EXERCISE I (A) Q1.

On adding ammonium hydroxide solution to Al2(SO4)3 (aq): (A) a precipitate is formed which does not dissolve in excess of ammonium hydroxide. (B) A precipitate is formed which dissolves in excess of ammonia solution. (C) No precipitate is formed (D) None of these The weakest Lewis acid is (A) BF3 (B) BCl3 (C) BBr3 (D) BI3

Q2. Q3.

Which statement is correct for B2H6: (A) 4BH bonds are of equal length and 4BH bonds are another but equal length (B) HBH angles are 1200 and 970 (C) BH bonds length (D) All of these Which ofthe following reaction will yield crystalline variety of boron: (A) B2O3 + 2Al 2B + Al2O3 (B) B2O3 + 3Mg 2B + 3MgO (C) B2O3 + 6Na 2B + 3Na2O (D) All of these Fluorine is more electronegative than either boron or phosphorus. What conclusion can be drawn from the fact that BF3 has no dipole moment but PF3 does. (A) BF3 is not sphericaly symmetrical, PF3 is not. (B) BF3 molecule must be linear (C) The atomic radius of P is larger than the atomic radius of B. (D) The BF3 molecule must be plaanr triangular BCl3 does not exist as dimer but BH3 exist as dimer (B2H6) becuase (A) Chlorine is more electronegative than hydrogen (B) There is p-p back bonding in BCl3 but does not contain such multiple bonding (C) Large sized chlorine atoms do not fit in between the small boron atoms whereas small sized hydrogen atoms get fitted between boron atoms (D) none of these Which of the following statement about boron carbide is wrong: (A) Its molecular formula is B4C (B) It is also called Norbia (C) It is the hardest substance (D) It is used for cutting glasses Select the correct statements for diborane 1. Boron is approximately sp3 hybridized 2. BHB angle is 1800 3. There are two terminal BH bonds for each boron atom 4. There are only 12 bonding electrons available of these statements (A) 1, 2 and 4 (B) 1, 2 and 3 (C) 2, 3 and 4 (D) 1, 3 and 4

Q4.

Q5.

Q6.

Q7.

Q8.

Q9.

The structure of aluminium bromide is best represented as:

(A)

(B) [AlBr2]+ [AlBr4]

(C) Q10. Q11.

(D) (D) B2H(CH3)5

Which one of the following methyl diboranes does not exist? (A) B2H4(CH3)2 (B) B2H3(CH3)3 (C) B2H2(CH3)4

Borax on heating strongly above its melting point melts to a liquid, then solidifies to a transparent mass commonly known as Borax Bead. The transparent glassy mass consists of: (A) sodium pyroborate (B) boric anhydride (C) sodium metaborate (D) mixture of sodium metaborate and boric anhydride Me3B, BH3 and BF3 are three Lewis acids. Which one of the following is the correct sequence of these acids in order of their increasing acid strength? (A) Me3B < BH3 < BF3 (B) Me3B < BF3 < BH3 (C) BF3 < Me3B < BH3 (D) BF3 < BH3 < Me3B Be and Al exhibit many properties which are similar, but the two elements differ in: (A) Exhibiting amphoteric nature in their oxides (B) Forming polymeric hydrides (C) Exhibiting maximum covalency in compounds (D) FOrming covalent halides Aluminium chloride exists as dimer, Al2Cl6 in solid state as well as in soluiton of non-polar solvents such as C6H6. When dissolved in water it gives: (A) Al2O3 + 6HCl (B) [Al(H2O)6]+ 3Cl (C) [Al(OH)6]3+ 3HCl (D) Al3+ + 3Cl Heating an aqueous solution of aluminium chloride to dryness will give: (A) AlCl3 (B) Al2Cl6 (C) Al2O3 (D) Al(OH)Cl2 The structure of diborane contains: (A) Four 2C2e bonds and two 3C2e bonds (B) Two 2C2e bonds and two 3C2e bonds (C) Two 2C2e bonds and two 3C3e bonds (D) Four 2C2e bonds and two 3C3e bonds H3BO3 is (A) Monobasic and weak Lewis acid (C) Monobasic and strong Lewis acid (B) Monobasic and weak Bronsted acid (D) Tribasic and weak Bronsted acid

Q12.

Q13.

Q14.

Q15. Q16.

Q17.

EXERCISE I (B) Q1. Correct match is: (A) Ordinary form of borax (B) Colemanite (C) Boronatrocalcite (D) Octahedral form of borac : : : : Na2B4O7 5H2O Ca2B6O115H2O 2Mg3B8O15MgCl2 Na2B4O710H2O

Q2.

Q3.

Which of the following is correct? (A) The members of BnHn+6 are less stable than BnHn+4 series (B) Diborane is coloured and unstable at room temperature (C) The reaction of diborane with oxygen is endothermic (D) All of the above In which of the following, a salt of the type KMO2 is obtained? (A) B2H6 + KOH (aq) (B) Al + KOH (aq) (C) Both (D) None Which of the following mineral does not contain aluminium? (A) Cryolite (B) Mica (C) Feldspar (D) Fluorspar The function of fluorspar in the electrolytic reduction of alumina dissolved in fused cryolite (Na3AlF6) is: (A) as a catalyst (B) to lower the temperature of melt and to make the fused mixture very conducting (C) to decrease the rate of oxidation of carbon anode (D) none of the above A layer of coke is spread over bauxite during electrolytic reduction of alumina by Hall Heroult process. This layer acts as a/an: (A) flux (B) slag to remove impurities (C) reducing agent (D) insulation and does not allow heat to escape Which of the following compound is formed in borax bead test? (A) Metaborate (B) Tetraborate (C) Double oxide (D) Orthoborate Aluminium chloride exists as a dimer, Al2Cl6, in solid state as well as in solution of nonpolar solvents such as benzene.When dissolved in water, it gives: (A) Al3+ +3Cl (B) [Al(H2)6]3+ + 3Cl (C) [Al(OH)6]3 + 3HCl (D) Al2O3 + 6HCl Inorganic graphite is: (A) B3N3H6 (B) B3N3 (C) SiC (D) P4S3

Q4.

Q5.

Q6.

Q7.

Q8.

Q9.

Q10.

Hydrated AlCl3 is used as: (A) catalysed in cracking of petroleum (B) catalysed in FriedelCraft's reaction (C) Mordant (D) all of the above EXERCISE II (A) Identify A, B and C in the given reaction sequence. C H Cl NH4Cl + BCl3 A B 140 150 C
6 5 0

Q1.

Q2. Q3.

Identify the product A and B in the given reaction sequence. H O diglyme A + CO B [CH3CH2]3 C OH
2 2

Q4.

An inorganic compound (A) shows the following reactions. It is white solid and exist as dimer. (i) It gives fumes of (B) with much wet air. (ii) It sublimes on 1800C and forms monomer if heated to 4000C. (iii) Its aqueous solution turns blue litmus to red. (iv) Addition of NH4OH and NaOH separately to a solution of (A) gives white precipitate which is however soluble in excess of NaOH. An inogranic compound (A) in its aqueous solution produced a white ppt. with NaOH, which dissolves in excess of NaOH. The aqueous solution of (A) also produced white ppt. with NH4OH which does not dissolve in excess of NH4OH. Also its aqueous solution produced light yellow ppt. with AgNO3 solution, soluble in dil. HNO3. Identify (A). A white crystalline compound (A) swells up on heating and gives violet colour flame on burning. It's aqueous solution gives: (A) White ppt. with BaCl2 (B) White gelatinous ppt. with excess of NH4OH which dissolves in NaOH but reappears on boiling with conc. NH4Cl solution. Identify the compound(A) and give the reactions. Complete the following reaction:
(i)B2H6 A (ii) H2 O2 /OH

Q5.

Q6.

Q7. Q8.

Write down the reduction products of RCN, RNO2 and RCHO by B2H6 Identify the gas produced during catalytic decomposition of C2H5OH by hot Al2O3, which decolorises Br2 water.

Q9.

Complete the following reactions: 140 C NaBH (i) BCl3 + NH4Cl [A] [B] C H Cl
0 4 6 5

(ii) BCl3 + LiAlH4 [C] + LiCl + AlCl3 1800 C (iii) BCl3 + H2 + Cfibre [D] + HCl red (iv) Na2B4O7 + NH4Cl [E] + B2O3 + NaCl + H2O heat
0

CHCl (v) BCl3 + (C2H5)4N+ Cl [F] (vi) B2O3 + CaF2 + H2SO4 [G] + [H] + [I] (vii) Al2O3 + Co(NO3)2 [J] + [K]+ [M]
3

Q10.

Starting from boric acid how would you prepare? (a) Boric anhydride (b) Boron trichloride (c) Boron trifluoride (d) Boron hydrides (e) Ethyl borate (f) Meta and tetraboric acids Boron on heating at 7000C in air gives white indusible amorphous powder (A), which is decomposed when heated in a current of steam to give a white powder (B) and a gas (C). Gas (C) turns red litmus blue and in aqueous solution gives yellow colour with Nesseler's reagent. Compound (B) on strong heating gives (D). A mixture of (D) and carbon on heating in current of Cl2 gives a colourless fuming liquid (E). (E) reacts with hydrogen to giev (F), which on strong heating produce a gas (G) and the fuming liquid (E). (G) on heating with (C) at 2000C produced inorganic benzene (H). Give (A) to (H) and explain the different reactions. A mineral (A) on fusion with Na2CO3 gives a white ppt. (B) and a solution which on concentration and cooling gives crystals of (C). Compound (B) on strong heating gives a colourless gas (D) and a solid (E). On passing gas (D) through aqueous solution of (E) again compound (B) is formed. COmpound (C) on treatment with hot conc. HCl followed by hydrolysis gives compound (F). COmpound (F) on strong heating gives (H) which on heating with chromic sulphate gives a green bead of chromic borate and SO3 gas. What are (A) to (H)? Explain the reactions involved. Describe acidic nature of Boric acid. Complete the following Low pressure (a) BCl3 + Hg electric arc (c) B + conc. HNO3 (b) AlCl3 + H2O (d) B2O3 + Hg(CN)2 EXERCISE II (B)

Q11.

Q12.

Q13. Q14.

Q1. Q2. Q3.

Although aluminium is above hydrogen in the electrochemical series yet it is stable in air and water. Explain. [IIT 1994] The hydroxides of aluminium and iron are insoluble in water. However, NaOH is used to separate one from the other. Explain. [IIT 1991] Aluminium sulphide gives a foul odour when it becomes damp. Write a balanced chemical equation for the reaction. [IIT, July 1997]

Q4.

Compound X on reduction with LiAlH4 gives a hydride Y containing 21.72 % hydrogen along with other products. The compound Y reacts with air explosively resulting in boron trioxide. Idensity X and Y. Give balanced reactions involved in the formation of Y and its reaction with air. Draw the structure of Y. [IIT 2001] A certain salt (X) gives the following tests: (i) Its aqueous solution is alkaline to litmus. (ii) On strongly heating it swells to give galssy material. (iii) When concentrated H2SO4 is added to a hot concentrated solution of (X), white crystals of a weak acid separate out. Identify (X) and write down the chemical equation for reaction at steps (i), (ii) and (iii). [Roorkee 1991] An inorganic Lewis acid (X) shows the following reactions: (i) It fumes in moist air. (ii) The intensity of fumes increases when a rod dipped in NH4OH is brought near it. (iii) An acidic solution of (X) on addition of NH4Cl and NH4OH gives a precipitate which dissolves in NaOH solution. (iv) An acidic solution of (X) does not give precipitate with H2S. Identify (X) and give chemical equations for reactions at steps (i) to (iii). [Roorkee 1994] (i) A white precipitate (B) is formed when a mineral (A) is boiled with Na2CO3 solution. (ii) The precipitate is filetered and the filterate contains two compounds (C) and (D). The compound (C) is removed by crystallisation and when CO2 is passed through the mother liquor left (D) changes to (C). (iii) The compound (X) on strong heating gives two compounds (D) and (E). (iv) (E) on heating with cobalt oxide produces blue coloured substance (F). Identify (A) to (F) and gives chemical equations for the reactions at steps (i) to (iv).
[Roorkee 1995]

Q5.

Q6.

Q7.

Q8. Q9. Q10.

Write the balanced equation for the reaction of Al4C3 and BF3 with water.
[IIT 2002]

Write the chemical reaction associated with the 'borax bead test' of cobalt (ii) oxide.
[IIT 2000]

How is boron obtained from borax. Give chemical equations with reaction conditions. Write the structure of B2H6 and its reaction with HCl.
[IIT 2002]

Q11.

Q12.

Identify A and B in the following reactions: Colemanite + (A) Na2B4O7 Na2B4O7 + (B) H3BO3 AlF3 is not soluble in anhydrous HF but soluble in KF. (a) Explain the observation

[IIT 1989]

Q13.

(b) When BF3 is added to above solution. AlF3 is precipitated. Write balanced chemical equation. [IIT 2004] Starting from boric acid how would you prepare? (a) Boric anhydride (b) Boric trichloride (c) Boron trifluoride (d) Boron hydrides (e) Ethyl borate (f) Meta and tetraboric acids

Q14.

Explain the following : (i) Boron and aluminium halides behave as Lewis acids. [Roorkee 1985] (ii) Boron tribromide is stronger acid than boron trifluoride. [Roorkee 1988] 3 ion but boron does not form [BF ]3 ion. (iii) Aluminium forms [AlF6] 6 (iv) Boron has high melting and boiling points. (v) The p-p back bonding occurs in the halide of boron and not in those of aluminium. Explain the following with appropriate reason: (i) Although aluminium is above hydrogen in the electrochemical series, it is stable in air and water.
[IIT1994]

Q15.

(ii) In the electrolytic manufacture of aluminium, carbon anodes are consumed. (iii) Cryolite is added to alumina in the electrolytic manufacture of aluminium.
[MLNR 1988]

(iv) Anhydrous AlCl3 fumes in air. [Roorkee 1986] (v) Alum is used in settling muddy water.
[Roorkee 1985]

ANSWER KEY EXERCISE I (A) Q1. Q5. Q9. Q13. Q17. Q1. Q5. Q9. (i) A D D B A B B B Q2. Q6. Q10. Q14. A C D C Q3. Q7. Q11. Q15. EXERCISE I (B) Q2. Q6. A D Q3. Q7. GROUP-III Isolation of "B" : Preperation of B2O3 from Borax or Colemanite Na 2 B4 O7 + HCl/H2 SO4 NaX + H2 B4 O7
H 2 B4 O7 + 5H2 O 4H3 BO3 B2 O3 + H2 O Reduction of B2O3 B2O3 + Na/K/Mg/Al B + Na2 O/K2 O/MgO/Al2 O3

D C D C

Q4. Q8. Q12. Q16.

A D A A

C A

Q4. Q8.

D B

(ii)

(i) (ii)

Chemical Props.: 4B + 3O 2 2B2 O3 Burning in air : 4Al + 3O 2 2Al2 O3 Reaction with water B + H 2O ( Cold & hot ) no reaction 2B + 3H 2 O B2 O3 + H2 (red hot) 3 Al + 3H 2 O Al ( OH ) 3 + H2 2 B + HCl no reaction B + H 2SO4 ( dil ) no reaction 2B + 3H 2SO4 ( conc.) 2H3 BO3 + 3SO2 B+3HNO3 H3 BO3 + 3NO2 2Al + 6H 2SO4 Al2 ( SO4 ) 3 + 3SO2 + 6H2 O 2B + NaOH + 2H 2 O 2NaBO2 + 3H2 2Al + NaOH + 2H 2O 2NaAl2 + 3H2 2B + N 2 2BN 2Al + N2 2AlN 4B + C B4 C 4Al + 3C 2Al4 C3

(iii)

Al + HNO3 ( 80% ) Al2 O3 ( passive layer ) and does not react further. (iv) (v)

(vi)

3Mg + 2B Mg 3B2 Preperation of B2H6 : Mg 3 B2 + HCl B2 H6 + B4 H10 + B5 H9 etc

( 10%)
V B4 H10 B2 H6 + H2 + higher borane 100o C Electric BCl3 ( or B Br3 ) + 6H2 B2 H6 + 6HCl discharge at low pressure

(i) (ii) (iii) (iv)

3LiAlH 4 + 4BF3 3LiF + 3AlF3 + 2B2 H6 or LiBH4 or 3(BF3) Reaction of B2H6 :

burns in B2 H 6 + O2 B2 O3 + H2 O air spontaneously

(i) (ii) (iii) *

B2 H 6 + H 2 O ( Cold is enough ) H3 BO3 + 6H2

anh. B2 H 6 + HCl ( dry ) B2 H5 Cl + H2 AlCl3

Heating of boric acid : 100o C 140o C H 3BO3 HBO2 H2 B4 O7 B2 O3 red hot Metaboric acid tetrabolic acid Glassy mass
O O NaOH Na 2 ( HO) 2 B B( OH) 2 6H2 O O O H3BO3+H2O2 (H2O)+(HO)2B O O H

Sodium peroxy brote used in washing powder as whitener Preparation of Borax : 2CaO 3B2 O3 + 2Na 2 CO3 2CaCO3 + Na2 B4 O7 + 2NaBO2
Filtered CaCO3(as residue)

Concentrated NaBO 2 + Na 2 B4 O7 10H2 O Na2 B4 O7 + NaBO2 and allowed to 24 3 as residue crystallise out 1 4 44solution 4 4 in
and filtered

CO2 passes and crystallise out again

[ 4NaBO2 + CO2 Na 2 B4 O7 + Na2 CO3 ]

Na 2 B4 O7 10H2 O as 2nd Corp. of the reaction. Uses of Borex : (i) In making glass, enamel and glaze of pottery.

(ii) As antiseptic in medicinal soaps preparation. Al2O3 preparation : (i) (ii) (iii)
300 C 2Al ( OH ) 3 Al2 O3 + 3H2 O
o

( NH 4 ) 2 SO4 Al2 ( SO4 ) 3 24H2 O Al2 O3 + 2NH3 + 4SO3 + 25H2 O

Al2 ( SO4 ) 3 Al2 O3 + 3SO3

Uses : (i) (ii) (iii)

In making refractory bricks as abrasive To make high alumina cement

(i) (ii)

AlCl3 preparation : 2Al + 6HCl(vap.) 2AlCl3 + 3H 2

(over heated) dry Al2 O3 + 3C + 3Cl2 2AlCl3 (vap.) + 3CO 1000o C

cooled Solid anh. AlCl3 Props : (i) Its anhydrous formed is deliquescent and fumes in air. (ii) It sublimes at 180oC. (iii) It is covalent and exists in the form of dimer even if in non polar solvents e.g. alc., either, benzene, where it is solible in fair extent.

Uses : (i) (ii) Alumns :

Friedel-Craft reaction Dyeing, drug & perfumes etc. M2SO4, M'2(SO4)3. 24 H2O

Props : Swelling characteristics where M = Na+, K+, Rb+, Cs+, As+, Tl+, M' = Al+3, Cr+3, Fe+3, Mn+3, Co+3 K2SO4.Al2(SO4)3.24H2O Potash alum (NH4)2SO4. Al2(SO4)3. 24H2O Ammonium alum . Cr (SO ) . 24H O K2SO4 2 Chrome alum 4 3 2

(NH4)2SO4. Fe2(SO4)3. 24H2O

Ferric alum

Preparation : Uses : (i) (ii) (iii) (iv) (v)

Al2 O3 + 3H 2SO4 Al2 ( SO4 ) 3 + 3H2 O Al2 ( SO4 ) 3 + K 2SO4 + aq.sol n crystallise Act as coagnlant Purification of water Tanning of leather Mordant in dying Antiseptic