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Oxidation Reduction
1. Addition of Oxygen 1. Removal of Oxygen
Ex. 2Mg + O2 2MgO Ex. CuO + C Cu + CO
Oxidation Number
It is an imaginary or apparent charge developed over atom of an element when it goes from its elemental free state
to combined state in molecules.
It is calculated on basis of an arbitrary set of rules.
It is a relative charge in a particular bonded state.
In order to keep track of electron-shifts in chemical reactions involving formation of compounds, a more practical
method of using oxidation number has been developed.
In this method, it is always assumed that there is a complete transfer of electron from a less electronegative atom to
a more electronegative atom.
Fluorine atom
Fluorine is most electronegative atom (known). It always has oxidation number equal to –1 in all its compounds
Oxygen atom
In general and as well as in its oxides , oxygen atom has oxidation number equal to –2.
In case of (I) peroxide (e.g. H2O2, , Na2O2 ) is –1,
(II) super oxide (e.g. KO2) is –1/2
(III) ozonide (e.g. KO3) is –1/3
(IV) in OF2 is + 2 & in O2F2 is +1
Hydrogen atom
In general, H atom has oxidation number equal to +1. But in metallic hydrides ( e.g. NaH, KH), it is –1.
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CHEMISTRY FOR JEE MAIN & ADVANCED
6 + (–2)
Now, you can also calculate Average Oxidation number of S = = + 2 (as we have calculated before)
2
ETOOS KEY POINTS
Miscellaneous Examples
In order to determine the exact or individual oxidation number we need to take help from the structures of the
molecules. Some special cases are discussed as follows:
O O
(i) The structure of CrO5 is Cr
||
O O O
From the structure, it is evident that in CrO5 there are two peroxide linkages and one double bond. The contribution
of each peroxide linkage is –2. Let the oxidation number of Cr is x.
x + (–2)2 + (–2) = 0 or x = 6
Oxidation number of Cr = + 6 Ans
O
(ii) The structure of H2SO5 is H O O S
O
H O
From the structure, it is evident that in H2SO5, there is one peroxide linkage, two sulphur-oxygen double bonds
and one OH group. Let the oxidation number of S = x.
(+ 1) + (– 2) + x + (–2) 2+ (–2) + 1 = 0
or x+ 2–8=0 or x–6 =0 or x= 6
Oxidation number of S in H2SO5 is + 6 Ans.
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REDOX REACTION AND EQUIVALENT CONCEPT
wt. in g
1. Number of moles of molecules =
Mol. wt.
wt. in g
Number of moles of atoms =
Atomic mass
Volume at STP
Number of moles of gases =
Standard molar volume
Number of particles
Number of moles of particles, e.g. atoms, molecular ions etc. =
Avogadro No.
Moles of solute in solution = M × V(L)
Atomic wt.
2. Equivalent wt. of element =
Valence
Mol.wt.
Equivalent wt. of compound =
Total charge on cation or anion
Mol wt.
Equivalent wt. of acid =
Basicity
Mol wt.
Equivalent wt. of base =
Acidity
Formula wt.
Equivalent wt. of an ion =
Charge on ion
Molecular wt.
Equivalent wt. of acid salt =
Replaceable H atom in acid salt
Mol.wt.
Equivalent wt. of oxidizing or reducing agent =
Change in oxidation number per mole
wt.in g
No. of equivalent = N × V(L) =
Eq.wt.
Ws ×1000 x × d ×10
3. Molarity (M) = =
Ms × V Ms
where
Ws = wt. of solute in g
Ms = Mol. wt. of solute
x = % by mass of solute
d = density of solution in g/ml
V = volume of solution in ml
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REDOX REACTION AND EQUIVALENT CONCEPT
SOLVED EXAMPLES
Ex. 1 The weight of sodium bromate required to prepare 55.5 mL of 0.672 N solution for cell reaction,
BrO3– + 6H+ + 6e– Br– + 3H2O, is
(A) 1.56 g (B) 0.9386 g (C) 1.23 g (D) 1.32 g
Sol. Meq. of NaBrO3 = 55.5 × 0.672 = 37.296
Let weight of NaBrO3 = W
W
× 6 × 1000 = 37.296 (equivalent weight = M/6) of n-factor = 6
M NaBrO3
M
× 6 × 1000 = 37.296
151
W = 0.9386 g
Hence, (B) is the correct answer.
Ex. 3 If 0.5 moles of BaCl2 is mixed with 0.1 moles of Na3PO4, the maximum amount of Ba3(PO4)2 that can be formed is
(A) 0.7 mol (B) 0.5 mol (C) 0.2 mol (D) 0.05 mol
Sol. Let us first solve this problem by writing the complete balanced reaction.
3BaCl2 + 2Na3PO4 Ba3(PO4)2 + 6NaCl
3
We can see that the moles of BaCl 2 used are times the moles of Na 3PO 4. Therefore, to react with
2
3
0.1 mol of Na3PO4, the moles of BaCl2 required would be 0.1 × = 0.15. Since BaCl2 is 0.5 mol, we can conclude that
2
3
Na3PO4 is the limiting reagent. Therefore, moles of Ba3(PO4)2 formed is 0.1 × = 0.05 mol.
2
Hence, (D) is the correct answer.
Ex. 4 A 0.1097 g sample of As2O3 required 36.10 mL of KMnO4 solution for its titration. The molarity of KMnO4 solution is.
(A) 0.02 (B) 0.04 (C) 0.0122 (D) 0.3
Sol. n-factor = 5
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REDOX REACTION AND EQUIVALENT CONCEPT
2. Match List-I (Compounds) with List-II (Oxidation states of nitrogen) and select answer using the codes given below
the lists :-
List-I List-II
(A) NaN3 1. +5
(B) N2H2 2. +2
(C) NO 3. –1/3
(D) N2O5 4. –1
Code : (A) (B) (C) (D)
(A) 3 4 2 1
(B) 4 3 2 1
(C) 3 4 1 2
(D) 4 3 1 2
4. 50 mL of 0.1 M solution of a salt reacted with 25 mL of 0.1 M solution of sodium sulphite. The half reaction for the
oxidation of sulphite ion is :-
SO32– (aq) + H2O () SO2– +
4 (aq) + 2H (aq) + 2e
–
If the oxidation number of metal in the salt was 3, what would be the new oxidation number of metal :
(A) zero (B) 1 (C) 2 (D) 4
5. An element A in a compound ABD has oxidation number An–. It is oxidised by Cr2O72– in acid medium. In the
experiment 1.68 × 10–3 moles of K2Cr2O7 were used for 3.26 × 10–3 moles of ABD. The new oxidation number of A after
oxidation is
(A) 3 (B) 3 – n (C) n – 3 (D) +n
7. In which of the following reaction is there a change in the oxidation number of nitrogen atoms :-
(A) 2 NO2 N2O4 (B) NH3 + H2O NH4+ + OH–
(C) N2O5 + H2O 2HNO3 (D) none
8. In the reaction
xHI + yHNO3 NO + I2 + H2O
(A) x = 3, y = 2 (B) x = 2, y = 3 (C) x = 6, y = 2 (D) x = 6, y = 1
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CHEMISTRY FOR JEE MAIN & ADVANCED
3. Which of the following samples of reducing agents is /are chemically equivalent to 25 mL of 0.2 N KMnO4 to be
reduced to Mn2+ and water :
(A) 25 mL of 0.2 M FeSO4 to be oxidized to Fe3+
(B) 50 mL of 0.1 M H3AsO3 to be oxidized to H3AsO4
(C) 25 mL of 0.1 M H2O2 to be oxidized to H+ and O2
(D) 25 mL of 0.1 M SnCl2 to be oxidized to Sn4+
4. 0.1 M solution of KI reacts with excess of H2SO4 and KO3 solutions, according to equation
5– + O3– + 6H+ 32 + 3H2O ; which of the following statements is/are correct :
(A) 200 mL of the K solution react with 0.004 mole KIO3.
(B) 100 mL of the K solution reacts with 0.006 mole of H2SO4.
(C) 0.5 litre of the K solution produced 0.005 mole of I2.
Molecular Weight
(D) Equivalent weight of KO3 is equal to .
5
6. There are two sample of HCl having molarity 1N and 0.25 N. Find volume of these sample taken in order to prepare
0.75 N HCl solution. (Assume no water is used) :
(A) 20 mL, 10 mL (B) 100 mL, 50 mL (C) 40 mL, 20 mL (D) 50 mL, 25 mL
7. To a 25 ml H2O2 solution excess acidified solution of KI was added. The iodine liberated 20 ml of 0.3 N sodium
thiosulphate solution. Use these data to choose the correct statements from the following :
(A) The weight of H2O2 present in 25 ml solution is 0.102 g
(B) The molarity of H2O2 solution is 0.12 M
(C) The weight of H2O2 present in 1 L of the solution is 0.816 g
(D) The volume strength of H2O2 is 1.344 L
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CHEMISTRY FOR JEE MAIN & ADVANCED
1. Column-I Column-II
Molecular weight
(A) Eq. wt. = (p) When CrI3 oxidises into Cr2O72– and IO4–
33
Molecular weight
(B) Eq. wt. = (q) When Fe(SCN)2 oxidises into Fe3+, SO42–, CO32–
27
and NO3–
Molecular weight
(C) Eq. wt. = (r) When NH4SCN oxidizes into SO42–, CO32– and
28
NO3–
Molecular weight
(D) Eq. wt. = (s) When As2S3 oxidises into AsO3– and SO42–
24
2. Column-I Column-II
(A) When Bi2S3 converted into Bi5+ and S (p) 18
(B) When Al2(Cr2O7)3 reduced into Cr3+ in (q) 11
acidic medium
(C) When FeS2 converted into Fe2O3 and (r) 2
SO2
(D) When Mn(NO3)2 converted into (s) 10
MnO42–and NO
3. Column-I Column-II
3M
(A) P2H4 →PH3 + P4H2 (p) E=
4
3M
(B) I2 →I – + IO3– (q) E=
5
15M
(C) MnO4– + Mn2+ + H2O →Mn3O4 + H+ (r) E=
26
5M
(D) H3PO2 →PH3 + H3PO3 (s) E=
6
4. Column-I Column-II
(A) Molarity (p) Dependent on temperature
MA × n A
(B) Molality (q) x 100
n A M A + n BM B
(C) Mole fraction (r) Independent of temperature
XA
(D) Mass % (s) XBMB × 1000
Where MA , MB are molar masses, nA , nB are no of moles & XA , XB are mole fractions of solute and solvent
respectively.
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REDOX REACTION AND EQUIVALENT CONCEPT
1. KMnO4 oxidizes Xn+ ion to XO3–, itself changing to Mn 2+ in acid medium. 2.68 × 10–3 mole of Xn+ requires
–3 –
1.61 × 10 mole of MnO4 . What is the value of n? Also calculate the atomic mass of X, if the weight of 1g equivalent
of XCln is 56.
2. In a quantitative determination of iron in an ore, an analyst converted 0.40 g, of the ore into its ferrous. This required
40.00 mL of 0.1 N solution of KMnO4 for titration.
(i) How many milliequivalents of KMnO4 does 40.00 mL of 0.1 N solution represent?
(ii) How many equivalents of iron were present in the sample of the ore taken for analysis?
(e) Cu(NH3)42+ (aq) + S2O42– (aq) SO32– (aq) + Cu (s) + NH3 (aq)
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REDOX REACTION AND EQUIVALENT CONCEPT
(3) N2O5 + H2O 2HNO3 (4) AgNO3 + KI AgI + KNO3
4. In the coordination compound, K4[Ni (CN)6], the oxidation state of nickel is [AIEEE-03]
(1) +1 (2) +2 (3) –1 (4) 0
5. The oxidation state of Cr in [Cr(NH3)4Cl2]+ is - [AIEEE-05]
(1) +2 (2) +3 (3) 0 (4) +1
6. The oxidation state of chromium in the final product formed by the reaction between Kl and acidified potassium
dichromate solution is - [AIEEE-05]
(1) +6 (2) +4 (3) +3 (4) +2
7. Which of the following chemical reaction depicts the oxidizing behaviour of H2SO4 ? [AIEEE-06]
(1) Ca(OH)2 + H2SO4 CaSO4 + 2H2O (2) NaCl + H2SO4 NaHSO4 + HCl
(3) 2PCl5 + H2SO4 2POCl3 + 2HCl + SO2Cl2 (4) 2HI + H2SO4 I2 + SO2 + 2H2O
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CHEMISTRY FOR JEE MAIN & ADVANCED
MOCK TEST
1. The number of moles of KMnO4 that will be needed to react completely with one mole of ferrous oxalate in acid
solution is
(A) 3/5 (B) 2/5 (C) 4/5 (D) 1
2. The number of moles of KMnO4 that will be needed to react with one mole of sulphite ions in acidic solution is
(A) 2/5 (B) 3/5 (C) 4/5 (D) 1
4. An aqueous solution of 6.3 gm of oxalic acid dihydrate is made upto 250 ml. The volume of 0.1 N NaOH required to
completely neutralize 10 ml of this solution is
(A) 40 ml (B) 20 ml (C) 10 ml (D) 4 ml
5. Consider a titration of potassium dichromate solution with acidified Mohr’s salt solution using diphenylamine as
indicator. The number of moles of Mohr’s salt required per mole of dichromate is
(A) 3 (B) 4 (C) 5 (D) 6
7. There are two sample of HCl having molarity 1N and 0.25 N. Find volume of these sample taken in order to prepare
0.75 N HCl solution. (Assume no water is used) :
(A) 20 mL, 10 mL (B) 100 mL, 50 mL (C) 40 mL, 20 mL (D) 50 mL, 25 mL
8. To a 25 ml H2O2 solution excess acidified solution of KI was added. The iodine liberated 20 ml of 0.3 N sodium
thiosulphate solution. Use these data to choose the correct statements from the following :
(A) The weight of H2O2 present in 25 ml solution is 0.102 g
(B) The molarity of H2O2 solution is 0.12 M
(C) The weight of H2O2 present in 1 L of the solution is 0.816 g
(D) The volume strength of H2O2 is 1.344 L
9. Statement-1 : In the redox reaction 8 H+ (aq) + 4 NO3– + 6 Cl– + Sn(s) SnCl62– + 4 NO2 + 4 H2O, the reducing
agent is Sn(s).
Statement-2 : In balancing half reaction, S2O32– S(s), the number of electrons added on the left is 4.
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11th Class Modules Chapter Details