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)
(a) The O.N. (oxidation number) of P decreases from 0 in P4 to -3 in PH3 and increases from 0 in P4 to + 2 in HPO-2. Hence, P4 acts both as an oxidizing agent as well as a reducing agent in this reaction.
Ion-electron method:
The oxidation half equation is:
P4(s) → H2PO-(aq)
The P atom is balanced as:
P0 4(s) → 4H2P+1O-(aq)
The O.N. is balanced by adding 4 electrons as:
P4(s) → 4H2PO-(aq) + 4e-
The charge is balanced by adding 8OH- as:
P4(s) + 8OH - (aq) → 4H2PO-2(aq)
The O and H atoms are already balanced. The reduction half equation is:
P4(s) → PH3(g)
The P atom is balanced as
P04(s) → 4 P-3H3(g)
The O.N. is balanced by adding 12 electrons as:
P4(s) + 12e- → 4 PH3(g)
The charge is balanced by adding 12OH- as:
P4(s) + 12e- → 4 PH3(g) + 12OH-(aq) .....(i)
The O and H atoms are balanced by adding 12H2O as:
P4(s) + 12H2O(l) + 12e- → 4 PH3(g) + 12OH-(aq) -- (ii)
By multiplying equation (i) with 3 and (ii) with 2 and then adding them, the balanced chemical equation can be obtained as:
P4(s) + 3OH-(aq) + 3H2O → PH3 + 3H2PO-2(aq)
(b)
The oxidation number of N increases from -2 in N2H4 to +2 in NO and the oxidation number of Cl decreases from + 5 in CIO-3 to -1 in Cl-. Hence, in this reaction, N2H4 is the reducing agent and CIO-3 is the oxidizing agent. Ion-electron method:
The oxidation half equation is:
N-22 H4(l) → N+2 O(g)
The N atoms are balanced as:
N2H4(l) → 2NO(g)
The oxidation number is balanced by adding 8 electrons as:
N2H4(l) → 2NO(g) + 8e-
The charge is balanced by adding 8 OH-ions as:
N2H4(l) + 8OH-(aq) → 2NO(g) + 8e-
The O atoms are balanced by adding 6H2O as:
N2H4(l) + 8OH-(aq) → 2NO(g) + 6H2O(l) + 8e- .... (i)
The reduction half equation is:
C+5IO-3(aq) → C-1l-(aq)
The oxidation number is balanced by adding 6 electrons as:
CIO-3(aq) + 6e- → Cl-(aq)
The charge is balanced by adding 6OH- ions as:
CIO-3(aq) + 6e- → Cl-(aq) + 6OH-(aq)
The O atoms are balanced by adding 3H2O as:
CIO-3(aq) + 3H2O(l) + 6e- → Cl-(aq) + 6OH-(aq) .... (ii)
The balanced equation can be obtained by multiplying equation (i) with 3 and equation (ii) with 4 and then adding them as:
3N2H4(l) + 4CIO-3(aq) → 6NO(g) + 4Cl-(aq) + 6H2O(l)
Oxidation number method:
Total decrease in oxidation number of N = 2 × 4 = 8
Total increase in oxidation number of Cl = 1 × 6 = 6
On multiplying N2H4 with 3 and CIO-3 with 4 to balance the increase and decrease in O.N., we get:
3N2H4(l) + 4CIO-3(aq) → NO(g) + Cl-(aq)
The N and Cl atoms are balanced as:
3N2H4(l) + 4CIO-3(aq) → 6NO(g) + 4Cl-(aq)
The O atoms are balanced by adding 6H2O as:
3N2H4(l) + 4CIO-3(aq) → 6NO(g) + 4Cl-(aq) + 6H2O(l)
This is the required balanced equation.
(c)
The oxidation number of Cl decreases from + 7 in Cl2O7 to + 3 in CIO-2and the oxidation number of O increases from -1 in H2O2 to zero in O2. Hence, in this reaction, Cl2O7 is the oxidizing agent and H2O2 is the reducing agent.
Ion-electron method:
The oxidation half equation is:
H2O-12(aq) → O02(g)
The oxidation number is balanced by adding 2 electrons as:
H2O2(aq) → O2(g) + 2e-
The charge is balanced by adding 2OH-ions as:
H2O2(aq) + 2OH-(aq) → O2(g) + 2e-
The oxygen atoms are balanced by adding 2H2O as:
H2O2(aq) + 2OH-(aq) → O2(g) + 2H2O(l) + 2e- ... (i)
The reduction half equation is:
C+7l2O7(g) → C+3lO-2(g)
The Cl atoms are balanced as:
Cl2O7(g) → 2ClO-2(g)
The oxidation number is balanced by adding 8 electrons as:
Cl2O7(g) + 8e- → 2ClO-2(g)
The charge is balanced by adding 6OH- as:
Cl2O7(g) + 8e- → 2ClO-2(g) + 6OH- (aq)
The oxygen atoms are balanced by adding 3H2O as:
Cl2O7(g) + 3H2O(l) + 8e- → 2ClO-2(g) + 6OH- (aq) .... (ii)
The balanced equation can be obtained by multiplying equation (i) with 4 and adding equation (ii) to it as:
Cl2O7(g) + 4H2O2(aq) + 2OH- (aq) → 2ClO-2(aq) + 4O2(g) + 5H2O(l)
Oxidation number method:
Total decrease in oxidation number of Cl2O7 = 4 × 2 = 8
Total increase in oxidation number of H2O2 = 2 × 1 = 2
By multiplying H2O2 and O2 with 4 to balance the increase and decrease in the oxidation number, we get:
Cl2O7(g) + 4H2O2(aq) → CIO-2(aq) + 4O2(g)
The Cl atoms are balanced as:
Cl2O7(g) + 4H2O2(aq) → 2CIO-2(aq) + 4O2(g)
The O atoms are balanced by adding 3H2O as:
Cl2O7(g) + 4H2O2(aq) → 2CIO-2(aq) + 4O2(g) + 3H2O(l)
The H atoms are balanced by adding 2OH- and 2H2O as:
Cl2O7(g) + 4H2O2(aq) + 2OH-(aq) → 2CIO-2(aq) + 4O2(g) + 5H2O(l)
This is the required balanced equation.
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)
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?
Calculate the oxidation number of sulphur, chromium and nitrogen in H2SO5, Cr2O2- 7 and NO– 3. Suggest structure of these compounds. Count for the fallacy.
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.
A 25 watt bulb emits monochromatic yellow light of wavelength of 0.57μm. Calculate the rate of emission of quanta per second.
For the process to occur under adiabatic conditions, the correct condition is:
(i) ΔT = 0
(ii) Δp = 0
(iii) q = 0
(iv) w = 0
What will be the conjugate bases for the Brönsted acids: HF, H2SO4 and HCO3?
Calculate the temperature of 4.0 mol of a gas occupying 5 dm3 at 3.32 bar.
(R = 0.083 bar dm3 K–1 mol–1).
How would you explain the following observations?
(i) BeO is almost insoluble but BeSO4 in soluble in water,
(ii) BaO is soluble but BaSO4 is insoluble in water,
(iii) LiI is more soluble than KI in ethanol.
Predict the formula of the stable binary compounds that would be formed by the combination of the following pairs of elements. (a) Lithium and oxygen
(b) Magnesium and nitrogen
(c) Aluminium and iodine
(d) Silicon and oxygen
(e) Phosphorus and fluorine
(f) Element 71 and fluorine
The enthalpy of combustion of methane, graphite and dihydrogen at 298 K are, –890.3 kJ mol–1 , –393.5 kJ mol–1, and –285.8 kJ mol–1 respectively. Enthalpy of formation of CH4(g) will be
(i) –74.8 kJ mol–1
(ii) –52.27 kJ mol–1
(iii) +74.8 kJ mol–1
(iv) +52.26 kJ mol–1
The ionization constant of nitrous acid is 4.5 x 10-4. Calculate the pH of 0.04 M sodium nitrite solution and also its degree of hydrolysis.
On the basis of quantum numbers, justify that the sixth period of the periodic table should have 32 elements.
How does H2O2 behave as a bleaching agent?
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