cu(aq) ; E° = +0.34V
H2O(l) + 2e- → H2(g) + 2OH- ; E° = -0.83V
Hence, Cu2+ ions are reduced at the cathode and get deposited.
Similarly, at the anode, either of Cl- or H2O is oxidized. The oxidation potential of H2O is higher than that of Cl-.
2Cl-(aq) → Cl2(g) + 2e- ; E° = -1.36V
2H2O(l) → O2(g) + 4H+(aq) + 4e- ; E° = -1.23V
But oxidation of H2O molecules occurs at a lower electrode potential than that of Cl- ions because of over-voltage (extra voltage required to liberate gas). As a result, Cl- ions are oxidized at the anode to liberate Cl2 gas.
Balance the following redox reactions by ion – electron method :
(a) MnO4 – (aq) + I – (aq) → MnO2 (s) + I2(s) (in basic medium)
(b) MnO4 – (aq) + SO2 (g) → Mn2+ (aq) + HSO4– (aq) (in acidic solution)
(c) H2O2 (aq) + Fe 2+ (aq) → Fe3+ (aq) + H2O (l) (in acidic solution)
(d) Cr2O7 2– + SO2(g) → Cr3+ (aq) + SO42– (aq) (in acidic solution)
Assign oxidation number to the underlined elements in each of the following species:
(a) NaH2PO4
(b) NaHSO4
(c) H4P2O7
(d) K2MnO4
(e) CaO2
(f) NaBH4
(g) H2S2O7
(h) KAl(SO4)2.12 H2O
What are the oxidation number of the underlined elements in each of the following and how do you rationalise your results ?
(a) KI3
(b) H2S4O6
(c) Fe3O4
(d) CH3CH2OH
(e) CH3COOH
Justify that the following reactions are redox reactions:
(a) CuO(s) + H2(g) → Cu(s) + H2O(g)
(b) Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g)
(c) 4BCl3(g) + 3LiAlH4(s) → 2B2H6(g) + 3LiCl(s) + 3 AlCl3 (s)
(d) 2K(s) + F2(g) → 2K+F– (s)
(e) 4 NH3(g) + 5 O2(g) → 4NO(g) + 6H2O(g)
Balance the following equations in basic medium by ion-electron method and oxidation number methods and identify the oxidising agent and the reducing agent.
(a) P4(s) + OH – (aq) → PH3(g) + HPO2 – (aq)
(b) N2H4(l) + ClO3 – (aq) → NO(g) + Cl–(g)
(c) Cl2O7 (g) + H2O2(aq) → ClO – 2(aq) + O2(g) + H + (aq)
Fluorine reacts with ice and results in the change:
H2O(s) + F2(g) → HF(g) + HOF(g)
Justify that this reaction is a redox reaction.
Write the formulae for the following compounds:
(a) Mercury(II) chloride
(b) Nickel(II) sulphate
(c) Tin(IV) oxide
(d) Thallium(I) sulphate
(e) Iron(III) sulphate
(f) Chromium(III) oxide
While sulphur dioxide and hydrogen peroxide can act as oxidising as well as reducing agents in their reactions, ozone and nitric acid act only as oxidants. Why?
Identify the substance oxidised, reduced, oxidising agent and reducing agent for each of the following reactions:
(a) 2AgBr (s) + C6H6O2(aq) → 2Ag(s) + 2HBr (aq) + C6H4O2(aq)
(b) HCHO(l) + 2[Ag (NH3)2]+(aq) + 3OH-(aq) → 2Ag(s) + HCOO-(aq) + 4NH3(aq) + 2H2O(l)
(c) HCHO (l) + 2Cu2+(aq) + 5 OH-(aq) → Cu2O(s) + HCOO-(aq) + 3H2O(l)
(d) N2H4(l) + 2H2O2(l) → N2(g) + 4H2O(l)
(e) Pb(s) + PbO2(s) + 2H2SO4(aq) → 2PbSO4(s) + 2H2O(l)
The compound AgF2 is an unstable compound. However, if formed, the compound acts as a very strong oxidizing agent. Why?
How do you account for the formation of ethane during chlorination of methane?
What are hybridisation states of each carbon atom in the following compounds ?
(i) CH2=C=O,
(ii) CH3CH=CH2,
(iii) (CH3)2CO,
(iv) CH2=CHCN,
(v) C6H6
What will be the minimum pressure required to compress 500 dm3 of air at 1 bar to 200 dm3 at 30°C?
What are the common physical and chemical features of alkali metals?
Calculate the molecular mass of the following:
(i) H2O
(ii) CO2
(iii) CH4
What is the basic theme of organisation in the periodic table?
Explain the formation of a chemical bond.
Choose the correct answer. A thermodynamic state function is a quantity
(i) used to determine heat changes
(ii) whose value is independent of path
(iii) used to determine pressure volume work
(iv) whose value depends on temperature only.
A liquid is in equilibrium with its vapour in a sealed container at a fixed temperature. The volume of the container is suddenly increased.
a) What is the initial effect of the change on vapour pressure?
b) How do rates of evaporation and condensation change initially?
c) What happens when equilibrium is restored finally and what will be the final vapour pressure?
Justify the position of hydrogen in the periodic table on the basis of its electronic configuration.
At 1127 K and 1 atm pressure, a gaseous mixture of CO and CO2 in equilibrium with soild carbon has 90.55% CO by mass
C (s) + CO2 (g) ↔ 2CO (g)
Calculate Kc for this reaction at the above temperature.
Classify the following reactions in one of the reaction type studied in this unit.
(a) CH3CH2Br + HS- → CH3CH2SH + Br-
(b) (CH3)2C = CH2 + HCl → (CH3)2ClC-CH3
(c) CH3CH2Br + HO- → CH2 = CH2 + H2O + Br-
(d) (CH3)3C - CH2OH + HBr → (CH3)2CBrCH2CH3 + H2O
Write the significance of a plus and a minus sign shown in representing the orbitals.
Which of the two: OO2NCH2CH2O- or CH3CH2O- is expected to be more stable and why?
The hydroxides and carbonates of sodium and potassium are easily soluble in water while the corresponding salts of magnesium and calcium are sparingly soluble in water. Explain.
Suggest a reason as to why CO is poisonous.
Arrange the bonds in order of increasing ionic character in the molecules: LiF, K2O, N2, SO2 and ClF3.
If the speed of light is 3.0 × 108 ms–1, calculate the distance covered by light in 2.00 ns.
Among the second period elements the actual ionization enthalpies are in the order
Li < B < Be < C < O < N < F < Ne.
Explain why
(i) Be has higher ΔiH than B
(ii) O has lower ΔiH than N and F?
Explain the physical significance of Van der Waals parameters.