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REFRESHMENT OF MEMORY

REDOX REACTIONS : These reactions involve transfer of electrons from one atom to another atom. We can divide various redox titrations into following category. (1) Simple Redox titrations involving oxidizing agent. (2) lodimetry (3) lodometry (4) Estimation of oxidizing agent (5) Complex reactions involving redox system as well as non-redox system. METHOD : It is more convenient to apply the equivalent concept in volumetric calculations involving redox changes. However while applying the equivalent method we have to consider various modifications of equivalents concept. However we can apply mole concept also but with mole concept generally problems become lengthier. n FACTOR IN REDOX SYSTEM : n Factor in redox reactions is calculated by maximum total moles of electrons transferred by one mole of reactant. Depending upon the kind of reactions we have various methods to find out n factor. For example : n factor for oxidation of I2 to IO3 is 10 because 1 mole I2 transfer 10 mole of electrons. EQUIVALENT WEIGHT OF REDOX REAGENTS :

Formula weight Formula weight = Change in O.No. per molecule = No. of electrons in half - cell equation .
n-FACTOR OF A SALT IN A REDOX PROCESS : 1. Salt that react in such a way that only one type of atoms in the salt undergoes change in oxidation state. Application
Mn2+ KMnO4 H 2CO2 C2O42 H S4O62 S2O 32 H Cr3+ Cr2O72 H
+ + + +

M/5 M/2 M/1 M/6 M/1 M/2

FeSO4 Fe2O3

Fe2O3 FeSO4

Note : See the moles of atoms of that element whose OS changes in the reactant. 2. (a) OS 2Mn+7 3Mn+7 3Mn+7 Mn+7 + Mn+2 Mn+7 + 2Mn+2 2Mn+7 + Mn+2 5/2 10/3 5/3 (Balanced equation) Element is present in two products in one with the same OS and in other different

(b) Element is present in the products, in both different OS such that both are result of either oxidation or reduction 2Mn+7 3Mn+7 3Mn+7 3. Mn+4 + Mn+2 2Mn+2 + Mn+4 Mn+2 + 2Mn+4 8/2 13/3 11/3 (Balanced equation)

Salts that react in such a way that two types of atoms in the salt undergo change in OS. (a) Both are either oxidized or reduced Cu2S Cu++ + SO2 + NO2 + CO2 + NO + Cr+6 8 4 3 10 7

Fe(NO3)3 FeC2O4 Fe(NO3)3 FeCr2O4

Fe2+ Fe3+ Fe2+ Fe3+

(b) One atom is oxidized & other is reduced KClO3 KCl + 3/2 O2 N2 + Cr2O3 + 4H2O M/6 M/6

(NH4)2Cr2O7 4.

n factor of a sub undergoing disproportionation :


M M E1 + E2 = n + n = 1 2

n1n2 n1 + n2

2H2O2 2HCuCl2 4KClO3

2H2O

O2

M/1 M/(1/2) M/(3/2) M/(5/3)

Cu + Cu++ + 4Cl + 2H+ 3KClO4 + KCl 5Br + BrO3 + 3H2O

3Br2 + 6OH

DOUBLE TITRATION :
It is used to find the % composition of an alkali mixture, eg.

(NaOH, Na2CO3

mix.)

or

(Na2CO3, NaHCO3

mix.)

using acid eg. HCI and indicators Phenolphthalein 1. and Methyl orange

In a mix of NaOH, Na2CO3 following reactions take place with acids NaOH + HCl Na2CO3 + HCl NaHCO3 + HCl NaHCO3 + HCl NaCl + H2O NaHCO3 + NaCl NaCl + H2O + CO2 NaCl + H2O + CO2 + ] Ph (Pink Colourless red)

MeOH (Yellow

2.

When a mixture of Na2CO3 Na2CO3 + HCl NaHCO3 + HCl

NaHCO3 is titrated with acid NaHCO3 + H2O NaCl + H2O + CO2 ] ] Ph MeOH

Note : Calculations for such titrations need the clear understanding of use of these indicators Ph & MeOH. PERCENTAGE OF AVAILABLE OXYGEN IN PYROLUSITE ORE It is amount of nascent oxygen obtained from pyrolusite ore which chiefly contains MnO2 as per reaction MnO2 MnO + (O)

Nascent Oxygen when ore acts as an oxidising agent. % available oxygen =

wt. of nascent oxygen 100 wt. of ore

PERCENTAGE OF AVAILABLE CHLORINE IN BLEACHING POWDER


It is amount of chlorine liberated per gram of bleaching powder when dissolved in water which can be known with the help of lodometry. CaOCl2 % available chlorine = + H2O Ca(OH)2 + Cl2

wt. of chlorine liberated 100 total wt. of bleaching powder

VOLUME STRENGTH OF H2O2 SOLUTION


H2O2 concentration is generally expressed in terms of volume strength. If a solution of H2O2 is labelled as 'V volumes', it means that 1 ml of H2O2 solution would liberate V ml of O2

on complete decomposition H2O2 H2O + 1/2 O2

At STP we can relate volume strength of H2O2 and Normality by the relation; Volume strength = 5.6 N

Some important Oxidizing / Reducing agents and their reaction products


Mn2+ alkaline MnO2 KMnO4 or neutral K 2MnO4

1.

R | S | T

acidic

U | V | W

n=5 n=3 n=1

2.

Cr3+ K2Cr2O7 acidic

n = 6

3. 4. 5. 6. 7.

H2O2

oxidation O2 reduction H2O


CO2 2Cl

n=2 n=2
n = 2 n = 1 n = 2

C2O42 Fe2+

Fe3+

CaOCl2

Mohr's salt.

FeSO4 Fe2(SO4)3, (NH4)2SO4 remains unaffected.

Redox reactions involving iodine are of particular importance. lodimetric Titrations involve reactions of iodine solution with reducing agents.

I2 + 2e

2I

n = 2

Iodometric Titrations involve oxidation of I to I2 by oxidation agents. The liberated I2 is determined by titration against standard hypo solution.

I2 + 2Na2S2O3

2NaI +

Na2S4O6

Note : Such a titration is difficult to carry out because iodine is highly volatile and less soluble. IMPORTANT REACTIONS : 1. With Cu2+

2Cu2+

+ 4I

Cu2I2 + I2

White ppt. Note that mole of I2, liberated different from moles of I reacted in this case. 2. 3. With IO3 With O3

:
:

IO3 + 5I + 6H+
O3 + 6I + 6H+

3I2 + 3H2O 3I2 + 3H2O

A final Note : Equivalents in acid-base reactions and redox reactions are different.
HCOONa. HCHO, on oxidation, gives HCOOH For example, consider HCHO oxidation
basic medium

(n = 2 reaction).

for redox reaction) which is monoprotic acid (hence n = 1 for acid-base

1.

Calculate n-factor of the reactants in the following (half) reaction :(i) KMnO4 (ii) KMnO4 (iii) KMnO4 (iv) NO3 (v) C2O42 (vi) S2O32 (vii) IO3 (ix) FeSO4 (x) Fe 2O 3 (xi) Cu2S (xii) FeC2O 4 (xiii) Fe(NO 3)3

H Mn2+
2 Mn4+

HO

OH Mn6+
NO

CO 2

S4O62 I2

(viii) K2Cr2O7 Cr3+

Fe2O 3 FeSO 4
Cu2+ + SO2
Fe 3+ + CO 3

Fe 2+ + NO 2
Cu2+ + Fe3+ + SO42 Fe2+ Fe2+ Fe3+ + CO2 + NO3

2.

Find the nfactor of reactant in following half reactions : (i) CuFeS2 (ii) Fe0.9H (iii) Fe0.93O (v) FeS2

(iv) [Fe(CN)6]4

Fe2O3 + SO2

3..

(i) What is the mass of sodium bromate and molarity of solution necessary to prepare 85.5 mL of 0.672 N solution when the half cell reaction is BrO3 + 6H+ + 6e (ii) What would be the mass as well 2BrO3 + 12H+ + 10e as Br + 3H2O. if the cell reaction is

molarity

Br2 + 6H2O ?

4.

KMnO4 oxidises Xn+ to XO3, itself changing to Mn2+ in acid solution. 2.68 x 103 moles of Xn+ requires 1.61 x 103 moles of MnO4. What is value of n ? Also calculate the atomic mass of X, if the weight of 1 g equivalent of XCIn is 56. A volume of 12.53 ml of 0.05093 M SeO2 reacted with exactly 25.52 ml of 0.1 M CrSO4. In the reaction, Cr2+ was oxidized to Cr3+. To what oxidation state was selenium converted by the reaction. Potassium acid oxalate K2C2O4. 3H2C2O4.4H2O can be oxidized by MnO4 in acid medium. Calculate the volume of 0.1 M KMnO4 reacting in acid solution with one gram of the acid oxalate. 2 gms of FeC2O4 are made to react in acid solution with 0.25M KMnO4 solution. What volume of KMnO4 solution would be required. The resulting solution is treated with excess of NH4CI and NH4OH solution. The precipitated Fe(OH)3 is filtered off, washed and ignited. What is the mass of the product obtained.

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8. 9.

0.2 g of the chloride of an element was dissolved in water and treated with excess of silver nitrate. 0.47 g of AgCl was precipitated. Find the equivalent weight of the element. Basic solution of Na4XeO6 are powerful oxidants. What mass of Mn(NO3)2.6H2O reacts with 125 mL 0.717 M basic solution of Na4XeO6 if the products include Xe and solution of sodium permanganate. 0.2828g of iron wire was dissolved in excess dilute H2SO4 and the solution was made upto 100mL. 20ml of this solution required 30mL of N/30 K2Cr2O7 solution for exact oxidation. Calculate percent purity of Fe in wire.

10.

11.

A solution of H2O2 labelled as '20 volumes', was left open. Due to this some H2O2 decomposed and the volume strength of the solution decreased. To determine the new volume strength of the H2O2 solution, 10 ml of the solution was taken and it was diluted to 100ml. 10ml of this diluted solution was titrated against 25ml of 0.0245 M KMnO4 solution under acidic condition. Calculate the volume strength of the H2O2 solution.

12.

How many mole FeCl3 can be prepared by the reaction of 10.0g KMnO4, 1.07 mol FeCI2, and 500 mL of 3.00 M HCI ? MnCI2 is the reduction product. A mixture of CaCI2 and NaCI weighing 2.385g was dissolved in water and treated with a solution of sodium oxalate which produces a precipitate of calcium oxalate. The precipitate was filtered from the mixture and then dissolved in HCI to give oxalic acid which when titrated against 0.2M KMnO4 consumed 19.64 mL of the latter. What was percentage by mass of CaCI2 in the original sample?

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1.44g pure FeC2O4 was dissolved in dil. HCI and solution diluted to 100 mL. Calculate volume of 0.01 M KMnO4 required to oxidize FeC2O4 solution completely. A 0.7160 g of a hydrated metallic sulphate of formula MX (SO4)y. 18H2O precipitated 0.7002 g of BaSO4. When mixed with K2SO4 and crystallized, the metallic sulphate yielded an alum isomorphous with potash alum. Find the atomic weight of the metal.

15.

16.

The reaction Cl2(g) + S2O32 SO42 + Cl is to be carried out in basic medium. Starting with 0.15 mol of Cl2, 0.01 mol S2O32 and 0.3 mol of OH, how many moles of OH will be left in solution after the reaction is complete. Assume no other reaction occurs.

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5g sample of brass was dissolved in one litre dil. H2SO4. 20 ml of this solution were mixed titration. Calculate the percentage of Cu in the alloy.

with KI, liberating I2 and Cu+ and the I2 required 20 ml of 0.0327 N hypo solution for complete 18. K2Cr2O7 oxidizes HCI to Cl2, which oxidizes K2MnO4 to KMnO4. Calculate the weight of KMnO4 formed from one gram of potassium dichromate by reacting it with excess HCI and using the generated chlorine for oxidizing K2MnO4. 19. To 100ml of KMnO4 solution containing 0.632 gm of KMnO4, 200 ml of SnCI2 solution containing 2.371 gm is added in presence of HCI. To the resulting solution excess of HgCI2 solution is added all at once. How many gms of Hg2Cl2 will be precipitated. 20. Exactly 40ml of an acidified solution of 0.4 M iron (II) ion is titrated with KMnO4 solution. After addition of 32ml KMnO4, one additional drop turns the iron solution purple. Calculate the concentration of permanganate solution. 21. Calculate the mass of oxalic acid which can be oxidized by 100ml of MnO4 solution, 10ml of which is capable of oxidizing 50ml of 1 N I 22.

soln. to I2.

The iodide content of a solution was determined by the titration with Cerium (IV) sulfate in the presence of HCI, in which I is converted to ICI. A 250 ml sample of the solution required 20 ml of 0.05 N Ce4+ solution. What is the iodide concentration in the original solution in g/Iitre.

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0.804 gm of a sample of iron ore was dissolved in acid. Iron was oxidized to +2 state and it required 117.2 ml of 0.112 N KMnO4 solution for titration. Calculate the percentage of Fe and FeO in the ore.

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A mixture of FeO and Fe2O3 is reacted with acidified KMnO4 solution having a concentration of 0.2278M, 100 ml of which was used. The solution was then titrated with Zn dust which converted Fe3+ of the solution to Fe2+. The Fe2+ required 1000 ml of 0.13 M K2Cr2O7 solution, Find the % of FeO and Fe2O3.

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Ten grams of a sample of bleaching powder were extracted with water and the solution made upto one litre. 25 ml of this solution was added to 50 ml of N/14 Mohr's salt solution containing enough sulphuric acid. After the reaction was completed, the whole solution required 22 ml of KMnO4 solution containing 2.257 gm of KMnO4 per litre for complete oxidation. Calculate the percentage of available chlorine in the sample of bleaching powder.

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A 1.0g sample containing BaCI2. 2H2O was dissolved and an excess of K2CrO4 solution added. After a suitable period, the BaCrO4 was filtered, washed and redissolved in HCI to convert CrO42 to Cr2O72. An excess of Kl was added, and the liberated iodine was

titrated with 84.7 mL of 0.137 M sodium thiosulphate. Calculate the percent purity of BaCl2. 2H2O. 27. A 0.517g sample containing Ba(SCN)2 was dissolved in a bicarbonate solution. 50.0 mL of 0.107N iodine was added, and the mixture was allowed to stand for five minutes. The solution was then acidified, and the excess I2 was titrated with 16.3 mL of 0.0965 M sodium thiosulphate. Write a balanced equation for the oxidation of SCN into SO42 and HCN. Calculate the percent Ba(SCN)2 in the sample. 28. On ignition, Rochelle salt NaKC4H4O6.4H2O (mol. wt. 282) is converted into NaKCO3 (mol. wt. 122). 0.9546 g sample of the Rochelle salt on ignition gives NaKCO3 which is titrated with 41.72 mL H2SO4. From the following data, find the percentage purity of the Rochelle salt. The solution for neutralisation requires 1.91 mL of 0.1297 N NaOH. The H2SO4 used for the neutralisation requires its 10.27 mL against 10.35 mL of 0.1297 N NaOH. 29. 1.0 g sample containing KO2 and some inert impurity is dissolved in excess of aqueous HI solution and finally diluted to 100 mL. The solution is filtered off and 20 mL of filtrate required 15 mL 0.4 M Na2S2O3 solution to reduce the liberated iodine. Determine mass % of KO2 in the original sample. 30. A 200 mL sample of a citrus fruit drinks containing ascorbic acid (vitamin C, mol. wt. 176.13) was acidified with H2SO4 and 10 mL of 0.0250 M I2 was added. Some of the iodine was reduced by the ascorbic acid to I. The excess of I2 required 4.6 mL of 0.01 M Na2S2O3 for reduction. What was the vitamin C content of the drink in mg vitamin per mL drink ? The reaction are: C6H8O6 + I2 C6H6O6 + 2HI 5H2O + S2O32 + 4I2 2SO42 + 8I + 10H+ 31. Chile salt peter, a source of NaNO3 also contains NaIO3. The NaIO3 can be used as a source of iodine, produced in the following reactions.

IO3 + 3HSO3 I + 3H+ + 3SO42


5I + IO3 + 6H+ 3I2(s) + 3H2O

........(i) .......(ii)

One litre of chile salt peter solution containing 5.80 g NaIO3 is treated with stoichiometric quantity of NaHSO3. Now an additional amount of same solution is added to reaction mixture to bring about the second reaction. How many grams of NaHSO3 are required in step I conversion of I to I2 ? 32.

and what additional volume of chile salt peter must be added in step II to bring in complete A 1.87 gm. sample of chromite ore (FeO.Cr2O3) was completely oxidized by the fusion of peroxide. The fused mass was treated with water and boiled to destroy the excess of peroxide. After acidification the sample was treated with 50ml. of 0.16 M Fe2+. In back titration 2.97 ml of 0.005M barium dichromate was required to oxidize the excess iron (II). What

is the percentage of chromite in the sample ? 33. A 10g sample of only CuS and Cu2S was treated with 100 mL of 1.25 M K2Cr2O7. The products obtained were Cr3+, Cu2+ and SO2. The excess oxidant was reacted with 50 mL of Fe2+ solution 25ml of the same Fe2+ solution required 0.875M acidic KMnO4 the volume of which used was 20mL. Find the % of CuS and Cu2S in the sample. 34. A sample of steel weighing 0.6 gm and containing S as an impurity was burnt in a stream of O2, when S was converted to its oxide SO2. SO2 was then oxidized to SO4 by using H2O2 solution containing 30 ml of 0.04 M NaOH. 22.48 ml of 0.024 M HCI was required to neutralize the base remaining after oxidation. Calculate the % of S in the sample.

OBJECTIVE PROBLEMS 1. 8 g of sulphur is burnt to form SO2, which is oxidised by Cl2 water. The solution is then treated with BaCl2 solution. The amount of BaSO4 precipited would be (A) 1 mole (B) 0.5 mole (C) 0.24 mole (D*) 0.25 mole The normality of 0.3 M H3PO3 when it undergoes the following reaction,
2H3PO3 + 2OH- HP O 3 + 2H2O would be (A*) 0.6 N (B) 0.15 N

2.

(C) 0.9 N

(D) 0.1 N

5.

A 10 g sample of a mixture of calcium chloride and sodium chloride is treated with Na2CO3 to percipitate calcium as calcium carbonate. This CaCO3 is heated to convert all the calcium to CaO and the final mass of CaO is 1.62 g. The % by mass of NaCl in the original mixture is (A) 15.2% (B*) 67.9% (C) 21.8% (D) 32.1% Equal volumes of 1 M each of KMnO4 and K2Cr2O7 are used to oxidise Fe(II) solution in acidic medium. The amount of Fe oxidised would be (A) more with KMnO4 (B) equal with both oxidising agents (C*) more with K2Cr2O7 (D) cannot be determined 10 ml oif a solution of H2O2 requires 25 ml of 0.1N KMnO4 for complete reaction. The volume strength of H2O2 would be (A*) 1.4 (B) 1.2 (C) 0.25 (D) 2.5 The equivalent mass of HCl in the following reaction K2Cr2O7 + 14HCl 2KCl + 2CrCl3 + 3Cl2 + H2O would be (A) 36.5 (B) 73 (C*) 85

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8.

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(D) 16.25

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A mixture of carbonates of two bivalent metals contains 13.6% of one metal. If 2.5 g of the mixture liberates 1.33 g CO2, the % by weight of the other metal would be (A) 13.6 (B) 12 (C*) 13.92 (D) 15 10.78 g of H3PO4 in 550 mL solution is 0.40 N. Thus this acid

11.

(A*) has been neutralised to HP O 2 4


2(B) has been changed to H2P O 3

(B) has been neutralised to P O 3 4

(D) has been neutralised to H2P O 4

13.

20 mL of x M HCl neutralizes completely 10 mL of 0.1 M NaHCO3 and a further 5 mL of 0.2 M Na2CO3 solution to methyl orange end point. The value of x is (A) 0.167 M (B) 0.133 M (C*) 0.150 M (D) 0.200 M 0.7 g of Na2CO3.xH2O is dissolved in 100 mL H2O, 20 mL of which required 19.8 mL of 0.1 N HCl. The value of x is (A) 4 (B) 3 (C*) 2 (D) 1 The equivalent weight of Fe3O4 in the reaction, Fe3O4 + KMnO4 Fe2O3 + MnO2 would be (A) M/6 (B*) M (C) 2M
4I- + Hg2+ Hg I 2 ; 1 mole each of Hg2+ and I- will form 4 (A) 1 mole of Hg I 2 4 (C*) 0.25 mole of Hg I 2 4 (B) 0.5 mole of Hg I 2 4 (D) 2 mole of Hg I 2 4

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(D) M/3

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0.3 g of an oxalate salt was dissolved in 100 mL solution. The solution required 90 mL of N/20 KMnO4 for complete oxidation. The % of oxalate ion in salt is (A) 33% (B*) 66% (C) 70% (D) 40% The equivalent weight of Na2S2O3 as reductant in the reaction, Na2S2O3 + H2O + Cl2 Na2SO4 + 2HCl + S would be (A) (Molecular weight)/1 (B*) (Molecular weight)/2 (C) (Molecular weight)/6 (D) (Molecular weight)/8 How many gram of I2 are present in a solution which requires 40 mL of 0.11 N Na2S2O3 to reacti
22with it. The reaction S2 O 3 + I2 S4 O 6 + 2I? (A) 12.4 g (B*) 0.558 g (C) 25.4 g

20.

21.

(D) 11.4 g

22.

Two elements A (atomic mass = 75) and B (atomic mass = 16) combine to yield a compound. The weight of A in the compound was found to be 75.08. The formula of the compound is (A) A2B (B*) A2B3 (C) AB (D) AB2 What weight of HNO3 is needed to convert 5 g of iodine into iodic acid according to the reaction, I2 + HNO3 HIO3 + NO2 + H2O? (A*) 12.4 g (B) 24.8 g (C) 0.248 g (D) 49.6 g In the reaction, VO + Fe2O3 FeO + V2O5, the equivalent weight of V2O5 is equal to its

23.

24.

(A) molecular weight (C*) molecular weight /6 25.

(B) molecular weight /4 (D) molecular weight /8

When BrO3 ion reacts with Br - ion in acid solution, Br2 is liberated. The equivalent weight of KBrO3 in this reaction is (A) M/8 (B) M/3 (C*) M/5 (D) M/6 The hydrated salt, Na2SO4.nH2O, undergoes 55.9% loss in weight on heating and becomes anhydrous. The value of n will be (A) 5 (B) 3 (C) 7 (D*) 10 When a metal is burnt, its weight is increased by 24%. The equivalent weight of the metal will be (A) 25 (B) 24 (C*) 33.3 (D) 76 One moleof potassium chlorate is thermally decomposed and excess of aluminium is burnt in the gaseous product. The moles of aluminium oxide formed would be (A*) 1 (B) 1.5 (C) 2 (D) 3 A certain compound has the molecular formula X4O6. If 10 g of compound contains 5.62 g of X, the atomic mass of X is approximately (A*) 31 amu (B) 30.8 amu (C) 42 amu (D) 48 amu Sulphuryl chloride. SO2Cl2, reacts with H2O to give mixture of H2SO4 and HCl. Aqueous solution of 1 mol of SO2Cl2 will be neutralised by (A) 3 mol of NaOH (B*) 2 mol of Ca(OH)2 (C) both (D) none of these A solution contains Na2CO3 and NaHCO3. 10 mL of the solution required 2.5 mL of 0.1 M H2SO4 for neutralisation using phenolphthalein as indicator. Methyl orange is then added when a further 2.5 mL of 0.2 M H2SO4 was required. The amount of Na2CO3 and NaHCO3 in 1 litre of the solution is (A) 5.3 g and 4.2 g (B) 3.3 g and 6.2 g (C) 4.2 g and 5.3 g (D*) 6.2 g and 3.3 g Which of the following is a disproportionation reaction? (A) CaCO3 + 2H+ Ca2+ + H2O + CO2
2(C) Cr2 O 7 + 2OH- 2 Cr O 2 + H2O 4 2(B) 2Cr O 2 + 2H+ Cr2 O 7 + H2O 4

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(D*) Cu2O + 2H+ Cu + Cu2+ + H2O

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When the same amount of zinc is treated separately with excess of H2SO4 and excess of NaOH, the ratio of volumes of H2 evolved is (A*) 1 : 1 (B) 1 : 2 (C) 2 : 1 (D) 9 : 4 Given that 50 mL of 0.01 M Na2S2O3 solution and 5 x 10-4 mole of Cl2 react according to equation,
2Cl2(g) + S2 O 3 + Cl- + S. S O2 4 The balanced molecular equation would be (A*) Cl2 + H2O + Na2S2O3 Na2SO4 + S + HCl (B) Cl2 + Na2S2O3 2NaCl + NaSO4

36.

2(C) Cl2 + S2 O 3 S O2 4 + S + Cl (D) none of these


2When the Cr2 O 7 ion acts as an oxidant in acidic medium, Cr3+ ion is formed. The number of mole of 2Sn2+ that are oxidised to Sn4+ by one mole of Cr2 O 7 ion would be (A) 2/3 (B) 3/2 (C) 2 (D*) 3

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38.

00.3 g of oxalate salt was dissolved in 100 mL water. This solution required 90 mL of n/20 KMnO4 for complete oxidation. The % of oxalate ion in the salt is (A) 33% (B*) 66% (C) 70% (D) 40% A 0.518 g sample of limestone is dissolved in HCl and then the calcium is precipitated as CaC2O4. After filtering and washing the precipitate, it requires 40.0 mL of 0.250 N KMnO4, solution acidified with H2SO4 to titrate it as. the percentage of CaO in the sample is
MnO4 + H+ + C2 O 2 Mn2+ + CO2 + 2H2O 4 (A*) 54.0% (B) 27.1% (C) 42%

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(D) 84%

40.

Hydrogen peroxide in aqueous solution decomposes on warming to give oxygen according to the equation, 2H2O2(aq) 2H2O(l) + O2(g) Under conditions where 1 mole of gas occupies 24 dm3, 100 cm3, of XM solution of H2O2 produces 3 dm3 of O2. Thus X is (A*) 2.5 (B) 1 (C) 0.5 (D) 0.25 The dehydration yield of cyclohexanol to cyclohexene is 75%. What would be the yield if 100 g of cyclohexanol is dehydrated? (A*) 61.5 g (B) 16.5 g (C) 6.15 g (D) 0.615 g What volume of O2 measured at standard condition will be formed by the action of 100 mL of 0.5 N KMnO4 on hydrogen peroxide in an acid solution? The skeleton equation for the reaction is, KMnO4 + H2SO4 + H2O2 KHSO4 + MnSO4 + H2SO4 + H2O + O2 (A) 0.12 litre (B*) 0.028 litre (C) 0.56 litre (D) 1.12 litre The equivalent weight of the salt KHC2O4. H2C2O4.4H2O used as reducing agent is (A) Molecular weight (B) Molecular weight /2 (C) Molecular weight /3 (D*) Molecular weight /4 100 mL of a sample of hard water requires 25.1 mL of 0.02 N H2SO4 for complete reaction. The hardness of water (density 1 g/mL) is (A) 200 ppm (B) 250 ppm (C*) 251 ppm (D) 258 ppm Over the years, thermite reaction has been used for welding railroad rails, in incendiary bonbs, and to ignite solid fuel rocket motors. The reaction is Fe2O3(s) + 2Al(s) 2Fe(s) + Al2O3(s) How much aluminum oxide would be producedc, if the yield were 93% and iron in iron oxide is 15 g? (A*) 12.7 g (B) 13.66 g (C) 27 g (D) 14.6 g The mass of an empty crucible and its cover is 37.23 g. The mass of the same crucible and cover with

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45.

46.

th ehydrate, Al2(SO4)3. 17H2O added is 57.45 g. What should be the mass of the crucible and cover and anhydrate Al2(SO4)3 after thorough heating has driven off all of the water? (A) 11.23 g (B) 10.67 g (C) 52.5 g (D*) 47.9 g 47. The red pigment in blood contains 0.32% iron by weight. Molecular mass of the pigment is 70000 g mol-1. The number of iron atoms in each molecule of the pigment would be (A) 1 (B) 2 (C) 3 (D*) 4 If the equivalent weight of a compound A is M/4 when it reacts with compound B whose equivalent weight is M/5, then 4 mol of A requires (A) 4 mol of B (B) 5 mol of B (C*) less than 4 mol of B (D) more than 5 mol of B One of the reactions in the petroleum industry for improving the octane rating of fuels is C7H14 C7H8 + 3H2 The two hydrocarbons in this equation are liquid while H2 is a gas. What is the percent reduction in liquid weight accompanying the above reaction? (A) 9.39% (B) 0.939% (C*) 6.1% (D) 0.61% The moles of O2 required for reacting with 8960 mL g of ammonia at STP is xNH3 + yO2 l aNO + bH2O is (A) 5 (B) 2.5 (C) 1 (D*) 0.5

49.

50.

51.

Question No. 52 and 53 are based on the following piece of information. Mark the appropriate options on the basis of information. 342 gm of 20% by mass of Ba(OH)2 solution (sp. gr. 0.57) is reacted with 200 ml of 2M HNO3 according to given balanced reaction. Ba(OH)2 + 2HNO3 Ba(NO3)2 + 2H2O 52. The nature of the final solution is (A) acidic (B) neutral (C*) basic (D) can't say

53.

If density of final solution is 1.01 gm /ml then find the molarity of the ion in resulting solution by which nature of the above solution is identified, is (A*) 0.5 M (B) 0.8 M (C) 0.4 M (D) 1 M Find the percentage labelling of a mixture containing 23 gm HNO3 and 27 gm N2O5. (A) 104.5% (B*) 109% (C) 113.5% (D) 118% Find the maxmum and minimum value of percentage labelling (A) 133.3 % (B) 116.66%, 0% (C*) 116.66%, 100% (D) None Find the new labelling if 100 gm of this mixture (original) is mixed with 4.5 gm water (A) 100 +
4 .5 1

54.

55.

56.

(B*) 100 +

4 .5 1.045

(C) 100 +

4 .5 104.5

(D) 100+

4.5 1.09

57.

a moles of X reacts with b moles of Y according to the reaction in which the stoichiometric ratio of X : Y equals to c : b where (a > c), then quantity left behind after complete reaction is (A*) X(a c) Y(0) (B) X (0) Y (c a) (C) X (0) Y (a c) (D) X (c a) Y (0) Al2(SO4)3 solution of 1 molal concentration is present in 1 litre solution of 2.684 gm/cc. How many moles of BaSO4 would be precipitated on adding BaCl2 in excess. (A) 2 moles (B) 3 moles (C) 2.684 3 moles (D*) 6 moles In an auto engine with no pollution controls, about 5% of the fuel (C8H18) is unburned. Molar ratio of CO and C8H18 emitted in the exhaust gas is: (A) 100 (B*) 152 (C) 50 (D) 5 A 40 ml of mixture of H2 & O2 was placed in a gas burette at 18C and 1 atm P. A spark was applied so that the formation of water was complete. The remaining pure gas had a volume of 10 ml at 18C & 1 atm P. If the remaining gas was H2, what was the initial mole % of H2 in mixture. (A*) 75 (B) 50 (C) 25 (D) 12.5 A mixture of carbon monoxide and carbon dioxide is found to have a density of 1.7 g/lit. at S.T.P. The mole fraction of carbon monoxide is (A*) 0.37 (B) 44.1 (C) 0.30 (D) 0.50 The advantage of using KO2 as gas masks in spaceships is that it absorbs Co2, at the same time releasing oxygen. If 0.001 mole of KO2 is present in an atmosphere containing 22.4 cm3 of CO2 at STP free for moisture, what will be the volume of O2 released at STP? 2KO2 + CO2 K2CO3 + (3/2)O2 (A) 22.4 cm3 (B) 11.2 cm3 (C*) 16.8 cm3 (D) 44.8 cm3 If 20% by weight of nitrogen is present in a compound, the molecular weight of the compound may be (A) 144 (B*) 28 (C) 100 (D) 140 Mole fraction of solvent in 0.2 m binary aqueous solution of camphor (m = molality) (A*) 0.996 (B) 0.004 (C) 0.96 (D) 0.976 Volume V1 ml of 0.1 M K2Cr2O7 is needed for complete oxidation of 0.678g N2H4 in acidic medium. The volume of 0.3 M KMnO4 needed for same oxidation in acidic medium will be (A*)
2 V1 5

58.

59.

60.

61.

62.

63.

64.

65.

(B)

5 V1 2

(C) 113 V1

(D) can't say

66.

Ocidation state of sulphur in Caro's acid, H2SO5 is (A) +8 (B*) +6

(C) +3

(D) - 2

67.

The molarity of Cl- in an aqueous solution which was (w/V) 2% NaCl, 4% CaCl2 and 6% NH4Cl will be (A) 0.342 (B) 0.721 (C) 1.12 (D*) 2.18 The molar ratio of Fe++ to Fe+++ in a mixture of FeSO4 and Fe2(SO4)3 having equal number of sulphate ion in both ferrous and ferric sulphate is

68.

69.

(A) 1 : 2 (B*) 3 : 2 (C) 2 : 3 (D) can't be determined How many mg of quick lime is required to remove hardness of 1 Kg of hard water having 366 ppm of HCO3 and Ca++ as the only cation (A) 72 mg (B) 84 mg (C*) 168 mg (D) 170 mg DNA has density 1.1 gm/ml and its molecular weight is 6 x 103 g/mol. Average volume occupied by its single molecule will be (A) 9.1 x 10-20cc (B*) 9.1 x 10-21cc (C) 9.8 x 10-21cc (D) 9.6 x 10-20cc How many ml of 0.3M K2Cr2O7 (acidic) is required for complete oxidation of 5 ml of 0.2 M SnC2O4 solution (A) 3.33 ml (B*) 2.22 ml (C) 11 ml (D) 4.44 ml In the balanced chemical reaction:
aCrO 2 4 + bFe(OH ) 2 + 4 H 2 O cCr (OH ) 3 + dFe( OH ) 3 + OH the value of a, b, c and d are respectively (A) 1, 4, 3, 1 (B*) 1, 3, 1, 3 (C) 1, 3, 4, 1

70.

71.

72.

(D) 3, 4, 3, 1

73.

In which of the compound(s) Iodine has positive oxidation state (A) Iodoform (B*) I2O5 (C*) ICl

(D*) HIO3

74.

For the conversion of 0.240 g NaH2PO4 in a solution to monohydrogen phosphate, 21.4 ml NaOH solution is needed. The molarity of NaOH solution will be (A*) 0.093 (B) 0.93 (C) 0.087 (D) 0.083 22.7 ml of N/10 Na2CO3 solution neutralises 10.2 ml of dilute H2SO4. Then the volume of water that must be added to 400 ml of same H2SO4 to make it exactly N/10 is (A) 245 ml (B) 484.6 ml (C) 480 ml (D*) 490.2 ml The volume of NH3(at STP) needed to pass into 30 ml of 1N H2SO4 solution to bring down its strength to M/10 is (A) 0.5 litre (B) 636 ml (C*) 537.6 ml (D) 540.3 ml 1.0 gm of a mixture of CaCO3 and NaCl reacts completely with 120 ml of N/10 HCl. The percentage of NaCl in the mixture is (A*) 40% (B) 50% (C) 60% (D) 66% 50 g of 8% by mass NaOH is mixed with 100 g of 8% by mass of HCl, the resulting solution is (A*) acidic (B) basic (C) neutral (D) strongly basis 0.62g Na2CO3 . xH2O completely neutralises 100 ml of N/10 H2SO4. The value of x muxt be (A*) 1 (B) 6 (C) 8 (D) 10 How many litre of O3 at STP will be needed to completely oxidise 10 ml of 0.4M KI into I2 (A) 0.448 (B*) 0.0448 (C) 4.48 (D) 2.24

75.

76.

77.

78.

79.

80.

81.

How many moles of FeCr2O4 can be oxidised completely by 1 mole of KMnO4 in acidic medium. (A) 7 (B) 5 (C) 7/5 (D*) 5/7 A sample of Ca3(PO4)2 contains 3.1 g phosphorous, the weight of Ca in the sample is (A*) 6 gm (B) 4 gm (C) 2 gm (D) 5.56 gm KI + I2 + HNO3 HIO3 + KIO3 + NO2 If 3 mole of KI & 2 moles I2 are reacted with excess of HNO3, volume of NO2 gas evolved at NTP is (A*) 716.8Lt (B) 1075.2Lt (C) 44.8Lt (D) 67.2Lt If a piece of iron gains 10% of its weight due to partial rusting into Fe2O3. the percentage of total iron that has rusted is (A) 23 (B) 13 (C*) 23.3 (D) 25.67 In which of the following reaction equivalent weight of oxidant is not difined (A) 2BrO3- + 12H+ + 10e- Br2 + 6H2O (B) BrO3 + eH+ + 6e- Br- + 3H2O (C*) 3Br2 + 6CO3 + 3H2O 5Br- + BrO3 + 6HCO3 (D*) CaOCl2 + H2O Ca(OH)2 + Cl2 In which of the following redox reaction 'n' factor of every reactant is non fractional (A) CsBr + Br2 CsBr3 (B*) Mn3O4 Mn++ (C) KI + I2 water (D) NaNH2 + N2O NaN3 + H2O KI3 How many mole of electron is needed for reduction of each mole of Cr in the reaction CrO5 + H2SO4 Cr2(SO4)3 + H2O + O2 (A) 4 (B*) 3 (C) 6 (D) 7 The moles of Ammonium sulphate needed to react with one mole of MnO2 in acidic medium in a reaction giving MnSO4 and (NH4)2S2O8 is (A*) 2 (B) 1/2 (C) 1 (D) 1/3 A 20 ml (specific gravity 1.02) of chlorine water is treated with excess of KI and thr liberated iodine required 25 ml of 0.2N Na2S2O3. The percentage of free chlorine in chlorine water is (A*) 0.87 (B) 87 (C) 0.78 (D) 0.82 If 1 gm of HCl and 1 gm of MnO2 heated together the maximum weight of Cl2 gas evolved will be (A) 2 gm (B) 0.975 gm (C*) 0.486 gm (D) 0.972 gm 35ml sample of hydrogen peroxide gives off 500 ml of O2 at 27oC and 1 atm pressure. Volume strength of H2O2 sample will be (A) 10 volume (B*) 12.8 volume (C) 11 volume (D) 12 volume When 143.6 mg ZnSO4 . xH2O is heated strongly in the absence of air, 40.5 mg yellow residue is obtained. Value of x is (A*) 7 (B) 5 (C) 6 (D) 2

82.

84.

85.

86.

87.

88.

90.

91.

93.

94.

95.

96.

Percentage of free SO3 in an oleum bottle labelled 113.5% H2SO4 is (A) 40 (B*) 60 (C) 50

(D) 45

97.

For 1.34 x 10-3 moles of KBrO3 to reduce into bromide 4.02 x 10-3 mole of Xn+ ion is needed. New oxidation state of X is (A*) n + 2 (B) n - 2 (C) 2 (D) -2 Each molecule of tear gas, Lewisite contains 2 Hydrogen atoms, 1.78 x 10-22 gm. Chlorine, 2 carbon atoms and 1.25 x 10-22 gm of an unknown metal. Its molecular weight will be (A) 206 (B*) 207.5+1 (C) 280 (D) 280.8 We have three separate solutions of KCl, MgCl2 and AlCl3. The concentration of Cl- ion is same in all three solution. Which solution will require the least volume to coagulate (precipitate) a negatively charged colloidal solution. (A) KCl solution (B*) MgCl2 solution (C) AlCl3 solution (D) All the same What volume of 0.3N Cr2O7--/H+ is needed for complete oxidation of 200 ml of 0.6M FeC2O4 soution. (A) 1.2 cc (B*) 1.2 Litre (C) 120 cc (D) 800 cc 25 ml of Na2CO3 solution requires 100 ml of 0.1N HCl to reach end point with Phenolphthalein as indicator. Molarity of resulting solution with respect to HCO3- ion (A) 0.008M (B) 0.004M (C) 0.16M (D*) 0.08M Which concentration of a solution will change on heating a solution (A) molality (B) mole fraction (C*) volume strength

98.

99.

100.

101.

102.

(D*) %(W/V)

103.

5 gm of a metal carbonate on heating strongly releases 1.51 litre CO2 gas at STP. The equivalent weight of metal is (A*) 7 (B) 23 (C) 21 (D) 5 If equal volumes of 0.1M KMnO4 and 0.1M K2Cr2O7 solutions are allowed to oxidise. Fe2+ to Fe3+ in acidic medium, then Fe2+ oxidised will be (A) more by KMnO4 (B*) more by K2Cr2O7 (C) equal in both cases (D) can't be determined. Equivalent weight of MnO4- in acidic, basic and nuetral medium are in the ratio of (A) 3 : 5 : 15 (B) 5 : 3 : 1 (C) 5 : 1 : 3 (D*) 3 : 15 : 5 Cl2 reacts with hot NaOH solution, oxidation number of chlorine changes from (A) -1 to 0 (B) 0 to -1 (C) 0 to +5 (D*) b; c.

104.

105.

106.

107.

Molarity of H2SO4 is 18 M. Its density is 1.8 g/cm3, hence molality is (A) 18 (B) 100 (C) 36

(D*) 500

108.

x g of the metal gave y g of its oxide. Hence equivalent weight of the metal

(A) 109.

y-x x8 x

(B*)

x x8 (y - x)

(C)

x x8 y

(D)

x+y x8 x

Mole fraction of ethyl alcohol in aqueous ethyl alcohol solution is 0.25. Hence percentage of ethyl alcohol by weight is (A) 54% (B) 25% (C) 75% (D*) 46% 254g of Iodine and 142 g of Chlorine are made to react completely to give a mixture of ICl and ICl3. The moles of each one formed is (A) 0.1M ICl and 0.1M ICl3 (B*) 1.0M ICl and 1.0M ICl3 (C) 0.5M ICl and 0.1M ICl3 (D) 0.5M ICl and 1.0M ICl3 0.1M of MnO4-(in acidic medium) can(Assume the volume of reducing agent will be same in the MnO4-) (A*) oxidise 0.25M C2O42(B*) oxidise 0.5M Fe2+ (C*) oxidise 0.166M FeC2O4 (D) oxidise 0.6M Cr2O72Which of the following are redox reactions? (A*) Zn + 2HCl ZnCl2 + H2 (B) Al(OH)3 + 2HCl AlCl3 + 3H2O (C*) Disproportionation of Cu+ ions in a gave solution (D) Ag+(aq.) + I-(aq.) AgI(s) In which of the following species, valency and oxidation numbers have different numerical values? (A) CO2 (B) CH4 (C*) CHCl3 (D) CCl4 15 ml of pure O2 is subject to silent electric discharge, when only 10% of it is converted to ozone. The volume of the resulting mixture and the volume that remains after absorption in turpentine are respectively (A*) 14.5 ml, 13.5 ml (B) 12 ml, 10 ml (C) 15 ml, 13.5 ml (D) 20 ml, 15 ml 0.5 g of a metallic oxide is converted to 1.165 g of the corresponding sulphate. If the atomic mass of the element is 88 g mol1, the metallic oxide is (A*) MO2 (B) M2O3 (C) MO (D) M2O A steel vessel of volume, one litre is filled with a mixture of methane and oxygen of a total pressure of one atm at 270C. The gas mixture is exploded. What would be the final pressure of the products at 1270C? (A) 3.13 atm (B*) 1.33 atm (C) 1.13 atm (D) 2.08 atm K2Cr2O7 is obtained in the following steps: 2FeCrO4 + 2Na2CO3 + O Fe2O3 + 2Na2CrO4 + 2CO2 2Na2CrO4 + H2SO4 Na2Cr2O7 + H2O + Na2SO4 Na2Cr2O7 + 2KCl K2Cr2O7 + 2NaCl To get 0.25 mol of K2Cr2O7, mol of 50% pure FeCrO4 required: (A*) 1 mol (B) 0.50 mol (C) 0.25 mol

110.

111.

112.

113.

114.

115.

116.

117.

(D) 0.125 mol

118.

A mixture of two gases A and B in the mole ratio 2 : 3 is kept in a 2 litre vessel. A second 3 litre vessel

has the same two gases in the mole ratio 3 : 5. Both gas mixtures have the same temperature and same pressure. They are allowed to intermix and the final temperature and pressure are the same as the initial values, the final volume being 5 litres. Given that the molar masses are M A and MB, what is the mean molar mass of the final mixture? (A) 119.
77 M A + 123M B 123M A + 77 M B 77 M A + 123M B 123M A + 77 M B (B*) (C) (D) 200 200 250 250

Which of the following 1 gmL1 has the highest molarity of H+ ions (A) H2SO4 (B*) HCl (C) HNO3

(D) CH3COOH

120.

The NH3 evolved from 1.40 gm sample of protein was absorbed in 45 ml of 0.4 M HNO3. The excess acid required 20 ml of 0.1 M NaOH. The % N in the sample is (A) 8 (B*) 16 (C) 19.42 (D) 24