+HIGHER ORDER THINKING QUESTIONS (HOTS)

UNIT-5:-SURFACE CHEMISTRY
ANSWER THE FOLLOWING : 1# colloid is not a substance but a state of substance. OR Same substance can act both as colloids and crystalloids

By A.k.panda,P.C.Panda,Rishi Verma,Umesh kumar, ,Satish Rajput

2# A sol is prepared by the addition of excess of KI to AgNO3 solution. Which one of the following will be most effective for its coagulation? [ Fe(CN)6]-4 , Al +3, PO4-3 , Mg +2 (2M) 3# Three gases A, B and C have critical temperatures 630 K, 33 K and 190 K respectively. Arrange them in increasing order of adsorption on activated charcoal. 4# What are the conditions when Tyndall effect can be observed? ( 2 M) 5# Why artificial rain can be cause by throwing common salt on the clouds?(1M) 6# What is CMC? What is its value for soap?(1M) 7 What is ZSM-5? Where it is used?(2 M) 8#100 mL of a colloidal solution is completely precipitated by the addition of 5 mL of 1 M NaCl solution. Calculate its coagulation value.( 2M ) 9# Action of soap is due to emulsification and micelle formation. Comment.(2M) 10# Why is it necessary to remove CO when ammonia is obtained by Habbers Process
11 # Why is the ester hydrolysis slow in the beginning and becomes faster after some time? 12# Why is it essential to wash the precipitate with water before estimating it quantitatively 13# What charge is likely to develop on the colloidal particles in the following cases ? (a) A sol is prepared by addition of excess of AgNO3 solution in KI solution (b) Ferric chloride is added to NaOH (c) If FeCl3 is added to excess of hot water (d) when KI solution is added to AgNO3 solution (e) when AgNO3 solution is added to KI solution 14 # In which of the following does adsorption occurs and why ? (a) silica gel placed in atmosphere get saturated with water (b) Anhydrous CaCl2 placed in the atmosphere gets saturated with water

1# The given statement is true . This is because the same substance may exist as colloid under certain conditions and as crystalloid under certain other conditions . For example , NaCl in water behaves as a crystalloid while in benzene , it behaves as a colloid . Similarly , dilute soap solution behaves like a crystalloid while concentrated soap solution behaves as a colloid ( associated colloid) . It is size of the particle which matters , i.e. , the state in which the substance exists . If the size of the particle lies in the range of 1nm to 1000 nm , it is in the colloidal state 2# the addition of excess of KI to AgNO3 solution will result into negative sol AgI/I , so Al +3 will be effective for coagulation 3# B < C < A . higher the critical temperature ,higher will be the Adsorption as van der waals forces are stronger near the critical temperature . 4# Tyndall effect is observed only when the following two conditions are satisfied. (i) The diameter of the dispersed particles is not much smaller than the wavelength of the light used; and (ii) The refractive indices of the dispersed phase and the dispersion medium differ greatly in magnitude.
when two oppositely charged clouds meet. It is possible to cause artificial rain by throwing electrified sand or spraying a sol carrying charge opposite to the one on clouds from an aeroplane. 6#The formation of micelles takes place only above a particular concentration called critical micelle concentration (CMC).
5# Clouds are aerosols having small droplets of water suspended in air. Sometimes, the rainfall occurs

ANSWER-

For soaps, the CMC is 104 to 103 mol L1. These colloids have both lyophobic and lyophilic parts. Micelles may contain as many as 100 molecules or more. 7# Zeolite sieve of microporosity-5 . It converts alcohols directly into gasoline(petrol) by dehydrating them to give a mixture of hydrocarbons. Molecular formula Hx[(AlO2)x(SiO2)96-x].16H2O 8# 50 .
9# A micelle consists of a hydrophobic hydrocarbon like central core. The cleansing action of soap is due to the fact that soap molecules form micelle around the oil droplet in such a way that hydrophobic part of the stearate ions is in the oil droplet and hydrophilic part projects out of the grease droplet like the bristles. Since the polar groups can interact with water, the oil droplet surrounded by stearate ions is now pulled in water and removed from the dirty surface. Thus soap helps in emulsification and washing away of oils and fats. The negatively charged sheath around the globules prevents them from coming together and forming aggregates.

Figure:(a) Grease on cloth (b) Stearate ions arranging around the grease droplet and (c) Grease droplet surrounded by stearate ions (micelle formed)

10# CO acts as a poison for the catalyst ( finely divided Fe) in Habers Process . Acitivity increases if it is used in finely divided state . 11# H+ which is generated from one of the product ( from acetic acid ) acts as a catalyst for the reaction [ a case of autocatalysis] . Hence the reaction becomes faster after sometime as production of H+ increases as time passes . 12# Some amount of the electrolyte mixed to form precipitate remains adsorbed on the surface of the particles of the precipitate . Hence , it is essential to wash the precipitate with water to remove the sticking electrolytes( or any other impurities) before estimating it quantitatively . 13# (a) positive sol i.e. , [AgI] Ag+ (b) Negative sol i.e. , [Fe(OH)3] OH (c) positive sol (d) positive sol AgI/Ag+

(e) negative sol AgI/I 14#(a) adsorption (b) Absorption

Unit-6: GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS ANSWER THE FOLLOWING : Q.1# (a) Metal A is extracted by pyrometallurgy process, metal B by electrolytic refining and metal C by simply heating the ore. Arrange these metals in the increasing order of reactivity.(1M) (b) What does a steep increase in the slope of a line on Ellingham diagram indicate?(1M) ( c) Why is Chalcopyrite roasted and not calcined during recovery of copper? ( 1M) (d) Why copper matte is put in silica lined converter? (e) Why is the extraction of copper from pyrites more difficult than that from its oxide ore through reduction? (f) Out of C and CO, which is a better reducing agent at 673 K ? (g) Copper can be extracted by hydrometallurgy but not zinc. Explain. (h) Out of C and CO, which is a better reducing agent for ZnO ? (i) The value of fG0 for formation of Cr2 O3 is 540 kJmol1and that of Al2 O3 is 827 kJmol 1Is the reduction of Cr2O3 possible with Al ? (j) Why is the reduction of a metal oxide easier if the metal formed is in liquid state at the temperature of reduction? (k) Although thermodynamically feasible, in practice, magnesium metal is not used for the reduction of alumina in the metallurgy of aluminium. Why ? (l) At a site, low grade copper ores are available and zinc and iron scraps are also available. Which of the two scraps would be more suitable for reducing the leached copper ore and why? (m) The reaction, Cr2 O3 + 2 Al Al2 O3 + 2 Cr (G0 = 421 kJ) is thermodynamically feasible as is apparent from the Gibbs energy value. Why does it not take place at room temperature? (n) Copper and silver lie below in the electrochemical series, yet they are found in combined state in the form of sulphide ores. Why? (2M) 2# Free energy of formation (fG) of MgO(s) and CO(g) at 1273K and 2273K are given below (Sample paper-2) fG (MgO(s)) = -941 kJ/mol at 1273K fG (MgO(s)) = -341 kJ/mol at 2273K fG (CO(g)) = - 439 kJ/mol at 1273K fG (CO(g)) = - 628 kJ/mol at 2273K On the basis of above data ,predict the temperature at which carbon can be used as a reducing agent for MgO(s) . Q.3 # The choice of reducing agent in a particular case depends on thermodynamic factor . How far do you agree with this statement ? Support your opinion with two examples Q.4# What chemical principle is involved in choosing a reducing agent for getting the metal from its oxide ore ? Consider the metal oxides , Al2O3 and Fe2O3 and justify the choice of reducing agent in each case . (3M) (AI-2008)

Q.5 # The standard Gibbs energy of reactions at 1773K are given below: ( 3M) (AI-2005) C + O2 CO2 : rG0 = -380 kJ/mol ; 2C +O2 2CO : rG0 = -500 kJ/mol Discuss the possibility of reducing Al2O3 and PbO with carbon at this temperature. 4Al + 3O2 2Al2O3 : rG0 = -22500 kJ/mol ; 2Pb + O2 2PbO : rG0 = -120 kJ/mol 6# How is the concept of coupling reactions useful in explaining the occurrence of a non-spontaneous reaction ? (2M)(AI-2005&06) ANSWER-UNIT-6 Answer--1:-- (a) C< A < B (b) The steep increase in thje slope of a line due to change in phase, i.e. solid to liquid . The temperature at which such change occurs is indicated by increase in slope on positive side .For example, the abrupt increase in Zn to ZnO plot shows the melting of Zn metal . (c) chalcopyrite is a sulphide ore , so it is roasted in presence of oxygen so as to convert into oxide ore for easy reduction . Carbonate ores are calcined . (d) Copper matte contains Cu2S and FeS .In the converter FeS gets converted into FeO when hot air blast is blown into the converter.Silica helps in removal of FeO impurity as slag. 2FeS + 3 O2 2FeO + 2 SO2 FeO (impurity) + SiO2 (silica) FeSiO3 (slag) (e) The reducing agent forms its oxide when the metal oxide is reduced. The role of reducing agent is to provide G0 negative and large enough to make the sum of G0 of the two reactions (oxidation of the reducing agent and reduction of the metal oxide) negative. Carbon is the poor reducing agent for sulphide ores wheras it is good reducing agent for oxide ores . ( f) At 673K , the G0 vs T line for CO,CO2 is lower than that of C, CO line . Carbon monoxide is the better reducing agent at 673 K (g) Metals (such as Cu) occupying lower positions in the electrochemical series can be extracted by hydrometallurgy because the metal ions(Mn+) of such metals can be easily reduced by treatment with some more electropositive metal. Metals occupying higher positions in the electrochemical series cannot be extracted by hydrometallurgy because the metal ions(Mn+) of such metals are difficult to reduce. Zn has large negative reduction potential. (h) The line for G0 ( CO ,CO2) lies above the line for G0 ( Zn ,ZnO) at the temperature employed for reduction of Zinc oxide.Hence reduction of ZnO with CO is not possible as the rG0 for this reaction would be positive ZnO + CO +1673K Zn + CO2 rG0 = + Ve ( not feasible) On the other hand , the line for G0 ( C ,CO) Vs T lies below the line for G0 ( Zn ,ZnO) .Hence ,coke can reduce Zinc oxide to zinc as the rG0 for this reaction would be negative and hence the reaction is feasible . ZnO + C +1673K + CO Zn rG0 = - Ve (feasible) Answer (i) # (i) 2 Cr + 3/2 O2 Cr2 O3 fG0 = -540 kj/mol 0 (ii) 2 Al + O2 Al2O3 fG = -827 kj/mol Equation (ii) (i) , we get 2Al + Cr2O3 Al2O3 + 2Cr rG0 =[ -827 (-540)] kJ = - 287 kJ Since the rG0 for the reduction of Cr2 O3 with Al is negative therefore, the reaction is possible (j) The entropy is higher if the metal is in liquid state than when it is in solid state. The value of entropy change (S) of the reduction process is more on +ve side when the metal formed is in liquid state and the metal oxide being reduced is in solid state. Thus the value of G0 becomes more on negative side and the reduction becomes easier. (k) Temperatures above the point of intersection of Al2O3 and MgO curves, magnesium can reduce alumina. But the temperature required would be so high that the process will be uneconomic and technologically difficult. (l) Zinc being above iron in the electrochemical series (more reactive metal is zinc), the reduction will be faster in case zinc scraps are used. But zinc is costlier metal than iron so using iron scraps will be advisable and advantageous (m) Certain amount of activation energy is essential even for such reactions which are thermodynamically feasible, therefore heating is required. Answer-2:-- The desired equation is MgO(s) + C(s) Mg (s) + CO(g) ,. rG = ? At 1273 K :Mg(s) + O2(g) MgO(s) ; fG (MgO(s)) = -941 kJ/mol at 1273K -----(1) C(s) + O2 (g) CO(g) ; fG (CO(g)) = - 439 kJ/mol at 1273K ------(2) Equation (2) (1) rG = fG (CO(g)) - fG (MgO(s)) = - 439 kJ/mol -(-941 kJ/mol) = + 502 kJ/mol Since rG is +ve this reduction is NOT FEASIBLE at this tempetrature . At 2273 K:Mg(s) + O2(g) MgO(s) ; fG (MgO(s)) = -341 kJ/mol at 2273K -----(3)

C(s) + O2 (g) CO(g) ; fG (CO(g)) = - 628 kJ/mol at 2273K ------(4) Equation (4) (3) rG = fG (CO(g)) - fG (MgO(s)) = - 628 kJ/mol -(-341 kJ/mol) = - 287 kJ/mol Since rG is -ve (NEGATIVE) this reduction is FEASIBLE at this tempetrature . So Carbon can acts as reducing agent at this temperature i.e at 2273K Answer-3The thermodynamic factor helps us in choosing a suitable reducing agent for the reduction of particular metal oxide to metal . The feasibility of thermal reduction can be predicted on the basis of G0 Vs T plots for the formation of oxides, known as Ellingham diagram . from the diagram it can be predicted that metals for which the fG0 ( of their oxides) is more negative can reduce those metal oxides for which standard free energy of formation of their respective oxides is less negative . In other words , a metal will reduce the oxides of the other metals which lie above it in the Ellingham Diagram because the fG0 of the combined redox reaction will be negative by an amount equal to the difference in fG0 of the two metal oxides . For example, both Al and Zn can reduce FeO to Fe but Fe cannot reduce ZnO to Zn and Al2O3 to Al . Similarly , Carbon can reduce ZnO to Zn but not CO . thus the choice of reducing agent in a depends on thermodynamic factor .

UNIT-7: p-Block Elements

I# IDENTIFY THE FOLLOWING:
1 # An element A exists as a yellow solid in standard state. It forms a volatile hydride B which is a foul smelling gas and is extensively used in qualitative analysis of salts. When treated with oxygen, B forms an oxide C which is colourless, pungent smelling gas. This gas when passed through acidified KMnO4 solution, decolourizes it. C gets oxidized to another oxide D in the presence of a Heterogeneous catalyst. Identify A, B, C, D and also give the chemical equation of reaction of C with acidified KMnO4 solution and for conversion of C to D. 2# When conc. sulphuric acid was added to an unknown salt present in a test tube, a brown gas (A) was evolved. This gas intensified when copper turnings were also added into this tube. On cooling, the gas A changed into a colourless gas B. (a) Identify the gases A and B. (b) Write the equations for the reactions involved. 3# A translucent white waxy solid A on heating in an inert atmosphere is converted in to its allotropic form (B). Allotrope A on reaction with very dilute aqueous KOH librates a highly poisonous gas C having rotten fish smell. With excess of chlorine A forms D which hydrolysis to compound E. Identify compounds A to E . 4# Concentrated sulphuric acid is added followed by heating to each of the following test tubes labelled (i) to (v)

Identify in which of the above test tube the following change will be observed. Support your answer with the help of a chemical equation. (a) Formation of black substance (b) Evolution of brown gas (c) Evolution of colourless gas (d) Formation of brown substance which on dilution becomes blue 5 # A gas X is soluble in water . Its aq. Solution turns red litmus blue with excess of aq. CuSO4 solution it give s deep blue colour with FeCl3 solution a brownish ppt. soluble in HNO3 is obtained. Identify gasX and write reactions for changes observed . 6# Element A burns in N2 to give a compound B which is ionic in nature . B on reaction with water gives C and D.The solution of C becomes milky on passing CO2 through it. Identify the compound A ,B ,C ,D . 7# An orange solid A on heating gives a green residueB, water vapours and a colourless gas C . The gas C in dry condition is passed over heated Mg to give solid D which further reacts with water to form E which gives dense white fumes with HCl . Identify the compound A ,B ,C ,D and E and write the reactions involved .

8# A colourless inorganic salt A decomposes at 2500C to form B and C leaving no residue . The oxide C is liquid at room temperature and is neutral towards litmus while B is neutral oxide and is used as anaesthetic in minor dental surgery . When Phosphorous burns in excess of B produces compound which is a strong dehydrating agent which when treated with HNO3 produces acid D and a gas E Identify A to E and write the reactions.

I# ANSWERS OF IDENTIFY THE FOLLOWING: ANS-1# S8[A] +8H2 + heat 8H2S[B]

8H2S + 12O2 8SO2 [C] ; 5SO2 + 2KMnO4(pink)/H+ +2H2O K2SO4 +2MnSO4(Colourless solution) 2SO2 +O2 + Pt/heat 2SO3 (D) ANS-2# 2NaNO3 +H2SO4 +heatNa2SO4 + 2HNO3 4HNO3+ heat4NO2+2H2O+O2 Cu+4HNO3Cu(NO3)2 +2NO2 +2H2O 2NO2[A] (cool)=> N2O4[B] ANS-3# P4(white Phosphorous)[A] +very dil KOHPH3[C] P4(white Phosphorous)[A] +heatRed- P(red Phosphorous)[B] P4(white Phosphorous)[A] +Cl2(excess)PCl5[D] PCl5[D] +H2O(excess)H3PO4[E] ANS-4#(a) Test tube(i): C12H22O11+Conc.H2SO411H2O +12C (black subs.) (b) Test tube(ii):2NaBr +3H2SO42NaHSO4 +SO2+Br2(brown gas) (c) Test tube(v): KCl +H2SO4 +heat KHSO4+HCl(colourless gas) (d) Test tube(iii): Cu +2 H2SO4 CUO(brown subs) On dilution: CuO(brown subs) +2 dil.H2SO4 CuSO4(blue substance) (e) Test Tube(iv) : S(yellow powder) + conc.H2SO4 ----SO2 +H2O ANS-5: NH3(g) +H2O NH4OH(aq) [basic and turn red litmus blue] 3 NH4OH(aq) + CuSO4 [Cu(NH3)4]SO4 +4H2O

(deep blue)

3 NH4OH(aq) +FeCl3Fe(OH)3 +3 NH4Cl Fe(OH)3 + 3HNO3 Fe(NO3)3( soluble) +3H2O ANS-6: 3Ca + N2Ca3N2 [B] [A] Ca3N2 + 6 H2O3 Ca(OH)2 [C] + 2NH3 [D] Ca(OH)2 +CO2 CaCO3 + H2O ANS-7: (NH4)2Cr2O7 +heat N2 + Cr2O3 + (Orange solid-A) [C] [green solid B ] N2 +3Mg +heat Mg3N2 [D] Mg3N2 [D] +6H2O 3 Mg(OH)2 +2NH3 [E] NH3 [E] +HCl NH4Cl (dense white fumes) ANS-8:NH4NO3[A]+heat at 2500C N2O(g) [B] + 2 H2O [C] 10 N2O +P4 10 N2 + P4O10 10 P4O10 is a dehydrating agent P4O10 + 4 HNO3 4 HPO3 [D] + 2 N2O5 (g)

II# Explain Why ? / Give reason ? / Account for the following ?

1# HBr and HI cant be prepared by treating metal bromides or iodides with conc. H2SO4 . 2# Why NO2 readily forms a dimmer, whereas ClO2 does not though both are odd electron molecule. 3# Write the balanced chemical equation for the reaction of Cl2 with hot and concentrated NaOH. Is this reaction a disproportionation reaction? Justify. 4# SCl6 is not known but SF6 is known . 5# In trimethylamine, the nitrogen has a pyramidal geometry whereas in trisilylamine,it has a planar 6# SF6 is resistant to hydrolysis whereas SF4 is readily hydrolysed. 7# NCl3 gets hydrolysed to form NH3 and HOCl while PCl3 gets hydrolysed to give H3PO3 and HCl . Explain . 8# In the solid state , PCl5 is in ionic nature . Explain. 9# I2 form I3 but F2 does not formF3 . 10# NO is paramagnetic in gaseous state but diamagnetic in the solid and liquid state. 11# Yellow ppt. of Sulphur disappear when boiled with sodium sulphite . 12# NF3 is more stable but NCl3 is less stable .

13# SH6 and PH5 are not formed but SF6 and PF5 are formed . 14# KHF2 is known but compound of formula KHCl2 or KHBr2 are not known . Why ? 15# Iodine is more soluble in KI solution than in water . 16# HF is stored in wax -coated bottle . 17# HCl is not used to make the medium acidic in titrations involving KMnO4 . 18 # Addition of Cl2 to KI solution gives it a brown colour but excess of Cl2 turns it colourless. 19# CN ion is known but CP is not ? 20# Comment on the nature of two SO bonds formed in SO2 molecule. Are the two SO bonds in this molecule. 21# Why anhydrous CaCl2 is not used to dry up Ammonia ? 22# What happens when Zinc is treated with Conc.H2SO4 . 23# Why conc.H2SO4 is not used for drying of H2S gas . 24# When HCl reacts with finely powdered iron , it forms ferrous Chloride and not ferric chloride . 25# Conc.HNO3 turns yellow on exposure to sunlight .Why ?

ANSWER-II# Explain Why ? / Give reason ? / Account for the following ?

ANS-1# Because Br- and I - will get oxidized by conc. H2SO4 to respective Br2 and I2 . ANS-2# odd electron molecule often get dimerise in order to pair the electrons but ClO2 does not .Thisis thought to be because the odd electron is delocalized. ANS-3# 6 NaOH ( hot and conc.)+ 3Cl2 5 NaCl + NaClO3 + H2O . yes it a disproportionation reaction because the OS of Cl2 is Zero and is oxidized to +5 (in NaClO3) and reduced to -1 (in NaCl) . Due to simultaneous oxidation and reduction occurs of the same species i.e Cl2 . ANS-4# SF6 is known because of small size and more electronegativity of Fluorine which can form strong bond and hence the energy released can compensate to promote electrons in vacant d-orbitals of S which is not possible in case of Chlorine . Due to large size of Cl which cannot be accommodated around Sulphur and stability will also be less due to inter electronic repulsion between lone pairs of Chlorine ( whose size is large as compared to F) ANS-5# Due to presence of Vacant d-orbitals in Si , it can form P-d bond with nitrogen . so reduced to SP2 hybridisation and becomes plannar with three sigma bonds . Which is not possible in case of trimethylamine as
Carbon does have vacant d-orbital. ANS-6# SF6 is octahedral ( which is symmetrical) where six F-atoms surroundingS protect it from attack of H2O molecules. So ,SF6 is sterically protected then SF4 towards the even thermodynamically favorable hydrolysis reaction. Also F-atoms do not have Vacant d-orbitals to accommodate electrons from water molecules . This makes SF6

chemically inert. Due to this it suppresses internal charges hence used in high voltage generators(gaseous insulators, and switch gears. ANS-7# The Cl of NCl3 has vacant d-orbital which can accommodate electrons from water molecules and get hydrolysed to produce HOCl and NH3 . But in case of PCl3 , it is the vacant d- orbital of P can accommodate electrons from water molecules and get hydrolysed to give H3PO3 and HCl . [PO bond strength > ClO] ANS-8# Due to unequal bond length of equatorial and axial bond that is why it is reactive . So, in solid state (in close range) , it can be stabilized by forming [PCl4]+ and [PCl6]- which are symmetrically stable tetrahedral and octahedral str. respectively . ANS-9# Due to presence of vacant d-orbital in Iodine it can accept the electrons of iodide ion . ANS-10# NO is an odd electron molecule (paramagnetic) . In solid and liquid state , dimer is formed and there is no unpaired electrons and act as diamagnetic . ANS-11# Na2SO3 + S ( yellow solid ) Na2 S2O3 ( sodium thiosulphate) ANS-12# Because of small size and more electronegativity of Fluorine which can form strong bond with Nitrogen and becomes stable as compared to large size Chlorine . ANS-13# It is because of two reason why hydrogen cannot form SH6 and PH5 though SF6 and PF5 are formed Reason-1: Hydrogen is less electronegative element as compared to fluorine . SH bond is weaker than SH bond . Reason-2: The enthalpy of atomization of HH is very high as compared to FF . High enthalpy of dissociation can not be compensated by energy released during bond formation .

ANS-14# KHF2 contains HF2 ion which is stable due to formation os H-bonding between HF and F . This is

possible because of high electronegativity of F ( FH ..H) on the other hand , Cl and Br cannot form hydrogen bonds due to low electronegativity . ANS-15# Due to formation of polyiodide ion .KI +I2 K+ [I3] . Ion dipole interaction between polyiodide ion and water responsible for solubility . ANS-16# Due to formation of complex called flurosilicic acid , H2[SiF6] ANS-17# Chloride gets oxidized to chlorine by conc. Sulphuric acid ( an oxidizing agent) ANS-18# Cl2 + KI ( solution) KCl + I2 ( brown ) . Iodide reduces chlorine to chloride ion. The I2 formed will react with excess Cl2 in presence of water to form HIO3 which makes it colourless . ANS-19# Nitrogen being small size can form stable and effective P-P bond ( in case of cyanide ion) but which is not possible in CP . P is larger size which cannot form stable and effective P-P bond . ANS-20# S 3s2 3px23py13pz1 (Ground state) ; S 3s2 3px13py13pz1 3d1 (excited state) Sp2 hybridisation in Sulphur . one half filled 3pz1 can form P-P bond with half-filled 2p orbital of one Oxygen and one half filled 3d1 of Sulphur with half-filled 2p orbital of another Oxygen can form P-d bond . And due to resonance the bond lengths are equal. ANS-21# Because it t forms CaCl2.8NH3 , addition compound . ANS-22# Zn reduces Sulphate to SO2 and ultimately colloidal sulphur .As Conc. H2SO4 is an oxidizing agent . ANS-23# H2S + Conc.H2SO4 ( an oxidizing agent ) Sulphur ANS-24# Its reaction with iron produces H2 Fe + 2 HCl FeCl2 + Cl2 . Liberation of hydrogen creates a reducing environment and prevents the formation of ferric chloride . ANS-25# In presence of light nitric acid decomposes to form NO2 (brown) , O2 and water .

II # Arrange the Following in increasing order against the properties mentioned :-

1# Bond Dissociation Enthalpy:- (a) BrBr , II , ClCl , FF (b) HI , HF, HBr,HCl (c) OH, HTe, HSe, HS. (d) NN, PP, AsAs 2# Acid strength:- (a) HI , HF , HBr , HCl (b) HF, CH4 , H2O , NH3 (c) H2O, H2Te , H2Se , H2S 3# Base Strength:- BiH3 , NH3 , AsH3 , SbH3 , PH3 4# Thermal Stability:- (a) H2O , H2Te , H2Se , H2S (b) PH3 , BiH3 , AsH3 , SbH3 , NH3 5# Oxidizing Ability:- (a) Cl2 , F2 , I2 , Br2 (b) HCl , HNO3 ,H2SO4 ,H3PO4 (c) HClO3 ,HClO , HClO2 ,HClO4 (d) F2 ,Cl2 ,O2 , O3 6# Catenation property:- (a) As , N, P , Sb (b) Se ,S , Te ,O (c) Si , Sn , C , Ge 7# Bond Angle:- (a) H2Se , H2O, H2S ,H2Te (b) PH3 , BiH3 , AsH3 , SbH3 , NH3 8# Boiling Point :- (a) H2S , H2O , H2Te , H2Se (b) PH3 , BiH3 , AsH3 , SbH3 , NH3 ++ ++ ++ ++ 9# Stability:- (a) Pb , C , Sn , Si (b) As3+ , Bi3+ , Sb3+ (c) Ga+ , Tl+ ,Al+, In+ 10 # Covalent Character :- (a) MCl , MBr , MI , MF (b) Cr2O3 , CrO, CrO3 (c) P2O5,Sb2O5, As2O5 (d) BeCl2, MgCl2 ,CaCl2, BaCl2 11# Acid Strength:- (a) HOClO2 , HOClO , HOCl ,HOClO3 (b) HOCl , HOI ,HOBr 12# Acidic Character -- (a) N2O, N2O5, N2O3 ,NO , N2O4 (b) ClO2 , Cl2O7 ,Cl2O , Cl2O6 (c) HNO2 & HNO3 (d) H2SO3 &H2SO4 (e)GeO2 ,ClO2 ,As2O3 ,Ga2O3 (f) P2O5 ,SO3 , N2O5 , CO2 , SiO2 (g) Al2O3 ,CaO, Cl2O7 ,SO3 (h) BF3 ,BBr3 , BCl3 13# Volatility:- H2O , H2Te , H2Se, H2S 14# Electron Gain Enthalpy :- (a) I , Br , Cl , F (b) N , O, P ,S (c) F, Cl , O , S 15 # Ionisation Enthalpy:- (a) O , N , F , C (b) Ar , Ne , He , Xe , Kr 16# Electronegativity:- (a) Cl ,F, Br, I (b) O , N , F , C 17# Stability:- F , I , Cl , Br 18# Reducing properties: (a) H2O, H2Te , H2Se , H2S (b) H3PO4 , H3PO2 , H3PO3 CHECK-UP LIST:- ARRANGEMENT (in terms of properties mentioned.) 1# II < FF < BrBr < ClCl (Bond Dissociation Enthalpy)Inter-electronic repulsion 2# HF < HCl < HBr < HI (Acid strength)Lower BDE of HI,large size of I 3# MI < MBr < MCl < MF ( Ionic Character)Fajans RuleLager polarizability of I 4# BiH3 < SbH3 < AsH3 < PH3 < NH3 ( Base Strength) small size of N High electron density in Ammonia 5# H2O < H2S < H2Se < H2Te ( Acid Strength and Reducing Character) --- BDE

6# H2Te < H2Se < H2S < H2O ( Thermal Stability) ---BDE 7# H2O < H2Te < H2Se < H2S (Volatility)--- H-Bond and Vander waals force 8# H2S < H2Se < H2Te < H2O ( Boiling Point) -- H-Bond and Vander waals force 9# PH3 < AsH3 < NH3 < SbH3 < BiH3 (Boiling Point) -- H-Bond and Vander waals force 10# I2 < Br2 < Cl2 < F2 (Oxidizing Ability) --Electron gain enthalpy, hydration enthalpy, dissociation enthalpy . 11# H2Te < H2Se < H2S < H2O ( Bond Angle )----- Size of central atom , electronegativity, repulsion of bond pairs. 12# HClO4 < HClO3 < HClO2 < HClO ( Oxidizing Power) 13# HOCl < HOClO < HOClO2 < HOClO3 ( Acid Strength) Stability of its conjugate base , charge dispersal , Oxidation states. 14 # HOI < HOBr < HOCl ( Acid Strength) ---Stronger the OX bond Weaker the OH bond More the acidic character. 15# Cl2O < ClO2 < Cl2O6 < Cl2O7 ( Acid Strength)-- Higher oxidation states, covalent character 16# ClO4 < BrO4 > IO4 or BrO4 > IO4 > ClO4 (Oxidizing Power) 17# Ga2O3 < GeO2 < As2O3 < ClO2 (Acidic Character) 18# BF3 < BCl3 < BBr3 (Acidic Character)Effective 2p2p overlap in BF3 reduces the electron deficiency of B , make it less acidic. 19# Pb < Sn = Ge < Si < < C ( Catenation Property) Sigma bond strength 20# C++ < Si++ < Sn++ < Pb++ ( Stability) ---- Inert pair effect 21# N2O < NO < N2O3 < N2O4 or NO2 < N2O5 (Acidic Character) Higher oxidation states, covalent character 23# HCl < H2SO4 < HNO3 (Oxidizing Acid) 24# (i) N < P > As > Sb (ii) O < S > Se > Te ( catenation property) --- ( P , N ) ; ( O ; S ) 25# (a) HNO2 < HNO3 (b) H2SO3 < H2SO4 (Acidic character) 26# I < Br < Cl < F (Stability) 27# Reactivity---ClF3 > BrF5 > IF7 > ClF7 > BrF3 >IF5 > BrF > IF3 >IF 28# StabilityClO4 > ClO3 > ClO2 >ClO

UNIT-8:d-Block Elements
Q.1 # Why is Cr2+ strongly reducing and Mn3+ strongly oxidising when both have d4 configuration. Ans:- Cr2+ is reducing as its configuration changes from d4 to d3, the latter having a half-filled t2g level .On the other hand, the change from Mn2+ to Mn3+ results in the half-filled (d5) configuration which has extra stability. Q.2 # Explain why Cu+ ion is not stable in aqueous solutions? Ans--Cu+ in aqueous solution underoes disproportionation, i.e., 2Cu+(aq) Cu2+(aq) + Cu(s) The E0 value for this is favourable. Cu++ has higher hydration enthalpy than Cu+ Q.3# Cobalt(II) is stable in aqueous solution but in the presence of complexing reagents it is easily oxidised. Ans Co(III) has greater tendency to form coordination complexes than Co(II) . Due to higher charge by radius ratio and also due to greater CFSE( Crystal Field Stabilisation Energy) . Co (III) Has d6 configuration . In case of of strong ligand , It is t2g 6 eg0 . So , Co(II) changes to Co(III) i.e. easily oxidized . Q.4 # Mn+2 compounds are more stable than Fe+2 toward oxidation to their + 3 state .(AI-06) OR , Why E 0 value for the Mn 3+ /Mn 2+ is much more positive than Fe 3+ /Fe 2+ ? Ans-Mn 3+ + e> Mn 2+ (d4 system , less stable ) (d5 system , more stable ) extra stable due to half-filled confN Fe3+ + e> Fe 2+ (d5system , more stable ) (d6 system , less stable ) 0 2+ Q.5 # The E (M /M) value for copper is positive (+0.34V). What is possibly the reason for this? (Hint: consider its high aH0 and low hydH0) Ans The reduction potential value depends on relative value of three enthalpies viz aH0 , iH0 and - hydH0 . The copper has high aH0 and iH0 . Therefore high enthalpy required to transform Cu(s) to Cu2+(aq) is not balanced by its low hydH0 . Q.6 # Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only? Ans-- Because of small size and high electronegativity oxygen or fluorine can oxidise the metal to its highest oxidation state. Oxygen has the ability to form multiple bond with transition metals . Q.7 # Which is a stronger reducing agent Cr2+ or Fe2+ and why ? Ans-- Cr2+ is stronger reducing agent than Fe2+ Reason: d4 d3 occurs in case of Cr2+ to Cr3+But d6 d5 occurs in case of Fe2+ to Fe3+ . In a medium (like water) d3 is more stable as compared to d5 (see CFSE) Q.8 # Why is the E0 value for the Mn3+/Mn2+ couple much more positive than that for Cr3+/Cr2+ or Fe3+/Fe2+? Explain. Ans--Much larger third ionisation energy of Mn (where the required change is d5 to d4) is mainly responsible for this. This also explains why the +3 state of Mn is of little importance. Q.9 # Give reason for it?. Ni+2 compounds are thermodynamically more stable than Pt+2 compounds whilst Pt(IV) are relatively more stable than Ni(IV) compounds . OR, K2PtCl6 is well known cpds. but corresponding Ni-compound is not known . Ans--The oxidation state of Pt in K2 Pt Cl6 is +4 .The sum of the first four ionization energies (IE1+IE2 +IE 3+IE 4) of pt is less than those of Ni. Q.10# E0 for Mn+3 / Mn+2 couple is more positive than for Fe+3 / Fe+2 or Cr+3 / Cr+2 . Ans-- Much larger third Ionisation enthalpy of Mn ( where the required change is d5 to d4) is mainly responsible for this . this also explains why the +3 state of Mn is of little importance . Q.11 #.Why is HCl not used to acidify a permanganate solutions in volumetric estimation of Fe+2 or C2O4 2 . Ans- Since Cl of Hydrochloric acid is oxidized to chlorine by MnO4 . so , actual amount of KMnO4 required to oxidize C2O4 2 couldnot be determined.

II# IDENTIFY THE FOLLOWING:

1# A mixed oxide of iron and chromium FeO.Cr2O3 is fused with Sodium Carbonate in presence of air to form a yellow coloured compound (A). On acidification the compound (A) forms an orange coloured compound (B) which is a strong oxidizing agent. (i) Identify the compounds (A) and (B) (ii) Write balanced chemical equations for each step. 2 # A green chromium compound (A) on fusion with alkali gives a yellow compound (B) which on acidification gives an orange coloured compound (C) . C on treatment with NH4Cl gives an orange coloured product (D) , which on heating decomposes to give back (A) . Identify A,B,C,D .Write equations for reactions . 3# (a) A blackish brown coloured solid (A) when fused with alkali metal hydroxides in presence of air produces a dark green compound (B), which on electrolytic oxidation in alkaline medium gives a dark purple compound (C). Identify (A), (B) and (C) and write balanced chemical equations for the reactions involved. (b) What happens when an acidic solution of the green coloured compound (B) is allowed to stand for some time? Give the equation of the reaction involved. What is this type of reaction called? (Hint: MnO42- changes to MnO4-) 4# (A) reacts with H2SO4 to form purple coloured solution (B) which reacts with KI to form colourless compound (C). The colour of (B) disappears with acidic solution of FeSO4. With concentrated H2SO4 (B) forms (D) which can decompose to give a black compound (E) and O2. Identify (A) to (E) and write equations for the reactions involved. 5# When an orange coloured crystalline compound A was heated with common salt and concentrated H2SO4, an orange red coloured gas B was evolved. The gas B on passing through NaOH solution gave an yellow solution C (i) Identify A,B and C. (ii) Write balanced chemical equation involved in the reactions. 6# Two gases (A) and (B) turns acidified K2Cr2O7 solution green. Gas(A) turns lead acetate paper black and when passed through gas(B) in aq. Solution , yellowish turbidity appears . Identify A and B and explain. 7# Explain why a green solution of K2MnO4 turns purple and a brown solid is precipitated when CO2 gas is bubbled into the solution . UNIT-9: CO-ORDINATION COMPOUNDS I#EXPLAIN ? 1# Why only Transition metals are known to form Pi-complexes 2#A solution of [Ni(H2O)6]2+ is green but a solution of [Ni(CN)4]2 is colourless. Explain. 3#Though CO is a weak lewis base yet it forms a number of stable metal carbonyls .Explain 4# What will be the correct order for the wavelengths of absorption in the visible region for the following: and why [Ni(NO2)6]4, [Ni(NH3)6]2+, [Ni(H2O)6]2+ ? 5# Explain why [Co(NH3)6]3+ is an inner orbital complex whereas [Ni(NH3)6]2+ is an outer orbital complex. 6# The spin only magnetic moment of [MnBr4]2 is 5.9 BM. Predict the geometry of the complex ion ? 7# A solution of [Ni(H2O)6]2+ is green but a solution of [Ni(CN)4]2 is colourless. Explain. 8# [Cr(NH3)6]3+ is paramagnetic while [Ni(CN)4]2 is diamagnetic. Explain why? 9# [Fe(CN)6]4 and [Fe(H2O)6]2+ are of different colours in dilute solutions. Why? 10# Amongst the following, which is the most stable complex and why ? (i) [Fe(H2O)6]3+ (ii) [Fe(NH3)6]3+ (iii) [Fe(C2O4)3]3 (iv) [FeCl6]3 10 11# Silver atom has completely filled d orbitals (4d ) in its ground state. How can you say that it is a transition element? 12# The ability of oxygen to stabilize the metal in higher oxidation states exceeds that of fluorine. 13# Why is that while making an aq. solution of FeCl3 lab. Reagent some HCl solution is also added besides FeCl3 ANSWERS TO I # E X P L A I N ? ANS-1: The transition metals have vacant d-orbitals which can accept electron pairs of ligand containing pielectrons(H2C=CH2 ,C5H5 , C6H6 )
ANS-3# CO is a pi acceptor ligand which forms stable synergic bond due to back bonding ANS-4# NO2 is a strong field ligand acc. to spectrochemical series , so it energy of absorption is in higher energy range . H2O < NH3 < NO2( spectrochemical series) The correct order for the wavelengths of absorption in the

region: [Ni(H2O)6]2+ [Ni(NH3)6]2+, [Ni(NO2)6]4,

visible

Ans-5:- In the presence of NH3, the 3d electrons pair up leaving two d orbitals empty to be involved in d2sp3 hybridisation forming inner orbital complex in case of [Co(NH3)6]3+. In [Ni(NH3)6 ]2+, Ni is in +2 oxidation state and has d8 configuration, the hybridisation involved is sp3d2 forming outer orbital complex.

Ans-6:- Since the coordination number of Mn2+ ion in the complex ion is 4, it will be either tetrahedral (sp3 hybridisation) or square planar (dsp2 hybridisation). But the fact that the magnetic moment of the complex ion is 5.9 BM, it should be tetrahedral in shape rather than square planar because of the presence of five unpaired electrons in the d orbitals. ANS:-7# Cyanide being the strong ligand , the orbital splitting energy is high in case of square plannar splitting in [Ni(CN)4]2 The electrons are paired up during the electron fill-up in case of square plannar splitting , the transition of electrons not occurs in visible spectrum so it is colorless. In case of [Ni(H2O)6]2+ it is green , as water is a weak ligand in Octahedral

splitting , The unpaired electron can take transition in visible spectrum and the complementary colour is green. ANS-8# [Ni(CN)4]2 forms square plannar (dsp2) complex with no unpaired electron so ,it is diamagnetic . [Cr(NH3)6]3+ forms octahedral (d2sp3) complex with unpaired electron so ,it is paramagnetic . ANS-9# Due the change in the nature of ligand , strong field and weak field , the orbital splitting energy changes . So ,the energy of absorption changes and hence , the complementary colour changes. ANS-10# (iii) [Fe(C2O4)3]3 , due to presence of bidentate ligand .

II# Explain these experimental results . 1 . Aqueous copper sulphate solution (blue in colour)gives: (a) a green precipitate with aqueous potassium fluoride , and (b) a bright green solution with aq. potassium chloride . Explain these experimental results . 2.What is the coordination entity formed when excess of aq. KCN is added to an aq.solution of CuSO4 ?Why is it that no precipitate of copper sulphide is obtained when H2S(g) is passed through the solution ? 3.A coordination compound has the formula CoCl3.4NH3 .It does not liberate NH3 but forms a precipitate of AgCl on treatement with AgNO3 solution .Write the formula and IUPAC name of the complex 4# 0.1 M solution of a complex obtained by mixing CoCl3 and NH3 in the molar ratio 1:4 froze at -0.3720C . What is the formula of the complex . (Kf = 1.86 0C C/m) ANSWERS TO II : Explain these experimental results Ans-3 :- As it does not liberate any ammonia ,it means all ammonia are acting as ligand . To form octahedral stable complex two more Cl- will also act as ligand . So only one Cl- will act as counter ion and link through primary linkage . Becxause it forms AgCl precipitate when the complex treated with AgNO3 The Complex is [Co(NH3)4Cl2]Cl -- tetraamminedicholridocobalt(III)chloride Ans-4 :- Tf (theoretical) = Kf . m = 1.86 0.1 = 0.1860 Tf (obs) = 0.3720 i = Tf (obs) /Tf (theoretical) = 0.3720 /0.1860 =2 The complex dissociate to form two ions [Co(NH3)Cl2]+ and Cl III# Write the IUPAC Name and draw the structures of all the isomers with this formula of complex. (optical & geometrical) (i) [Co(en)2Cl2]Cl (ii) [PtCl(NH3)5]Cl3 (iv) [Co(OX)3]3 (v) [CoCl2(en)2]+ (vi) [CoCl2(en)(NH3)2]+ + [CoCl (en)2(NH3)]

(vii)

1. Unlike phenols, alcohols are easily protonated. Explain. (1M) 2. Why absolute alcohol can not be obtained from rectified spirit by simple distillation? (1M) 3. Explain why is o- nitro phenol more acidic than o-methoxy phenol? (1M) 4. Out of two isomeric aromatic compounds X,Y with formula C7H7OH only X gives purple colour with neutral ferric chloride.Identify X and Y. (1M) 1. A gives positive lucas test in 5 minutes. Its molecular mass is 60u. It reacts with PBr3 to give B which when treated with benzene in presence of AlCl3 gives compound C. Write structural formula of A,B and C. (2M) 2. An organic compound A having formula C6H6O gives a characteristic colour with Aq. FeCl3 solution.When A is treated with CO2 and NaOH at 400K under pressure B is obtained. The compound B on acidification gives C which reacts with acetyl chloride to form D which is a Popular pain killer. Deduce strutures of A,B,C and D. (3M) ANSWERS 1. In alcohols the lone pair of electrons on oxygen are localised and hence are easily available For protonation.But in phenols the lone pair of electrons on oxygen are delocalised over the benzene ring due to resonance and hence are not easily available for protonation.

UNIT 11:

ALCOHOLS PHENOLS AND ETHERS

2. Rectified spirit contains 95% ethyl alcohol and 5% water and forms an azeotropic mixture Which distils at a constant temperature of 351.13K. 3. NO2 group is an electron withdrawing group.So nitro phenol is more acidic than phenol -OCH3 group is an electron releasing group so it is less acidic than phenol. Hence o-nitro Phenol is more acidic than ortho methoxy phenol. 4. X is Cresol (o,mor p) Y is Benzyl Alcohol 5. A is Secondary alcohol wiyh molar mass 60g/mol Therefore A is CH3-CH-CH3 OH UNIT 12: ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 1. Compound A (C4H8Cl2) is hydrolysed and then dehydrated to form a compound B C4H8O which forms an oxime with NH2OH and gives negative tollens test. Write the structure of A and B. 2. Arrange the following i) in increasing order of acid strength CH2ClCOOH, CHCl2COOH, CH3COOH, CCl3COOH ii) in increasing order of reactivity towards HCN CH3CHO, CH3COCH3, HCHO, C2H5COCH3 3. Identify the compounds A B and C in the following reactions

4. Complete the following CH3COOH Cl2/P ..

NaCN .. H2O/H+ Heat ..

5. Explain Why i) Di-tert butyl ketone does not give ppt with NaHSO3 where as acetone does. ii) Benzoic acid does not give Friedel Crafts reaction

UNIT 13 (Amines) 1. Give reason a) p-methoxy aniline is a stronger base than aniline while p-nitroaniline is a weaker base than aniline. (1M) b) Aromatic primary amines cant be prepared by Gabriel Phthalamide synthesis.(1M) c) CH3CONH2 is a weaker base than CH3CH2NH2.(1M) d) Carbon-nitrogen bond length is aromatic amines is shorter than in aliphatic amines. e) Aniline does not undergo Friedal-Craft reaction.(1M) 2. . i) Arrange in decreasing order of pkb values C2H5NH2, C6H5NHCH3, (C2H5)2 NH, C6H5NH2 (1M) ii) Arrange in increasing order of basic character Aniline, p-nitro aniline, p-toulidine 3. The compound C5H13N is optically active and reacts with HNO2 to give C5H11OH and liberates N2 gas. Identify the compound and write the reactions involved. (2M) 4. Name A,B,C in the following equation a) CH3CH2COOH A + Heat B in presence of Br2/KOH C b) A Br2/KOH B HNO2 C Red P/I2 CH3I

ANSWERS 1. a) Methoxy group is electron releasing group whereas Nitro group is electron withdrawing group therefore in p-methoxy aniline the electron density on N- atom of NH2 group increases making it more basic but in p-nitro aniline the electron density on N- atom of NH2 group is decreased making it less basic. b) Aromatic primary amines can not be prepared by Gabriel Phthalimide Synthesis because aryl halides do not under go nucleophillic substitution with the anion formed by phthalimide on reaction with KOH. c) Due to resonance in CH3CONH2 , the lone pair of electrons in CH3CONH2 is delocalised .

Due to this electron density on N-atom in acetamide decreses. In CH3CH2NH2 due to +I effect of CH3CH2 group electron density on N- atom increses . As a result CH3CONH2 is a weaker base than CH3CH2NH2 d) It is because in aromatic amines C-N bond acquires some double bond character and thus becomes shorter than in aliphatic amines. e) AlCl3 used as catalyst in Friedelcrafts reaction forms a salt with aniline .Due to this nitrogen aquires positive charghe . Thus it acts as strong deactivating group for electrofilic reaction. Hence anilie does not give Foriedelcraft reaction. 2. i. C6H5NH2 > C6H5NHCH3> C2H5NH2>(C2H5)2NH ii. p-nitroamiline<amiline<p-tolidine 5) i. A=CH3CH2COONH4 B= CH3CH2CONH2 C= CH3CH2NH2 ii. A=CH3CONH2 B=CH3NH2 C=CH3OH

ORGANIC REASONING QUESTIONS ( for practice) Q.1 # Amino group is o,p-directing for aromatic electrophilic substitution . Why does aniline on nitration gives a substantial amount of meta-nitroaniline ? Q.2# Aniline does not undergo Friedel-Crafts reaction (alkylation and acetylation) (PN-395) Q.3# Diazonium salts of aromatic amines are more stable than those of aliphatic amines. Q.4# Gabriel phthalimide synthesis is preferred for synthesising primary amines. Q. 5 # Why cannot aromatic primary ammines be prepared by Gabriel phthalimide synthesis . Q.6# Why sec- & tert- alkyl halides are not used during Williamsons Synthesis . Q.7 # Although haloalkanes are usually prepared from alcohols , haloarenes cant be prepared from phenols. Q.8 # Give reason for the higher boiling point of ethanol in comparison to methoxy methane ? Q.9# Preparation of ethers by acid dehydration of secondary and tertiary alcohols is not a suitable method . Give reason .

Q.10# Why is sulphuric acid not used during the reaction of alcohols with KI?

ANSWERS ANS-1-- in the strongly acidic medium, aniline is protonated to form the anilinium ion which is meta

directing. That is why besides the ortho and para derivatives, significant amount of meta derivative is also formed. ANS-2-Aniline does not undergo Friedel-Crafts reaction (alkylation and acetylation) due to salt formation with aluminium chloride, the Lewis acid, which is used as a catalyst. Due to this, nitrogen of aniline acquires positive charge and hence acts as a strong deactivating group for further reaction. ANS-3- Primary aliphatic amines form highly unstable alkyldiazonium salts . Primary aromatic amines form arenediazonium salts which are stable for a short time in solution at low temperatures (273-278 K). The stability of arenediazonium ion is explained on the basis of resonance.

ANS-4- Because we obtain pure primary amines in Gabriel phthalimide synthesis which is not possible in
ammonolysis .

ANS-5- Aromatic primary amines cannot be prepared by this method because aryl halides do not
undergo nucleophilic substitution with the anion formed by phthalimide. Due to resonance it developes partial double bond character between aromatic carbon and nitrogen. Ans-6:- In case of secondary and tertiary alkyl halides, elimination competes over substitution. If a tertiary alkyl halide is used, an alkene is the only reaction product and no ether is formed. For example, the reaction of CH3ONa with (CH3)3CBr gives exclusively 2-methylpropene. It is because alkoxides are not only nucleophiles but strong bases as well. They react with alkyl halides leading to elimination reactions Ans-7:- Because the carbon of phenyl group is sp2 hybridised and there is a partial double bond character due to resonance

Ans-8 :- Ethanol get associated with H-bonding but methoxy methane does not .
ANS-9--The method is suitable for the preparation of ethers having primary alkyl groups only. The alkyl group should be unhindered and the temperature be kept low. Otherwise the reaction favours the formation of alkene. The reaction follows SN1 pathway when the alcohol is secondary or tertiary. However, the dehydration of secondary and tertiary alcohols to give corresponding ethers is unsuccessful as elimination competes over substitution and as a consequence, alkenes are easily formed. Answer-10-H2SO4 cannot be used along with KI in the conversion of an alcohol to an alkyl iodide as it converts KI to corresponding HI and then oxidizes it to I2.

Organic CONVERSION With Word Problems (5 Marks) FOR PRACTICE IDENTIFY THE COMPOUNDS A,B,C etc. by akp Q.1# An organic compound (A) with molecular formula C8H8O forms an orange-red precipitate(B) with 2,4-DNP reagent and gives yellow precipitate( C ) on heating with iodine in the presence of sodium hydroxide along with a colourless compound( D ) . ( A ) neither reduces Tollens or Fehlings reagent, nor does it decolourise bromine water or Baeyers reagent. On drastic oxidation of ( A ) with chromic acid, it gives a carboxylic acid (E) having molecular formula C7H6O2. Deduce the structures of organic compounds (A) to (E) and explain the reactions involved. (TBQ and Sample Paper-1) Q.2# An organic compound with the molecular formula C9H10O forms 2,4-DNP derivative, reduces Tollens reagent and undergoes Cannizzaro reaction. On vigorous oxidation, it gives 1,2-benzenedicarboxylic acid. Identify the compound. (TBQ) Q.3# An organic compound (A) (molecular formula C8H16O2) was hydrolysed with dilute sulphuric acid to give a carboxylic acid (B) and an alcohol (C). Oxidation of (C) with chromic acid produced (B). (C) on dehydration gives but-1-ene. Write equations for the reactions involved. (TBQ) Q.4# An organic compound contains 69.77% carbon, 11.63% hydrogen and rest oxygen. The molecular mass of the compound is 86. It does not reduce Tollens reagent but forms an addition compound with sodium hydrogensulphite and give positive iodoform test. On vigorous oxidation it gives ethanoic and propanoic acid. Write the possible structure of the compound. (TBQ) Q.5# Primary alkyl halide C4H9Br (a) reacted with alcoholic KOH to give compound (b). Compound (b) is reacted with HBr to give (c) which is an isomer of (a). When (a) is reacted with sodium metal it gives compound (d), C8H18 which is different from the compound formed when n-butyl bromide is reacted with sodium. Give the structural formula of (a) and write the equations for all the reactions. (TBQ) Q.6# An organic compound (A) with molecular formula C5H8O2 is reduced to n-pentane on treatment with Zn-Hg/ HCl . A forms a dioxime with hydroxylamine and gives a positive iodoform test and Tollens test.Identify the compound A and deduce its structure.( SP-2) (2 Marks)

Q.7# An organic compound (A) with molecular formula C8H8O gives a positive DNP and iodoform test . It does not reduce Tollens or Fehlings reagent and does not decolourise bromine water also. On oxidation with Chromic acid(H2CrO4) , It gives carboxylic acid (B) with a molecular formula C7H6O2 . Deduce the structures of organic compounds (A) and (B). (SP-2)(3 M) Q.8 # An unknown aldehyde A on reacting with alkali gives a -hydroxy aldehyde , which losses water to form an unsaturated aldehyde , 2-butenal . Another aldehyde B undergoes disproportionation reaction in the presencence of conc.alkali to form products C and D . C is an aryl alocohol with a formula C7H8O. (i) Identify A and B (ii) Write the sequence of reactions involved (iii) Name the product , when B reacts with Zinc amalgam and hydrochloric acid . (SP-3) ( 5 Marks) Q.9# A compound X (C2H4O ) on oxidation gives Y (C2H4O2) . X undergoes haloform reaction.On treatment with HCN X forms a product Z which on hydrolysis gives 2-hydroxy propanoic acid . (i) Write down structures of X and Y (ii) Name the product when X reacts with dil NaOH (iii) Write down the equations for the reactions involved. (SP-3) ( 5 Marks) Q.10 # An optically active compound having molecular formula C7H15Br reacts with aqueous KOH to give a racemic mixture of products .Write the structures of the compounds . Additional Questions for practice Q.11# A compound (A) with molecular formula C5H12O , on oxidation forms compound (B) with molecular formula C5H10O .The compound (B) gives iodoform test ,but does not reduce ammoniacal silver nitrate solution.(B) on reduction with amalgamated zinc and conc.HCl gives compound (C)with molecular formula C5H12. Identify (A),(B),(C), write down the chemical reaction involved . (3) Q.12# An organic compound (A) with a molecular formula C3H6O2 when treated wit h excess of NH3 and then heated formed B (C3H7ON). B on treatment with P2O5 formed C with molecular formula C3H5N. C on complete acid hydrolysis formed A . C on reduction with complex metal hydride formed a basic nitrogeneous compound D with molecular formula C3H9N . D on treatment with HNO2 formed an alcohol E (C3H8O).E on oxidation gave A . Give structures of A to E and write reactions . ( 5 Marks) Q.13# An organic compound A has a molecular formula C3H7O2N on reaction with Fe and Conc.HCl give a compound B of molecular formula C3H9N . Compound B on treatment with NaNO2 and HCl give another compound C of molecular formula C3H8O.The compound C gives effervescence with Na.On oxidation with CrO3, the compound C gives a saturated aldehyde containing three carbon atoms .Deduce the structures of A, B and C and write the chemical equations for the reactions involved. Q.14# A compound A of molecular formula C7H7NO. On treatment with Br2 and NaOH it gives B .B gives a foul smelling substance C on treatment with CHCl3 and KOH . B on treatment with NaNO2 and HCl at 00C and mixing with alkaline phenol give a red dye D.Identify A to D Q.15 # An organic compound A which has characteristic odour, on treatment with NaOH forms two compounds B and C .Compound B has a molecular formula C7H8O which on oxidation gives back compound A.Compound C is the sodium salt of an acid .C when heated with sodalime yields an aromatic hydrocarbonD.Deduce the structure A,B,C,D . Q.16# An organic compound A has a molecular formula C5H10O.It does not reduce Fehlings Solution but forms a bisulphite compound .It also positive iodoform test.What is the possible structure of A? Explain your reasoning which helped to arrive at the structure. Q.17 # A compound A has a molecular formula C5H10O gave a positive 2,4-DNP test but a negative Tollens test. It was oxidized to carboxylic acid B with molecular formula C3H6O2 when treated with alkaline KMnO4 under vigorous condition .Sodium salt of B gave a hydrocarbon C on Kolbes electrolytic reduction Identify A,B and C and write chemical equations for the reaction. Q.18 # An organic compound A having molecular formula ,C6H6O gives a characteristic colour with aqueous FeCl3 solution.Aon treatment with CO2 and NaOH at 400K under pressure gives B which on acidification gives a compound C . C reacts with acetyl chloride to give D which is a popular pain killer .Deduce the structures of A,B,C and D . .

ORGANIC DISTINGUISH BETWEEN PAIRS OF COMPOUNDS FOR CBSE (2 MARKS)

GIVE SIMPLE CHEMICAL TEST TO DISTINGUISH BETWEEN FOLLOWING PAIRS OF COMPOUNDS PRIORITY-I 1# Benzyl chloride and Chlorobenzene 2# Methanol and Ethanol 3# Phenol and Benzoic acid 4# Ethanol and Ethoxyethane 5# Propanal and Propanone 6# Ethylamine and Aniline. PRIORITY-II 1 # Vinyl Chloride and Allyl Chloride 2# Formic acid and Acetic acid . 3# Phenol and Ethanol 4# Phenol and cyclohexanol 5# Propanoyl chloride and Propanoic acid. 6# Benzamide and p-Aminobenzoic acid . 7# Propanal and Diethyl ether. 8# Acetaldehyde and Benzaldehyde. 9# Propanol-1 and Propanol-2

7# Ethylamine and Nethylaniline. 8# t-butylalcohol and Butan-2ol . 9# Ethanenitrile and

Methylcarbylamine 10# Nitromethane and Methyl nitrite 11# Benzoic acid and Ethyl benzoate . 12# Acetophenone and Benzophenone. 13# Benzalehyde and Acetophenone. 14# Pentanone -2 and Pentanone-3. 15# Ethanal and Propanal 16# Methylamine and dimethylamine 17# Aniline and benzylamine 18# Aniline and N-methylaniline 19# Methyl acetate and Ethyl acetate. 20# Formaldehyde and Acetaldehyde REAGENTS TO BE USED ***********

10# Butanol and 2-methyl propan-2-ol 11# Propanal and butanone 12# Isopropyl alcohol and propanol

1# Iodoform test [POSITIVE TEST for ethanal, ethanol, --2one , -2-ol , terminal CH3CO group, acetophenone ] ( NaOH + I2 ) OR (Na 2CO3 + I2 ) OR NaOI (Iodoform tests )--- yellow ppt. of iodoform forms. 2# Test for phenol (a)Neutral Ferric Chloride solution Phenol gives violet colour complex with neutral FeCl3. (b) Bromine water test:Phenol and Aniline readily decolourises bromine water giving a white ppt. of 2,4,6-tribromophenol /2,4,6tribromoaniline 3# Test for Aldehydes and Formic acid (a)Tollens Reagent (ammoniacal AgNO 3 solution)--- silver mirror appears. (b) Fehlings solution(alkaline sol. Of CuSO4 + sod.pot.tartarate)---- redish brown ppt. of cuprous oxide forms. 4# TEST FOR ALCOHOLS[ Na metal test] -- hydrogen gas evolved (effervescence) [ether does not responds this test] 5# TEST FOR CARBOXYLIC ACIDS [NaHCO3 solution ]----carbon dioxide evolves with acids. (effervescence) 6# ISOCYANIDE TEST OR CARBYLAMINE TEST ( test for primary amine) CHCl3 + alcoholic KOH solution----an offensive smell of isocyanide results when treated with primary amine . 7# AZODYE TEST [Test for primary aromatic amines] ( NaNO2 +HCl) and beta-napthol (diazo test)----an orange or red dye will appear with primary aromatic amine 8# Hinsbergs reagent ( benzene sulphonyl chloride and KOH ) ----To distinguish p-,s-,t- amines Both 10 and 20 Amine reacts with benzene sulphonyl chloride ,the reaction product of 10 amine soluble in KOH due to presence of acidic hydrogen but 20 Amine does not. 30 Amine does not react at all with benzene sulphonyl chloride 09# TEST FOR CHLORIDE ION [aq.NaOH and AgNO3 test ] -- white ppt. of AgCl forms due to free chloride ion [ In a compound when Cl attached with SP3 carbon responds this testeasy for SN reaction] 10# Lucas Test ( anh. ZnCl2 + conc.HCl )---( turbidity appears immediately for tert-alcohol, after 5 minutes for sec alcohol , after heating with primary alcohol ) 11# Acidic hydrolysis of ester + Iodoform test. ( to distinguish methyl acetate and ethyl acetate ) 12 # Reduction ( LiAlH4 ) and carbylamine test . (for nitrile and isonitrile)

JUST FOR PRACTICE ---- ORGNIC CHEMISTRY ( EXAM SPECIAL) 1# Explain why ? Give reason

by A.K.Panda

(i) Treatment of C6H5CHO and HCN gives a mixture of two isomers which cannot be separated even by very careful fractional distillation .Why ? (1) (ii) Why is vinyl chloride less reactive than ethyl chloride towards nucleophile ? (1) (iii)Why formaldehyde does not respond Aldol condensation reaction ? (1) (iv) Why CF3C+HCH3 is much less stable than isopropyl cation? (1) (v) Explain why this takes place with anti-Markownikoffs regiochemistry (1) CF3CH=CH2 + HCl CF3CH2CH2Cl (vi) Why does the reactivity of NH2 get reduced in acetanilide ? (1) (vii) Amino group is o,p-directing for aromatic electrophilic substitution . Why does aniline on nitration gives a substantial amount of meta-nitroaniline ? (1) (viii) There are two NH2 groups in semicarbazide. However, only one is involved in the formation of semicarbazones. (1) (ix) Haloalkanes react with KCN to form alkyl cyanides as main product while AgCN forms isocyanides as the chief product. Explain. (1) (x) Why sec- & tert- alkyl halides are not used during Williamsons Synthesis . (1) (xi) Why N,N-Diethylbenzenesulphonamide is not soluble in alkali . (1) (xii) Which compound will react faster in SN2 reaction with OH and why ? (CH2=CHBr and CH2=CHCH2Br ) (1)

(xiii) Although phenoxide ion has more number of resonating structures than carboxylate ion , carboxylic acid is a
stronger acid than phenol . Why? (1)

2#(A) Give the structures of the major product(s) which are obtained when

(i) 2-methyl-2-methoxypropane is treated with hydroiodic acid . (ii) Methyl magnesium bromide is treated with CO2 and subsequently hydrolysed . (iii) Salicylic acid is acetylated (iv) butan-1-ol is treated with Jones reagent (v) Hex-4-ene-nitrile is treated with DIBAL-H (vi) ethanoyl chloride is treated with diethyl cadmium . (vii) benzene diazonium chloride treated with DMA in presence of a base . (viii) Methanamine treated with benzoyl chloride . (ix) Propanoic acid is treated with NABH4 . (x) 1-bromo-1-methylcyclohexane is treated with alcoholic KOH (xi) Cyclohexene is treated with hot acidified KMnO4 . (xii) Cyclohehanone is treated with semicarbazide . (xiii) Benzaldehyde is treated with Acetophenone in presence of dilute NaOH . (B) How do products differ when ethyl bromide reacts separately with (i) aq . KOH and alc. KOH (ii) KNO2 and AgNO2 (iii) KCN and AgCN 3# Write chemical test to distinguish between (i) Formic acid and acetic acid (ii) C6H5CH2NH2 and C6H5NH2 ( iii) Propanoyl chloride and Propanoic acid. (iv) Vinyl Chloride and Allyl Chloride 4# Write the mechanism of (i) Hydration of propene to yield propanol . (ii) Ethanamine is converted into N-Ethylethanamide . (iii) 1-propoxypropane from propan-1-ol (iv) Reaction of HI with methoxy ethane 5 # Give the IUPAC Name of (i) Methyl vinyl ketone . (ii) Benzophenone (iii) Sulphanilic caid (iv) Aspirin (v) Terepthalic acid (vi) Adipic acid (vii) Phenetole (viii) Propiophenone (ix) DDT (x) Freon

UNIT-14# BIOMOLECULES
PART-I : Answer the following : 1# An optically active compound having molecular formula C6H12O6 is found in two isomeric forms(A) and (B) .When (A) and (B) are dissolved in water they show the following equilibrium: (A)-------------- equilibrium mixture --------------(B) [] = 1110 52.20 19.20 (i) What are such isomers called ? (ii) Can they be called enantiomers ? Justify your answer . (iii) Draw the cyclic structure of isomer (A) . 2# An optically active amino acid (A) can exist in three forms depending on the PH of the medium.If the molecular formula of (A) is C3H7NO2 then write (i) Structure of compound (A) in aqueous medium. What are such ions called ? (ii) In which medium will the cationic form of compound (A) exist ? (iii) In alkaline medium, towards which electrode will the compound (A) migrate in electric field ? 3 # When RNA is hydrolysed, there is no relationship among the quantities of different bases obtained unlike DNA ? What does this fact suggest about the structure of RNA? 4# What are reducing and non-reducing sugars ? Give two examples. .What is the structural feature characterizing reducing sugars ? 5# Write down the structures and names of the products obtained when D-Glucose is treated with (a) HI (b) Br2 Water (c) HNO3 (d) NH2OH (e) Acetic Anhydride (f) HCN (g) ammoniacal AgNO3 6# What is the significance of D and (+) in -D(+)-glucopyranose 7 # What are the expected products hydrolysis of (i) Lactose (ii) sucrose (iii) Maltose 8# What type of bonding helps in stabilising the -helix structure of proteins?

9#What is the effect of denaturation on the structure of proteins? 10# The two strands in DNA are not identical but are complementary . 11# Enumerate the reactions of D-glucose which cannot be explained by its open chain structure. 12# How do you explain the absence of aldehyde group in the pentaacetate of D-glucose?
Ans-1-(i) Anomers (ii) No, they are not enantiomers . - and -anomers are not mirror images of each other . They are not having nonsuper imposable mirror images ( which is the conditions of showing enantiomerism)

ANSWERS TO (I)

(iii) ANS-2-(i) they are called Zwitter ions (ii) In acidic medium ,the cationic form of compound will exist (iii) In alkaline medium , it will behave as anion and migrates towards anode in electric field ANS-3- This indicates that RNA does not exist as double strand but exist as single strand. DNA exist as double strand . The sequence of bases on one strand of DNA is complimentary to the sequence of bases on the other strand . Therefore , the quantities of four bases obtained on hydrolysis of DNA have relationships . Since in case of RNA there is no relationship among the quantities of bases it indicates that RNA exists in the form of single strand and not double strand ANS-4- Reducing Sugars:- All those carbohydrates which contain free aldehydic or ketonic groups

which reduce Fehlings solution and Tollens reagent are referred to as reducing sugars. Eg. Glucose, fructose, maltose, lactose. Non- Reducing Sugars :- All those carbohydrates which do not contain free aldehydic or ketonic groups cannot reduce Fehlings solution and Tollens reagent are referred to as reducing sugars .e.g sucrose . These two monosaccharides are held together by a glycosidic linkage between C1 of -glucose and C2 of -fructose. Since the reducing groups of glucose and fructose are involved in glycosidic bond formation, sucrose is a non reducing sugar. ANS-5- (a) n-hexane (b) Gluconic acid (c) Saccharic acid or glucaric acid (d) Glucose monooxime (e) Glucose Pentaacetate (f) Glucose cyanohydrin (g) Gluconic acid ANS-6- D before the name of glucose represents the configuration whereas (+) represents dextrorotatory nature of the molecule. [*** It may be remembered that D and L have no relation with the optical activity of the compound.] ANS-7 : (i) -D-Galactose and -D-Glucose (C-1 and C-4 glycosidic linkage) (ii) - D(+)-Glucose and -fructose (C1C2 glycosidic linkage) (iii) -D Glucose and -D- Glucose (C-1 and C-4 glycosidic linkage) Ans-8:-Due all possible hydrogen bonds, by twisting into a right handed screw (helix) with the NH group of each amino acid residue hydrogen bonded to the >C= O of an adjacent turn of the helix . Ans-9:- During denaturation 2 and 3 structures are destroyed but 1 structure remains intact . Due to this, globules unfold and helix get uncoiled and protein loses its biological activity Ans-10: Two nucleic acid chains are wound about each other and held together by hydrogen bonds between pairs of bases. The two strands are complementary to each other because the hydrogen bonds are formed between specific pairs of bases. Adenine forms hydrogen bonds with thymine whereas cytosine forms hydrogen bonds with guanine. Ans-11# The following experimental facts could not be explained by its open chain structure (i) Despite having the aldehyde group, glucose does not give 2,4-DNP test, Schiffs test and it does not form the hydrogensulphite addition product with NaHSO3. (ii). The pentaacetate of glucose does not react with hydroxylamine indicating the absence of free CHO group. (iii) Glucose is found to exist in two different crystalline forms which are named as and -form. Ans-12# Pentaacetate of D-glucose does not react with hydroxylamine indicating the absence of free CHO group .

1. 2. 3. 4. 5. 6. 7.

PART-II Cellulose in the form of plants is a food for cattles but not for human beings.Explain. Upon heating glucose with tollens reagent, a shining mirror is obtained.Explain why? Name a water soluble vitamin which is a powerful antioxidant. Except for B12, all other vitamins of this group B should be supplied regularily in diet, why? Name the protein responsible for blood clotting . Glucose form an oxime but glucose pentaacetate does not why? Name the following a) A water soluble vitamin b) A vitamin which is neither water soluble nor fat soluble c) What is meant by avitaminosis? d) Vitamin which prevent loss of hairs e) The disease caused by deficiency of B12

ANSWER KEY PART-II: UNIT 14 1. Due to absence of enzymes needed for breakdown of glucose in human beings. 2. CHO COOH (CHOH) 4 + 2[Ag(NH3) 2]OH (CHOH) 4 + 2Ag +4NH3 + 2H2O CH2OH CH4OH 3. Vitamin C 4. Because it can be stored in liver while others could not. 5. Fibrinogen 6. Due to absence of free aldehyde group on glucose pentaacetate. 7. a) Vitamin B or C b) Vitamin H c) Deficiency of more than one vitamin in human body d) Vitamin H (Biotin) e) Anaemia

Q.I# Answer the following: (1) How double bonds in rubber molecules influence their structure and reactivity ? (2) Write the free radical mechanism for the polymerization of ethene (3) Write the name and structure of one of the common initiators used in free radical addition polymerisation. (4) Is ( NH-CHR-CO )n, a homopolymer or copolymer? (5) Explain the term copolymerisation and give two examples. (6) Discuss the main purpose of vulcanisation of rubber. Or Mention advantages of Vulcanised rubber over natural rubber . OR , How does vulcanization change the character of natural rubber ? (7) Can a copolymer be formed in both addition and condensation polymerization ? Explain with examples. (8) What are biodegradable polymers?Give two examples. (9)(a) What is the role of Benzoyl peroxide in polymerization of ethane .(b)How do you explain the functionality of a monomer (10) What are LDPE and HDPE ? How are they prepared

UNIT-15: POLYMERS

11). Give two examples of biodegradable polymers. 12). What is plastisizer? 13).. What is the commercial name of PMMA? What is its use?

14).the monomers for the following a) Teflon b) Cellulose c) Neoprene 16)What is the main constituent of bubble gum? 17) Why are the numbers 66 and 6 put in the names of nylon66 and nylon 6?

d) Polythene

Q.II # Arrange the following polymers in increasing order of Intermolecular Forces ? (a) Nylon-66 , Buna-S , Polythene (b) Polyisoprene , PTFE , Decron (c) Nylon-6 , PVC , Neoprene

UNIT 15:

1# How double bonds in rubber molecules influence their structure and reactivity ? Ans-From the structural point of view, the natural rubber is a linear cis-1,4- polyisoprene(2-methyl-1, 3-butadiene). In this polymer the double bonds are located between C2 and C3 of isoprene units. This cis-configuration about double bonds do not allow the chains to come closer for effective attraction due to weak intermolecular attractions. Hence, the natural rubber has a coiled structure and it can be stretched like a spring and exhibits elastic properties. The double bonds in the rubber molecules, in additions to determining their configurations act as reactive sites. The allylic --CH2- - .On vulcanization, sulphur establishes cross links at these reactive sites .Thus ,the rubber gets stiffened and intermolecular movement of rubber springs is prevented resulting in change of physical character of rubber

ANSWER KEY Answers

2# FREE RADICAL MECHANISM-(P.N-329) 3# Free radical generating initiator (catalyst) like benzoyl peroxide, acetyl peroxide, tert-butyl peroxide

4# Homopolymer because of similar type of monomer 5# Copolymerisation is a polymerisation reaction in which a mixture of more than one monomeric species is allowed to polymerise and form a copolymer. For example, (1) Buna-S, a mixture of 1, 3 butadiene and styrene can form a copolymer.(chain growth) (2) Nylon-66 , a mixture of Adipic acid and hexamethylene diammine (step growth) 6# Vulcanised rubber Raw rubber + Sulphur + additive(ZnO) at 373K to 415 K Vulcanised rubber On vulcanization sulphur forms cross links at the reactive sites of double bonds and thus the rubber gets stiffened .Excellent elasticity, Low water absorption tendency, resistance to oxidation and organic solvents , Hard ,non-sticky ,high tensile strength ,insoluble in all common solvents , works at higher temperature range from -400C to 1000 C . High abrasion resistance 7# Yes. addition polymerization--- Buna-S, a mixture of 1, 3 butadiene and styrene can form a copolymer.(chain growth) and condensation polymerization--- Nylon-66 , a mixture of Adipic acid and hexamethylene diammine (step growth) 8# Synthetic biodegradable polymers contain functional groups similar to the functional groups present in biopolymers which can be easily degraded through environmental process by microorganisms. Aliphatic polyesters are one of the important classes of biodegradable polymers e.g. PHBV 1. Poly- -hydroxybutyrate co--hydroxy valerate (PHB ) [ 3-hydroxybutanoic acid and 3-hydroxypentanoic acid] and PHBV undergoes bacterial degradation in the environment. 2. Nylon 2nylon 6 . It is an alternating polyamide copolymer of glycine (H2NCH2COOH) and amino caproic acid [H2N (CH2)5 COOH] 9# (a)Benzoyl peroxide acts as a free radical generating initiator (catalyst) in free radical polymerization reaction (b) Functionality is the number of bonding sites in a monomer . 10# Low Density PolyeheneIt is obtained by the polymerization of ethene under high pressure of 1000 to 2000 atmospheres at a temperature of 350 K to 570 K in the presence of traces of dioxygen or a peroxide initiator (catalyst). The low density polythene (LDP) obtained through the free radical addition and H-atom abstraction has highly branched structure. High Density PolyeheneIt is formed when addition polymerisation of ethene takes place in a hydrocarbon solvent in the presence of a catalyst such as triethylaluminium and titanium tetrachloride (Ziegler-Natta catalyst) at a temperature of 333 K to 343 K and under a pressure of 6-7 atm 11# PHBV Poly- beta- hydroxybutyrate- Co beta hydroxyl valerate and Polyglycolic acid and Polylactic acid 12# Those plastics which do not soften on heating can be made sof by addition of certain organic compounds called plasticizers. 13# Polymethyl methacrylate 14# a) Tetrafluoro ethane (b) Beta D-Glucose (c) 2 chloro 1,3 butadiene (d) Ethene 15# Styrene- Butadiene 16# In nylon 66 both monomers have 6 numbered carbon chain and in nylon 6 only one monomer is present which has six membered carbon chain. ANSWER-II:- (a) Buna-S < Polythene < Nylon-66 (c) Neoprene < PVC < Nylon-6 (b) Polyisoprene < PTFE < Decron (d) SBR < Polystryne < Terylene

UNIT-16 : Chem in everyday life

1# Why are cimetidine and ranitidine better antacids than sodium hydrogencarbonate or magnesium or aluminium hydroxide ? (TBQ)

2#(a)

While antacids and antiallergic drugs interfere with the function of histamines, why do these not interfere with the function of each other ?
(b) Metal hydroxides are better alternatives than Sodium bicarbonates for treating acidity. 3# Sleeping pills are recommended by doctors to the patients suffering from sleeplessness but it is not advisable to take its doses without consultation with the doctor. Why ? (TBQ) 4# Explain the term, target molecules or drug targets as used in medicinal chemistry. 5 # Account for the following:(i) aspirin drug helps in the prevention of heart attack (ii) Detergents are non-biodegradable while soaps are biodegradable (iii) Diabetic patients are advised to take artificial sweeteners instead of natural sweeteners 6# Low level of noradrenaline is the cause of depression. What type of drugs are needed to cure this problem ? Name two drugs. 7# Define the term chemotherapy. What are the criteria of classification of drugs. 8# With reference to which classification has the statement, ranitidine is an antacid been given? (TBQ) 9# Differentiate between (i)Antiseptic and disinfectant (ii)Soaps and Detergents (iii)Antagonist and agonists (iv) Enzymes and Receptors

10#Name a drug used for treatment of tuberculosis. What type of drug it is? 11# What are sulpha drugs? Give two examples. 12# Which of the following is hypnotic? Whats its function? a) Luminal b) Catechol c) salol d) Paracetamol 13# What is the use of a) Benadryl b) BHA c) Sodium Benzoate d) Progesetrone 14# Name the drugs which are used to control allergy. 15# Classify synthetic detergents giving an example in each case.

UNIT 16 : ANSWER KEY 1# Sodium hydrogencarbonate or magnesium or aluminium hydroxide used as antacids These treatments control only symptoms, and not the cause. Therefore, with these metal salts, the patients cannot be treated easily. Histamine, stimulates the secretion of pepsin and hydrochloric acid in the stomach. cimetidine (Tegamet) prevent the interaction of histamine with the receptors present in the stomach wall. This resulted in release of lesser amount of acid. 2# (a) Antiallergic and antacid drugs work on different receptors. Antihistamines (antiallergic drugs) do not affect the secretion of acid in stomach because they do not interact with receptors present in the stomach wall. (b) Excessive hydrogencarbonate can make the stomach alkaline and trigger the production of even
more acid. Metal hydroxides are better alternatives because of being insoluble, these do not increase the pH above neutrality.

3 # Most of the drugs taken in doses higher than recommended may cause harmful effect and act as poison. Therefore, a doctor should always be consulted before taking medicine. 4# Target molecules or drug targets are the macromolecules such as carbohydrates , proteins,lipids,nucleic acids with which the drug interacts in our body to produce therapeutic
effect

5 #(a)Aspirin prevents platelet coagulation. Because of its anti blood clotting action, aspirin finds use
in prevention of heart attacks. (b) Main problem that appears in the use of detergents is that if their hydrocarbon chain is highly branched, then bacteria cannot degradethis easily. Slow degradation of detergents leads to their accumulation. Effluents containing such detergents reach the rivers, ponds, etc. These persist in water even after sewage treatment and cause foaming in rivers, ponds and streams and their water gets polluted. (c) natural sweeteners contains calorie i.e sugars which cannot be metabolized by diabetic patients as they do not have the insulin to metabolise them

6# Antidepressant drugs. E.g.- Iproniazid and Phenelzine. 7# Use of chemicals for therapeutic effect is called chemotherapy. Drugs can be classified mainly on
criteria outlined as follows: (a) On the basis of pharmacological effect (d) On the basis of molecular targets (b) On the basis of drug action (c) On the basis of chemical structure

8# This statement refers to the classification according to pharmacological effect of the drug because any drug which will be used to counteract the effect of excess acid in the Antiseptics
*Antiseptics are chemical substances which prevent the growth or kill the microorganisms and not harmful to the living human tissues *Antiseptics are applied to the living tissues such as wounds, cuts,ulcers and diseased skin surfaces. *Examples are furacine,soframicine, etc. These are not ingested like antibiotics.

Disinfectants
*Disinfectants are chemical substances which kill the microorganismsor stop their growthbut are harmful to human tissues *Disinfectants are applied to inanimate objects such as floors, drainage system, instruments, etc. * 1% Phenol , 0.2 0.4 ppm Chlorine in aqeous solution etc

stomach will be called antacid.

9# (i)

(ii) Soaps 1.Soaps are sodium salts of higher fatty acids 2.Soaps are prepared from natural oils and fats 3 .Soaps forms insoluble salts(curdy white ppt) with calcium and magnesium which are presenting hard water and hence cannot be used in hard water 4.Soaps cannot be used in acidic medium as they are decomposed into carboxylic acids in acidic medium 5.Soaps are biodegradable

Detergents 1.Synthetic detergents are sodium alkyl sulphates or sodium alkyl benzene sulphonates with alkyl groups having more than 10 carbon atoms 2.Synthetic detergents are prepared from the hydrocarbon of petroleum 3.Calsium and magnesium salts of detergents are soluble in water and, therefore ,no curdy white ppt. are obtained in hard water and hence ,can be used even in hard water 4.They can be used in acidic medium as they are the salts of strong acids and are not decomposed in acidic medium 5.Some of the synthetic detergents are not biodegradable
Agonists. There are other types of drugs that mimic the natural messenger by switching on the receptor, these are called agonists

(iii) Antagonists. Drugs that bind to the receptor site and inhibit its natural function are called antagonists. These are useful when blocking of message is required.

(iv) Enzymes proteins which perform the role of biological catalysts in the body are called enzymes

Receptors Proteins which are crucial to communication system in the body are called receptors

10# Streptomycin and it is narrow spectrum antibiotic 11# A group of drugs which are derivatives of sulphanilamide and are used in place of antibiotics. Examples Sulphadiazine and Sulphanilamide 12# Luminal is sleep inducing drug 13# a) Antihistamine b) Antioxidant c) Preservative d) Antifertility drug 14# Antihistamines 15# These are cleansing agents which have all the properties of soap but actually contain no soap. They are a) Anionic Detergents e.g. sodium lauryl sulphonate b) Cationic detergent e.g. Cetyltrimethylammonium Bromide c) Non Ionic detergents e.g. Detergent formed when stearic acid reacts with polyethylene glycol

By A.k.panda,P.C.Panda,Rishi Verma,Umesh kumar, ,Satish Rajput

UNIT-5:-SURFACE CHEMISTRY
ANSWER THE FOLLOWING : 1# colloid is not a substance but a state of substance. OR Same substance can act both as colloids and crystalloids

2# A sol is prepared by the addition of excess of KI to AgNO3 solution. Which one of the following will be most effective for its coagulation? [ Fe(CN)6]-4 , Al +3, PO4-3 , Mg +2 (2M) 3# Three gases A, B and C have critical temperatures 630 K, 33 K and 190 K respectively. Arrange them in increasing order of adsorption on activated charcoal. 4# What are the conditions when Tyndall effect can be observed? ( 2 M) 5# Why artificial rain can be cause by throwing common salt on the clouds?(1M) 6# What is CMC? What is its value for soap?(1M) 7 What is ZSM-5? Where it is used?(2 M) 8#100 mL of a colloidal solution is completely precipitated by the addition of 5 mL of 1 M NaCl solution. Calculate its coagulation value.( 2M ) 9# Action of soap is due to emulsification and micelle formation. Comment.(2M) 10# Why is it necessary to remove CO when ammonia is obtained by Habbers Process
11 # Why is the ester hydrolysis slow in the beginning and becomes faster after some time? 12# Why is it essential to wash the precipitate with water before estimating it quantitatively 13# What charge is likely to develop on the colloidal particles in the following cases ? (a) A sol is prepared by addition of excess of AgNO3 solution in KI solution (b) Ferric chloride is added to NaOH (c) If FeCl3 is added to excess of hot water (d) when KI solution is added to AgNO3 solution (e) when AgNO3 solution is added to KI solution 14 # In which of the following does adsorption occurs and why ? (a) silica gel placed in atmosphere get saturated with water (b) Anhydrous CaCl2 placed in the atmosphere gets saturated with water

1# The given statement is true . This is because the same substance may exist as colloid under certain conditions and as crystalloid under certain other conditions . For example , NaCl in water behaves as a crystalloid while in benzene , it behaves as a colloid . Similarly , dilute soap solution behaves like a crystalloid while concentrated soap solution behaves as a colloid ( associated colloid) . It is size of the particle which matters , i.e. , the state in which the substance exists . If the size of the particle lies in the range of 1nm to 1000 nm , it is in the colloidal state

ANSWER-

2# the addition of excess of KI to AgNO3 solution will result into negative sol AgI/I , so Al +3 will be effective for coagulation 3# B < C < A . higher the critical temperature ,higher will be the Adsorption as van der waals forces are stronger near the critical temperature . 4# Tyndall effect is observed only when the following two conditions are satisfied. (i) The diameter of the dispersed particles is not much smaller than the wavelength of the light used; and (ii) The refractive indices of the dispersed phase and the dispersion medium differ greatly in magnitude.
5# Clouds are aerosols having small droplets of water suspended in air. Sometimes, the rainfall occurs

when two oppositely charged clouds meet. It is possible to cause artificial rain by throwing electrified sand or spraying a sol carrying charge opposite to the one on clouds from an aeroplane. 6#The formation of micelles takes place only above a particular concentration called critical micelle concentration (CMC).

For soaps, the CMC is 104 to 103 mol L1. These colloids have both lyophobic and lyophilic parts. Micelles may contain as many as 100 molecules or more. 7# Zeolite sieve of microporosity-5 . It converts alcohols directly into gasoline(petrol) by dehydrating them to give a mixture of hydrocarbons. Molecular formula Hx[(AlO2)x(SiO2)96-x].16H2O 8# 50 .
9# A micelle consists of a hydrophobic hydrocarbon like central core. The cleansing action of soap is due to the fact that soap molecules form micelle around the oil droplet in such a way that hydrophobic part of the stearate ions is in the oil droplet and hydrophilic part projects out of the grease droplet like the bristles. Since the polar groups can interact with water, the oil droplet surrounded by stearate ions is now pulled in water and removed from the dirty surface. Thus soap helps in emulsification and washing away of oils and fats. The negatively charged sheath around the globules prevents them from coming together and forming aggregates. Figure:(a) Grease on cloth (b) Stearate ions arranging around the grease droplet and (c) Grease droplet surrounded by stearate ions (micelle formed)

10# CO acts as a poison for the catalyst ( finely divided Fe) in Habers Process . Acitivity increases if it is used in finely divided state . 11# H+ which is generated from one of the product ( from acetic acid ) acts as a catalyst for the reaction [ a case of autocatalysis] . Hence the reaction becomes faster after sometime as production of H+ increases as time passes . 12# Some amount of the electrolyte mixed to form precipitate remains adsorbed on the surface of the particles of the precipitate . Hence , it is essential to wash the precipitate with water to remove the sticking electrolytes( or any other impurities) before estimating it quantitatively . 13# (a) positive sol i.e. , [AgI] Ag+ (b) Negative sol i.e. , [Fe(OH)3] OH (c) positive sol (d) positive sol AgI/Ag+

(e) negative sol AgI/I 14#(a) adsorption (b) Absorption

Unit-6: GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS ANSWER THE FOLLOWING : Q.1# (a) Metal A is extracted by pyrometallurgy process, metal B by electrolytic refining and metal C by simply heating the ore. Arrange these metals in the increasing order of reactivity.(1M) (b) What does a steep increase in the slope of a line on Ellingham diagram indicate?(1M) ( c) Why is Chalcopyrite roasted and not calcined during recovery of copper? ( 1M) (d) Why copper matte is put in silica lined converter? (e) Why is the extraction of copper from pyrites more difficult than that from its oxide ore through reduction? (f) Out of C and CO, which is a better reducing agent at 673 K ? (g) Copper can be extracted by hydrometallurgy but not zinc. Explain. (h) Out of C and CO, which is a better reducing agent for ZnO ? (i) The value of fG0 for formation of Cr2 O3 is 540 kJmol1and that of Al2 O3 is 827 kJmol 1Is the reduction of Cr2O3 possible with Al ? (j) Why is the reduction of a metal oxide easier if the metal formed is in liquid state at the temperature of reduction? (k) Although thermodynamically feasible, in practice, magnesium metal is not used for the reduction of alumina in the metallurgy of aluminium. Why ? (l) At a site, low grade copper ores are available and zinc and iron scraps are also available. Which of the two scraps would be more suitable for reducing the leached copper ore and why? (m) The reaction, Cr2 O3 + 2 Al Al2 O3 + 2 Cr (G0 = 421 kJ) is thermodynamically feasible as is apparent from the Gibbs energy value. Why does it not take place at room temperature? (n) Copper and silver lie below in the electrochemical series, yet they are found in combined state in the form of sulphide ores. Why? (2M) 2# Free energy of formation (fG) of MgO(s) and CO(g) at 1273K and 2273K are given below (Sample paper-2) fG (MgO(s)) = -941 kJ/mol at 1273K fG (MgO(s)) = -341 kJ/mol at 2273K fG (CO(g)) = - 439 kJ/mol at 1273K fG (CO(g)) = - 628 kJ/mol at 2273K On the basis of above data ,predict the temperature at which carbon can be used as a reducing agent for MgO(s) . Q.3 # The choice of reducing agent in a particular case depends on thermodynamic factor . How far do you agree with this statement ? Support your opinion with two examples

Q.4# What chemical principle is involved in choosing a reducing agent for getting the metal from its oxide ore ? Consider the metal oxides , Al2O3 and Fe2O3 and justify the choice of reducing agent in each case . (3M) (AI-2008) Q.5 # The standard Gibbs energy of reactions at 1773K are given below: ( 3M) (AI-2005) C + O2 CO2 : rG0 = -380 kJ/mol ; 2C +O2 2CO : rG0 = -500 kJ/mol Discuss the possibility of reducing Al2O3 and PbO with carbon at this temperature. 4Al + 3O2 2Al2O3 : rG0 = -22500 kJ/mol ; 2Pb + O2 2PbO : rG0 = -120 kJ/mol 6# How is the concept of coupling reactions useful in explaining the occurrence of a non-spontaneous reaction ? (2M)(AI-2005&06) ANSWER-UNIT-6 Answer--1:-- (a) C< A < B (b) The steep increase in thje slope of a line due to change in phase, i.e. solid to liquid . The temperature at which such change occurs is indicated by increase in slope on positive side .For example, the abrupt increase in Zn to ZnO plot shows the melting of Zn metal . (c) chalcopyrite is a sulphide ore , so it is roasted in presence of oxygen so as to convert into oxide ore for easy reduction . Carbonate ores are calcined . (d) Copper matte contains Cu2S and FeS .In the converter FeS gets converted into FeO when hot air blast is blown into the converter.Silica helps in removal of FeO impurity as slag. 2FeS + 3 O2 2FeO + 2 SO2 FeO (impurity) + SiO2 (silica) FeSiO3 (slag) (e) The reducing agent forms its oxide when the metal oxide is reduced. The role of reducing agent is to provide G0 negative and large enough to make the sum of G0 of the two reactions (oxidation of the reducing agent and reduction of the metal oxide) negative. Carbon is the poor reducing agent for sulphide ores wheras it is good reducing agent for oxide ores . ( f) At 673K , the G0 vs T line for CO,CO2 is lower than that of C, CO line . Carbon monoxide is the better reducing agent at 673 K (g) Metals (such as Cu) occupying lower positions in the electrochemical series can be extracted by hydrometallurgy because the metal ions(Mn+) of such metals can be easily reduced by treatment with some more electropositive metal. Metals occupying higher positions in the electrochemical series cannot be extracted by hydrometallurgy because the metal ions(Mn+) of such metals are difficult to reduce. Zn has large negative reduction potential. (h) The line for G0 ( CO ,CO2) lies above the line for G0 ( Zn ,ZnO) at the temperature employed for reduction of Zinc oxide.Hence reduction of ZnO with CO is not possible as the rG0 for this reaction would be positive ZnO + CO +1673K Zn + CO2 rG0 = + Ve ( not feasible) On the other hand , the line for G0 ( C ,CO) Vs T lies below the line for G0 ( Zn ,ZnO) .Hence ,coke can reduce Zinc oxide to zinc as the rG0 for this reaction would be negative and hence the reaction is feasible . ZnO + C +1673K Zn + CO rG0 = - Ve (feasible) Answer (i) # (i) 2 Cr + 3/2 O2 Cr2 O3 fG0 = -540 kj/mol 0 (ii) 2 Al + O2 Al2O3 fG = -827 kj/mol Equation (ii) (i) , we get 2Al + Cr2O3 Al2O3 + 2Cr rG0 =[ -827 (-540)] kJ = - 287 kJ Since the rG0 for the reduction of Cr2 O3 with Al is negative therefore, the reaction is possible (j) The entropy is higher if the metal is in liquid state than when it is in solid state. The value of entropy change (S) of the reduction process is more on +ve side when the metal formed is in liquid state and the metal oxide being reduced is in solid state. Thus the value of G0 becomes more on negative side and the reduction becomes easier. (k) Temperatures above the point of intersection of Al2O3 and MgO curves, magnesium can reduce alumina. But the temperature required would be so high that the process will be uneconomic and technologically difficult. (l) Zinc being above iron in the electrochemical series (more reactive metal is zinc), the reduction will be faster in case zinc scraps are used. But zinc is costlier metal than iron so using iron scraps will be advisable and advantageous (m) Certain amount of activation energy is essential even for such reactions which are thermodynamically feasible, therefore heating is required. Answer-2:-- The desired equation is MgO(s) + C(s) Mg (s) + CO(g) ,. rG = ? At 1273 K :Mg(s) + O2(g) MgO(s) ; fG (MgO(s)) = -941 kJ/mol at 1273K -----(1) C(s) + O2 (g) CO(g) ; fG (CO(g)) = - 439 kJ/mol at 1273K ------(2)

Equation (2) (1) rG = fG (CO(g)) - fG (MgO(s)) = - 439 kJ/mol -(-941 kJ/mol) = + 502 kJ/mol Since rG is +ve this reduction is NOT FEASIBLE at this tempetrature . At 2273 K:Mg(s) + O2(g) MgO(s) ; fG (MgO(s)) = -341 kJ/mol at 2273K -----(3) C(s) + O2 (g) CO(g) ; fG (CO(g)) = - 628 kJ/mol at 2273K ------(4) Equation (4) (3) rG = fG (CO(g)) - fG (MgO(s)) = - 628 kJ/mol -(-341 kJ/mol) = - 287 kJ/mol Since rG is -ve (NEGATIVE) this reduction is FEASIBLE at this tempetrature . So Carbon can acts as reducing agent at this temperature i.e at 2273K Answer-3The thermodynamic factor helps us in choosing a suitable reducing agent for the reduction of particular metal oxide to metal . The feasibility of thermal reduction can be predicted on the basis of G0 Vs T plots for the formation of oxides, known as Ellingham diagram . from the diagram it can be predicted that metals for which the fG0 ( of their oxides) is more negative can reduce those metal oxides for which standard free energy of formation of their respective oxides is less negative . In other words , a metal will reduce the oxides of the other metals which lie above it in the Ellingham Diagram because the fG0 of the combined redox reaction will be negative by an amount equal to the difference in fG0 of the two metal oxides . For example, both Al and Zn can reduce FeO to Fe but Fe cannot reduce ZnO to Zn and Al2O3 to Al . Similarly , Carbon can reduce ZnO to Zn but not CO . thus the choice of reducing agent in a depends on thermodynamic factor .

UNIT-7: p-Block Elements

I# IDENTIFY THE FOLLOWING:
1 # An element A exists as a yellow solid in standard state. It forms a volatile hydride B which is a foul smelling gas and is extensively used in qualitative analysis of salts. When treated with oxygen, B forms an oxide C which is colourless, pungent smelling gas. This gas when passed through acidified KMnO4 solution, decolourizes it. C gets oxidized to another oxide D in the presence of a Heterogeneous catalyst. Identify A, B, C, D and also give the chemical equation of reaction of C with acidified KMnO4 solution and for conversion of C to D. 2# When conc. sulphuric acid was added to an unknown salt present in a test tube, a brown gas (A) was evolved. This gas intensified when copper turnings were also added into this tube. On cooling, the gas A changed into a colourless gas B. (a) Identify the gases A and B. (b) Write the equations for the reactions involved. 3# A translucent white waxy solid A on heating in an inert atmosphere is converted in to its allotropic form (B). Allotrope A on reaction with very dilute aqueous KOH librates a highly poisonous gas C having rotten fish smell. With excess of chlorine A forms D which hydrolysis to compound E. Identify compounds A to E . 4# Concentrated sulphuric acid is added followed by heating to each of the following test tubes labelled (i) to (v)

Identify in which of the above test tube the following change will be observed. Support your answer with the help of a chemical equation. (a) Formation of black substance (b) Evolution of brown gas (c) Evolution of colourless gas (d) Formation of brown substance which on dilution becomes blue 5 # A gas X is soluble in water . Its aq. Solution turns red litmus blue with excess of aq. CuSO4 solution it give s deep blue colour with FeCl3 solution a brownish ppt. soluble in HNO3 is obtained. Identify gasX and write reactions for changes observed . 6# Element A burns in N2 to give a compound B which is ionic in nature . B on reaction with water gives C and D.The solution of C becomes milky on passing CO2 through it. Identify the compound A ,B ,C ,D .

7# An orange solid A on heating gives a green residueB, water vapours and a colourless gas C . The gas C in dry condition is passed over heated Mg to give solid D which further reacts with water to form E which gives dense white fumes with HCl . Identify the compound A ,B ,C ,D and E and write the reactions involved . 8# A colourless inorganic salt A decomposes at 2500C to form B and C leaving no residue . The oxide C is liquid at room temperature and is neutral towards litmus while B is neutral oxide and is used as anaesthetic in minor dental surgery . When Phosphorous burns in excess of B produces compound which is a strong dehydrating agent which when treated with HNO3 produces acid D and a gas E Identify A to E and write the reactions.

I# ANSWERS OF IDENTIFY THE FOLLOWING: ANS-1# S8[A] +8H2 + heat 8H2S[B]

8H2S + 12O2 8SO2 [C] ; 5SO2 + 2KMnO4(pink)/H+ +2H2O K2SO4 +2MnSO4(Colourless solution) 2SO2 +O2 + Pt/heat 2SO3 (D) ANS-2# 2NaNO3 +H2SO4 +heatNa2SO4 + 2HNO3 4HNO3+ heat4NO2+2H2O+O2 Cu+4HNO3Cu(NO3)2 +2NO2 +2H2O 2NO2[A] (cool)=> N2O4[B] ANS-3# P4(white Phosphorous)[A] +very dil KOHPH3[C] P4(white Phosphorous)[A] +heatRed- P(red Phosphorous)[B] P4(white Phosphorous)[A] +Cl2(excess)PCl5[D] PCl5[D] +H2O(excess)H3PO4[E] ANS-4#(a) Test tube(i): C12H22O11+Conc.H2SO411H2O +12C (black subs.) (b) Test tube(ii):2NaBr +3H2SO42NaHSO4 +SO2+Br2(brown gas) (c) Test tube(v): KCl +H2SO4 +heat KHSO4+HCl(colourless gas) (d) Test tube(iii): Cu +2 H2SO4 CUO(brown subs) On dilution: CuO(brown subs) +2 dil.H2SO4 CuSO4(blue substance) (e) Test Tube(iv) : S(yellow powder) + conc.H2SO4 ----SO2 +H2O ANS-5: NH3(g) +H2O NH4OH(aq) [basic and turn red litmus blue] 3 NH4OH(aq) + CuSO4 [Cu(NH3)4]SO4 +4H2O

(deep blue)

3 NH4OH(aq) +FeCl3Fe(OH)3 +3 NH4Cl Fe(OH)3 + 3HNO3 Fe(NO3)3( soluble) +3H2O ANS-6: 3Ca + N2Ca3N2 [B] [A] Ca3N2 + 6 H2O3 Ca(OH)2 [C] + 2NH3 [D] Ca(OH)2 +CO2 CaCO3 + H2O ANS-7: (NH4)2Cr2O7 +heat N2 + Cr2O3 + (Orange solid-A) [C] [green solid B ] N2 +3Mg +heat Mg3N2 [D] Mg3N2 [D] +6H2O 3 Mg(OH)2 +2NH3 [E] NH3 [E] +HCl NH4Cl (dense white fumes) ANS-8:NH4NO3[A]+heat at 2500C N2O(g) [B] + 2 H2O [C] 10 N2O +P4 10 N2 + P4O10 10 P4O10 is a dehydrating agent P4O10 + 4 HNO3 4 HPO3 [D] + 2 N2O5 (g)

II# Explain Why ? / Give reason ? / Account for the following ?

1# HBr and HI cant be prepared by treating metal bromides or iodides with conc. H2SO4 . 2# Why NO2 readily forms a dimmer, whereas ClO2 does not though both are odd electron molecule. 3# Write the balanced chemical equation for the reaction of Cl2 with hot and concentrated NaOH. Is this reaction a disproportionation reaction? Justify. 4# SCl6 is not known but SF6 is known . 5# In trimethylamine, the nitrogen has a pyramidal geometry whereas in trisilylamine,it has a planar 6# SF6 is resistant to hydrolysis whereas SF4 is readily hydrolysed. 7# NCl3 gets hydrolysed to form NH3 and HOCl while PCl3 gets hydrolysed to give H3PO3 and HCl . Explain . 8# In the solid state , PCl5 is in ionic nature . Explain. 9# I2 form I3 but F2 does not formF3 .

10# NO is paramagnetic in gaseous state but diamagnetic in the solid and liquid state. 11# Yellow ppt. of Sulphur disappear when boiled with sodium sulphite . 12# NF3 is more stable but NCl3 is less stable . 13# SH6 and PH5 are not formed but SF6 and PF5 are formed . 14# KHF2 is known but compound of formula KHCl2 or KHBr2 are not known . Why ? 15# Iodine is more soluble in KI solution than in water . 16# HF is stored in wax -coated bottle . 17# HCl is not used to make the medium acidic in titrations involving KMnO4 . 18 # Addition of Cl2 to KI solution gives it a brown colour but excess of Cl2 turns it colourless. 19# CN ion is known but CP is not ? 20# Comment on the nature of two SO bonds formed in SO2 molecule. Are the two SO bonds in this molecule. 21# Why anhydrous CaCl2 is not used to dry up Ammonia ? 22# What happens when Zinc is treated with Conc.H2SO4 . 23# Why conc.H2SO4 is not used for drying of H2S gas . 24# When HCl reacts with finely powdered iron , it forms ferrous Chloride and not ferric chloride . 25# Conc.HNO3 turns yellow on exposure to sunlight .Why ?

ANSWER-II# Explain Why ? / Give reason ? / Account for the following ?

ANS-1# Because Br- and I - will get oxidized by conc. H2SO4 to respective Br2 and I2 . ANS-2# odd electron molecule often get dimerise in order to pair the electrons but ClO2 does not .Thisis thought to be because the odd electron is delocalized. ANS-3# 6 NaOH ( hot and conc.)+ 3Cl2 5 NaCl + NaClO3 + H2O . yes it a disproportionation reaction because the OS of Cl2 is Zero and is oxidized to +5 (in NaClO3) and reduced to -1 (in NaCl) . Due to simultaneous oxidation and reduction occurs of the same species i.e Cl2 . ANS-4# SF6 is known because of small size and more electronegativity of Fluorine which can form strong bond and hence the energy released can compensate to promote electrons in vacant d-orbitals of S which is not possible in case of Chlorine . Due to large size of Cl which cannot be accommodated around Sulphur and stability will also be less due to inter electronic repulsion between lone pairs of Chlorine ( whose size is large as compared to F) ANS-5# Due to presence of Vacant d-orbitals in Si , it can form P-d bond with nitrogen . so reduced to SP2 hybridisation and becomes plannar with three sigma bonds . Which is not possible in case of trimethylamine as
Carbon does have vacant d-orbital. ANS-6# SF6 is octahedral ( which is symmetrical) where six F-atoms surroundingS protect it from attack of H2O molecules. So ,SF6 is sterically protected then SF4 towards the even thermodynamically favorable hydrolysis reaction. Also F-atoms do not have Vacant d-orbitals to accommodate electrons from water molecules . This makes SF6

chemically inert. Due to this it suppresses internal charges hence used in high voltage generators(gaseous insulators, and switch gears. ANS-7# The Cl of NCl3 has vacant d-orbital which can accommodate electrons from water molecules and get hydrolysed to produce HOCl and NH3 . But in case of PCl3 , it is the vacant d- orbital of P can accommodate electrons from water molecules and get hydrolysed to give H3PO3 and HCl . [PO bond strength > ClO] ANS-8# Due to unequal bond length of equatorial and axial bond that is why it is reactive . So, in solid state (in close range) , it can be stabilized by forming [PCl4]+ and [PCl6]- which are symmetrically stable tetrahedral and octahedral str. respectively . ANS-9# Due to presence of vacant d-orbital in Iodine it can accept the electrons of iodide ion . ANS-10# NO is an odd electron molecule (paramagnetic) . In solid and liquid state , dimer is formed and there is no unpaired electrons and act as diamagnetic . ANS-11# Na2SO3 + S ( yellow solid ) Na2 S2O3 ( sodium thiosulphate) ANS-12# Because of small size and more electronegativity of Fluorine which can form strong bond with Nitrogen and becomes stable as compared to large size Chlorine . ANS-13# It is because of two reason why hydrogen cannot form SH6 and PH5 though SF6 and PF5 are formed Reason-1: Hydrogen is less electronegative element as compared to fluorine . SH bond is weaker than SH bond .

Reason-2: The enthalpy of atomization of HH is very high as compared to FF . High enthalpy of dissociation can not be compensated by energy released during bond formation . ANS-14# KHF2 contains HF2 ion which is stable due to formation os H-bonding between HF and F . This is possible because of high electronegativity of F ( FH ..H) on the other hand , Cl and Br cannot form hydrogen bonds due to low electronegativity . ANS-15# Due to formation of polyiodide ion .KI +I2 K+ [I3] . Ion dipole interaction between polyiodide ion and water responsible for solubility . ANS-16# Due to formation of complex called flurosilicic acid , H2[SiF6] ANS-17# Chloride gets oxidized to chlorine by conc. Sulphuric acid ( an oxidizing agent) ANS-18# Cl2 + KI ( solution) KCl + I2 ( brown ) . Iodide reduces chlorine to chloride ion. The I2 formed will react with excess Cl2 in presence of water to form HIO3 which makes it colourless . ANS-19# Nitrogen being small size can form stable and effective P-P bond ( in case of cyanide ion) but which is not possible in CP . P is larger size which cannot form stable and effective P-P bond . ANS-20# S 3s2 3px23py13pz1 (Ground state) ; S 3s2 3px13py13pz1 3d1 (excited state) Sp2 hybridisation in Sulphur . one half filled 3pz1 can form P-P bond with half-filled 2p orbital of one Oxygen and one half filled 3d1 of Sulphur with half-filled 2p orbital of another Oxygen can form P-d bond . And due to resonance the bond lengths are equal. ANS-21# Because it t forms CaCl2.8NH3 , addition compound . ANS-22# Zn reduces Sulphate to SO2 and ultimately colloidal sulphur .As Conc. H2SO4 is an oxidizing agent . ANS-23# H2S + Conc.H2SO4 ( an oxidizing agent ) Sulphur ANS-24# Its reaction with iron produces H2 Fe + 2 HCl FeCl2 + Cl2 . Liberation of hydrogen creates a reducing environment and prevents the formation of ferric chloride . ANS-25# In presence of light nitric acid decomposes to form NO2 (brown) , O2 and water .

II # Arrange the Following in increasing order against the properties mentioned :-

1# Bond Dissociation Enthalpy:- (a) BrBr , II , ClCl , FF (b) HI , HF, HBr,HCl (c) OH, HTe, HSe, HS. (d) NN, PP, AsAs 2# Acid strength:- (a) HI , HF , HBr , HCl (b) HF, CH4 , H2O , NH3 (c) H2O, H2Te , H2Se , H2S 3# Base Strength:- BiH3 , NH3 , AsH3 , SbH3 , PH3 4# Thermal Stability:- (a) H2O , H2Te , H2Se , H2S (b) PH3 , BiH3 , AsH3 , SbH3 , NH3 5# Oxidizing Ability:- (a) Cl2 , F2 , I2 , Br2 (b) HCl , HNO3 ,H2SO4 ,H3PO4 (c) HClO3 ,HClO , HClO2 ,HClO4 (d) F2 ,Cl2 ,O2 , O3 6# Catenation property:- (a) As , N, P , Sb (b) Se ,S , Te ,O (c) Si , Sn , C , Ge 7# Bond Angle:- (a) H2Se , H2O, H2S ,H2Te (b) PH3 , BiH3 , AsH3 , SbH3 , NH3 8# Boiling Point :- (a) H2S , H2O , H2Te , H2Se (b) PH3 , BiH3 , AsH3 , SbH3 , NH3 9# Stability:- (a) Pb++ , C++ , Sn++ , Si++ (b) As3+ , Bi3+ , Sb3+ (c) Ga+ , Tl+ ,Al+, In+ 10 # Covalent Character :- (a) MCl , MBr , MI , MF (b) Cr2O3 , CrO, CrO3 (c) P2O5,Sb2O5, As2O5 (d) BeCl2, MgCl2 ,CaCl2, BaCl2 11# Acid Strength:- (a) HOClO2 , HOClO , HOCl ,HOClO3 (b) HOCl , HOI ,HOBr 12# Acidic Character -- (a) N2O, N2O5, N2O3 ,NO , N2O4 (b) ClO2 , Cl2O7 ,Cl2O , Cl2O6 (c) HNO2 & HNO3 (d) H2SO3 &H2SO4 (e)GeO2 ,ClO2 ,As2O3 ,Ga2O3 (f) P2O5 ,SO3 , N2O5 , CO2 , SiO2 (g) Al2O3 ,CaO, Cl2O7 ,SO3 (h) BF3 ,BBr3 , BCl3 13# Volatility:- H2O , H2Te , H2Se, H2S 14# Electron Gain Enthalpy :- (a) I , Br , Cl , F (b) N , O, P ,S (c) F, Cl , O , S 15 # Ionisation Enthalpy:- (a) O , N , F , C (b) Ar , Ne , He , Xe , Kr 16# Electronegativity:- (a) Cl ,F, Br, I (b) O , N , F , C 17# Stability:- F , I , Cl , Br 18# Reducing properties: (a) H2O, H2Te , H2Se , H2S (b) H3PO4 , H3PO2 , H3PO3 CHECK-UP LIST:- ARRANGEMENT (in terms of properties mentioned.) 1# II < FF < BrBr < ClCl (Bond Dissociation Enthalpy)Inter-electronic repulsion 2# HF < HCl < HBr < HI (Acid strength)Lower BDE of HI,large size of I 3# MI < MBr < MCl < MF ( Ionic Character)Fajans RuleLager polarizability of I

4# BiH3 < SbH3 < AsH3 < PH3 < NH3 ( Base Strength) small size of N High electron density in Ammonia 5# H2O < H2S < H2Se < H2Te ( Acid Strength and Reducing Character) --- BDE 6# H2Te < H2Se < H2S < H2O ( Thermal Stability) ---BDE 7# H2O < H2Te < H2Se < H2S (Volatility)--- H-Bond and Vander waals force 8# H2S < H2Se < H2Te < H2O ( Boiling Point) -- H-Bond and Vander waals force 9# PH3 < AsH3 < NH3 < SbH3 < BiH3 (Boiling Point) -- H-Bond and Vander waals force 10# I2 < Br2 < Cl2 < F2 (Oxidizing Ability) --Electron gain enthalpy, hydration enthalpy, dissociation enthalpy . 11# H2Te < H2Se < H2S < H2O ( Bond Angle )----- Size of central atom , electronegativity, repulsion of bond pairs. 12# HClO4 < HClO3 < HClO2 < HClO ( Oxidizing Power) 13# HOCl < HOClO < HOClO2 < HOClO3 ( Acid Strength) Stability of its conjugate base , charge dispersal , Oxidation states. 14 # HOI < HOBr < HOCl ( Acid Strength) ---Stronger the OX bond Weaker the OH bond More the acidic character. 15# Cl2O < ClO2 < Cl2O6 < Cl2O7 ( Acid Strength)-- Higher oxidation states, covalent character 16# ClO4 < BrO4 > IO4 or BrO4 > IO4 > ClO4 (Oxidizing Power) 17# Ga2O3 < GeO2 < As2O3 < ClO2 (Acidic Character) 18# BF3 < BCl3 < BBr3 (Acidic Character)Effective 2p2p overlap in BF3 reduces the electron deficiency of B , make it less acidic. 19# Pb < Sn = Ge < Si < < C ( Catenation Property) Sigma bond strength 20# C++ < Si++ < Sn++ < Pb++ ( Stability) ---- Inert pair effect 21# N2O < NO < N2O3 < N2O4 or NO2 < N2O5 (Acidic Character) Higher oxidation states, covalent character 23# HCl < H2SO4 < HNO3 (Oxidizing Acid) 24# (i) N < P > As > Sb (ii) O < S > Se > Te ( catenation property) --- ( P , N ) ; ( O ; S ) 25# (a) HNO2 < HNO3 (b) H2SO3 < H2SO4 (Acidic character) 26# I < Br < Cl < F (Stability) 27# Reactivity---ClF3 > BrF5 > IF7 > ClF7 > BrF3 >IF5 > BrF > IF3 >IF 28# StabilityClO4 > ClO3 > ClO2 >ClO

UNIT-8:d-Block Elements
Q.1 # Why is Cr2+ strongly reducing and Mn3+ strongly oxidising when both have d4 configuration. Ans:- Cr2+ is reducing as its configuration changes from d4 to d3, the latter having a half-filled t2g level .On the other hand, the change from Mn2+ to Mn3+ results in the half-filled (d5) configuration which has extra stability. Q.2 # Explain why Cu+ ion is not stable in aqueous solutions? Ans--Cu+ in aqueous solution underoes disproportionation, i.e., 2Cu+(aq) Cu2+(aq) + Cu(s) The E0 value for this is favourable. Cu++ has higher hydration enthalpy than Cu+ Q.3# Cobalt(II) is stable in aqueous solution but in the presence of complexing reagents it is easily oxidised. Ans Co(III) has greater tendency to form coordination complexes than Co(II) . Due to higher charge by radius ratio and also due to greater CFSE( Crystal Field Stabilisation Energy) . Co (III) Has d6 configuration . In case of of strong ligand , It is t2g 6 eg0 . So , Co(II) changes to Co(III) i.e. easily oxidized . Q.4 # Mn+2 compounds are more stable than Fe+2 toward oxidation to their + 3 state .(AI-06) OR , Why E 0 value for the Mn 3+ /Mn 2+ is much more positive than Fe 3+ /Fe 2+ ? Ans-Mn 3+ + e> Mn 2+ (d4 system , less stable ) (d5 system , more stable ) extra stable due to half-filled confN Fe3+ + e> Fe 2+ (d5system , more stable ) (d6 system , less stable ) 0 2+ Q.5 # The E (M /M) value for copper is positive (+0.34V). What is possibly the reason for this? (Hint: consider its high aH0 and low hydH0) Ans The reduction potential value depends on relative value of three enthalpies viz aH0 , iH0 and - hydH0 . The copper has high aH0 and iH0 . Therefore high enthalpy required to transform Cu(s) to Cu2+(aq) is not balanced by its low hydH0 . Q.6 # Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only? Ans-- Because of small size and high electronegativity oxygen or fluorine can oxidise the metal to its highest oxidation state. Oxygen has the ability to form multiple bond with transition metals . Q.7 # Which is a stronger reducing agent Cr2+ or Fe2+ and why ? Ans-- Cr2+ is stronger reducing agent than Fe2+ Reason: d4 d3 occurs in case of Cr2+ to Cr3+But d6 d5 occurs in case of Fe2+ to Fe3+ . In a medium (like water) d3 is more stable as compared to d5 (see CFSE) Q.8 # Why is the E0 value for the Mn3+/Mn2+ couple much more positive than that for Cr3+/Cr2+ or Fe3+/Fe2+? Explain. Ans--Much larger third ionisation energy of Mn (where the required change is d5 to d4) is mainly responsible for this. This also explains why the +3 state of Mn is of little importance. Q.9 # Give reason for it?. Ni+2 compounds are thermodynamically more stable than Pt+2 compounds whilst Pt(IV) are relatively more stable than Ni(IV) compounds . OR, K2PtCl6 is well known cpds. but corresponding Ni-compound is not known . Ans--The oxidation state of Pt in K2 Pt Cl6 is +4 .The sum of the first four ionization energies (IE1+IE2 +IE 3+IE 4) of pt is less than those of Ni. Q.10# E0 for Mn+3 / Mn+2 couple is more positive than for Fe+3 / Fe+2 or Cr+3 / Cr+2 . Ans-- Much larger third Ionisation enthalpy of Mn ( where the required change is d5 to d4) is mainly responsible for this . this also explains why the +3 state of Mn is of little importance . Q.11 #.Why is HCl not used to acidify a permanganate solutions in volumetric estimation of Fe+2 or C2O4 2 .

Ans- Since Cl of Hydrochloric acid is oxidized to chlorine by MnO4 . so , actual amount of KMnO4 required to oxidize C2O4 2 couldnot be determined.

II# IDENTIFY THE FOLLOWING:

1# A mixed oxide of iron and chromium FeO.Cr2O3 is fused with Sodium Carbonate in presence of air to form a yellow coloured compound (A). On acidification the compound (A) forms an orange coloured compound (B) which is a strong oxidizing agent. (i) Identify the compounds (A) and (B) (ii) Write balanced chemical equations for each step. 2 # A green chromium compound (A) on fusion with alkali gives a yellow compound (B) which on acidification gives an orange coloured compound (C) . C on treatment with NH4Cl gives an orange coloured product (D) , which on heating decomposes to give back (A) . Identify A,B,C,D .Write equations for reactions . 3# (a) A blackish brown coloured solid (A) when fused with alkali metal hydroxides in presence of air produces a dark green compound (B), which on electrolytic oxidation in alkaline medium gives a dark purple compound (C). Identify (A), (B) and (C) and write balanced chemical equations for the reactions involved. (b) What happens when an acidic solution of the green coloured compound (B) is allowed to stand for some time? Give the equation of the reaction involved. What is this type of reaction called? (Hint: MnO42- changes to MnO4-) 4# (A) reacts with H2SO4 to form purple coloured solution (B) which reacts with KI to form colourless compound (C). The colour of (B) disappears with acidic solution of FeSO4. With concentrated H2SO4 (B) forms (D) which can decompose to give a black compound (E) and O2. Identify (A) to (E) and write equations for the reactions involved. 5# When an orange coloured crystalline compound A was heated with common salt and concentrated H2SO4, an orange red coloured gas B was evolved. The gas B on passing through NaOH solution gave an yellow solution C (i) Identify A,B and C. (ii) Write balanced chemical equation involved in the reactions. 6# Two gases (A) and (B) turns acidified K2Cr2O7 solution green. Gas(A) turns lead acetate paper black and when passed through gas(B) in aq. Solution , yellowish turbidity appears . Identify A and B and explain. 7# Explain why a green solution of K2MnO4 turns purple and a brown solid is precipitated when CO2 gas is bubbled into the solution . UNIT-9: CO-ORDINATION COMPOUNDS I#EXPLAIN ? 1# Why only Transition metals are known to form Pi-complexes 2#A solution of [Ni(H2O)6]2+ is green but a solution of [Ni(CN)4]2 is colourless. Explain. 3#Though CO is a weak lewis base yet it forms a number of stable metal carbonyls .Explain 4# What will be the correct order for the wavelengths of absorption in the visible region for the following: and why [Ni(NO2)6]4, [Ni(NH3)6]2+, [Ni(H2O)6]2+ ? 5# Explain why [Co(NH3)6]3+ is an inner orbital complex whereas [Ni(NH3)6]2+ is an outer orbital complex. 6# The spin only magnetic moment of [MnBr4]2 is 5.9 BM. Predict the geometry of the complex ion ? 7# A solution of [Ni(H2O)6]2+ is green but a solution of [Ni(CN)4]2 is colourless. Explain. 8# [Cr(NH3)6]3+ is paramagnetic while [Ni(CN)4]2 is diamagnetic. Explain why? 9# [Fe(CN)6]4 and [Fe(H2O)6]2+ are of different colours in dilute solutions. Why? 10# Amongst the following, which is the most stable complex and why ? (i) [Fe(H2O)6]3+ (ii) [Fe(NH3)6]3+ (iii) [Fe(C2O4)3]3 (iv) [FeCl6]3 10 11# Silver atom has completely filled d orbitals (4d ) in its ground state. How can you say that it is a transition element? 12# The ability of oxygen to stabilize the metal in higher oxidation states exceeds that of fluorine. 13# Why is that while making an aq. solution of FeCl3 lab. Reagent some HCl solution is also added besides FeCl3 ANSWERS TO I # E X P L A I N ? ANS-1: The transition metals have vacant d-orbitals which can accept electron pairs of ligand containing pielectrons(H2C=CH2 ,C5H5 , C6H6 )
ANS-3# CO is a pi acceptor ligand which forms stable synergic bond due to back bonding ANS-4# NO2 is a strong field ligand acc. to spectrochemical series , so it energy of absorption is in higher energy range .

H2O < NH3 < NO2( spectrochemical series) The correct order for the wavelengths of absorption in the visible region: [Ni(H2O)6]2+ [Ni(NH3)6]2+, [Ni(NO2)6]4,

Ans-5:- In the presence of NH3, the 3d electrons pair up leaving two d orbitals empty to be involved in d2sp3 hybridisation forming inner orbital complex in case of [Co(NH3)6]3+. In [Ni(NH3)6 ]2+, Ni is in +2 oxidation state and has d8 configuration, the hybridisation involved is sp3d2 forming outer orbital complex. Ans-6:- Since the coordination number of Mn2+ ion in the complex ion is 4, it will be either tetrahedral (sp3 hybridisation) or square planar (dsp2 hybridisation). But the fact that the magnetic moment of the complex ion is 5.9 BM, it should be tetrahedral in shape rather than square planar because of the presence of five unpaired electrons in the d orbitals. ANS:-7# Cyanide being the strong ligand , the orbital splitting energy is high in case of square plannar splitting in [Ni(CN)4]2 The electrons are paired up during the electron fill-up in case of square plannar splitting , the transition of electrons not occurs in visible spectrum so it is colorless. In case of [Ni(H2O)6]2+ it is green , as water is a weak ligand in Octahedral

splitting , The unpaired electron can take transition in visible spectrum and the complementary colour is green. ANS-8# [Ni(CN)4]2 forms square plannar (dsp2) complex with no unpaired electron so ,it is diamagnetic . [Cr(NH3)6]3+ forms octahedral (d2sp3) complex with unpaired electron so ,it is paramagnetic . ANS-9# Due the change in the nature of ligand , strong field and weak field , the orbital splitting energy changes . So ,the energy of absorption changes and hence , the complementary colour changes. ANS-10# (iii) [Fe(C2O4)3]3 , due to presence of bidentate ligand .

II# Explain these experimental results . 1 . Aqueous copper sulphate solution (blue in colour)gives: (a) a green precipitate with aqueous potassium fluoride , and (b) a bright green solution with aq. potassium chloride . Explain these experimental results . 2.What is the coordination entity formed when excess of aq. KCN is added to an aq.solution of CuSO4 ?Why is it that no precipitate of copper sulphide is obtained when H2S(g) is passed through the solution ? 3.A coordination compound has the formula CoCl3.4NH3 .It does not liberate NH3 but forms a precipitate of AgCl on treatement with AgNO3 solution .Write the formula and IUPAC name of the complex 4# 0.1 M solution of a complex obtained by mixing CoCl3 and NH3 in the molar ratio 1:4 froze at -0.3720C . What is the formula of the complex . (Kf = 1.86 0C C/m) ANSWERS TO II : Explain these experimental results Ans-3 :- As it does not liberate any ammonia ,it means all ammonia are acting as ligand . To form octahedral stable complex two more Cl- will also act as ligand . So only one Cl- will act as counter ion and link through primary linkage . Becxause it forms AgCl precipitate when the complex treated with AgNO3 The Complex is [Co(NH3)4Cl2]Cl -- tetraamminedicholridocobalt(III)chloride Ans-4 :- Tf (theoretical) = Kf . m = 1.86 0.1 = 0.1860 Tf (obs) = 0.3720 i = Tf (obs) /Tf (theoretical) = 0.3720 /0.1860 =2 The complex dissociate to form two ions [Co(NH3)Cl2]+ and Cl III# Write the IUPAC Name and draw the structures of all the isomers with this formula of complex. (optical & geometrical) (i) [Co(en)2Cl2]Cl (ii) [PtCl(NH3)5]Cl3 (iv) [Co(OX)3]3 (v) [CoCl2(en)2]+ (vi) [CoCl2(en)(NH3)2]+ [CoCl (en)2(NH3)]+

(vii)

1. Unlike phenols, alcohols are easily protonated. Explain. (1M) 2. Why absolute alcohol can not be obtained from rectified spirit by simple distillation? (1M) 3. Explain why is o- nitro phenol more acidic than o-methoxy phenol? (1M) 4. Out of two isomeric aromatic compounds X,Y with formula C7H7OH only X gives purple colour with neutral ferric chloride.Identify X and Y. (1M) 1. A gives positive lucas test in 5 minutes. Its molecular mass is 60u. It reacts with PBr3 to give B which when treated with benzene in presence of AlCl3 gives compound C. Write structural formula of A,B and C. (2M) 2. An organic compound A having formula C6H6O gives a characteristic colour with Aq. FeCl3 solution.When A is treated with CO2 and NaOH at 400K under pressure B is obtained. The compound B on acidification gives C which reacts with acetyl chloride to form D which is a Popular pain killer. Deduce strutures of A,B,C and D. (3M) ANSWERS 1. In alcohols the lone pair of electrons on oxygen are localised and hence are easily available For protonation.But in phenols the lone pair of electrons on oxygen are delocalised over the benzene ring due to resonance and hence are not easily available for protonation. 2. Rectified spirit contains 95% ethyl alcohol and 5% water and forms an azeotropic mixture Which distils at a constant temperature of 351.13K. 3. NO2 group is an electron withdrawing group.So nitro phenol is more acidic than phenol -OCH3 group is an electron releasing group so it is less acidic than phenol. Hence o-nitro Phenol is more acidic than ortho methoxy phenol. 4. X is Cresol (o,mor p) Y is Benzyl Alcohol 5. A is Secondary alcohol wiyh molar mass 60g/mol Therefore A is CH3-CH-CH3 OH UNIT 12: ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 1. Compound A (C4H8Cl2) is hydrolysed and then dehydrated to form a compound B C4H8O which forms an oxime with NH2OH and gives negative tollens test. Write the structure of A and B. 2. Arrange the following i) in increasing order of acid strength CH2ClCOOH, CHCl2COOH, CH3COOH, CCl3COOH ii) in increasing order of reactivity towards HCN CH3CHO, CH3COCH3, HCHO, C2H5COCH3 3. Identify the compounds A B and C in the following reactions

UNIT 11:

ALCOHOLS PHENOLS AND ETHERS

4. Complete the following CH3COOH Cl2/P ..

NaCN .. H2O/H+ Heat ..

5. Explain Why i) Di-tert butyl ketone does not give ppt with NaHSO3 where as acetone does. ii) Benzoic acid does not give Friedel Crafts reaction

UNIT

13 (Amines)

1. Give reason a) p-methoxy aniline is a stronger base than aniline while p-nitroaniline is a weaker base than aniline. (1M) b) Aromatic primary amines cant be prepared by Gabriel Phthalamide synthesis.(1M) c) CH3CONH2 is a weaker base than CH3CH2NH2.(1M) d) Carbon-nitrogen bond length is aromatic amines is shorter than in aliphatic amines. e) Aniline does not undergo Friedal-Craft reaction.(1M) 2. . i) Arrange in decreasing order of pkb values C2H5NH2, C6H5NHCH3, (C2H5)2 NH, C6H5NH2 (1M) ii) Arrange in increasing order of basic character Aniline, p-nitro aniline, p-toulidine 3. The compound C5H13N is optically active and reacts with HNO2 to give C5H11OH and liberates N2 gas. Identify the compound and write the reactions involved. (2M) 4. Name A,B,C in the following equation a) CH3CH2COOH A + Heat B in presence of Br2/KOH C b) A Br2/KOH B HNO2 C Red P/I2 CH3I ANSWERS 1. a) Methoxy group is electron releasing group whereas Nitro group is electron withdrawing group therefore in p-methoxy aniline the electron density on N- atom of NH2 group increases making it more basic but in p-nitro aniline the electron density on N- atom of NH2 group is decreased making it less basic. b) Aromatic primary amines can not be prepared by Gabriel Phthalimide Synthesis because aryl halides do not under go nucleophillic substitution with the anion formed by phthalimide on reaction with KOH. c) Due to resonance in CH3CONH2 , the lone pair of electrons in CH3CONH2 is delocalised .

Due to this electron density on N-atom in acetamide decreses. In CH3CH2NH2 due to +I effect of CH3CH2 group electron density on N- atom increses . As a result CH3CONH2 is a weaker base than CH3CH2NH2 d) It is because in aromatic amines C-N bond acquires some double bond character and thus becomes shorter than in aliphatic amines. e) AlCl3 used as catalyst in Friedelcrafts reaction forms a salt with aniline .Due to this nitrogen aquires positive charghe . Thus it acts as strong deactivating group for electrofilic reaction. Hence anilie does not give Foriedelcraft reaction. 2. i. C6H5NH2 > C6H5NHCH3> C2H5NH2>(C2H5)2NH ii. p-nitroamiline<amiline<p-tolidine 5) i. A=CH3CH2COONH4 B= CH3CH2CONH2 C= CH3CH2NH2 ii. A=CH3CONH2 B=CH3NH2 C=CH3OH

ORGANIC REASONING QUESTIONS ( for practice) Q.1 # Amino group is o,p-directing for aromatic electrophilic substitution . Why does aniline on nitration gives a substantial amount of meta-nitroaniline ? Q.2# Aniline does not undergo Friedel-Crafts reaction (alkylation and acetylation) (PN-395) Q.3# Diazonium salts of aromatic amines are more stable than those of aliphatic amines. Q.4# Gabriel phthalimide synthesis is preferred for synthesising primary amines. Q. 5 # Why cannot aromatic primary ammines be prepared by Gabriel phthalimide synthesis . Q.6# Why sec- & tert- alkyl halides are not used during Williamsons Synthesis . Q.7 # Although haloalkanes are usually prepared from alcohols , haloarenes cant be prepared from phenols. Q.8 # Give reason for the higher boiling point of ethanol in comparison to methoxy methane ? Q.9# Preparation of ethers by acid dehydration of secondary and tertiary alcohols is not a suitable method . Give reason .

Q.10# Why is sulphuric acid not used during the reaction of alcohols with KI?
ANSWERS ANS-1-- in the strongly acidic medium, aniline is protonated to form the anilinium ion which is meta

directing. That is why besides the ortho and para derivatives, significant amount of meta derivative is also formed. ANS-2-Aniline does not undergo Friedel-Crafts reaction (alkylation and acetylation) due to salt formation with aluminium chloride, the Lewis acid, which is used as a catalyst. Due to this, nitrogen of aniline acquires positive charge and hence acts as a strong deactivating group for further reaction. ANS-3- Primary aliphatic amines form highly unstable alkyldiazonium salts . Primary aromatic amines form arenediazonium salts which are stable for a short time in solution at low temperatures (273-278 K). The stability of arenediazonium ion is explained on the basis of resonance.

ANS-4- Because we obtain pure primary amines in Gabriel phthalimide synthesis which is not possible in
ammonolysis .

ANS-5- Aromatic primary amines cannot be prepared by this method because aryl halides do not

undergo nucleophilic substitution with the anion formed by phthalimide. Due to resonance it developes partial double bond character between aromatic carbon and nitrogen. Ans-6:- In case of secondary and tertiary alkyl halides, elimination competes over substitution. If a tertiary alkyl halide is used, an alkene is the only reaction product and no ether is formed. For example, the reaction of CH3ONa with (CH3)3CBr gives exclusively 2-methylpropene. It is because alkoxides are not only nucleophiles but strong bases as well. They react with alkyl halides leading to elimination reactions Ans-7:- Because the carbon of phenyl group is sp2 hybridised and there is a partial double bond character due to resonance

Ans-8 :- Ethanol get associated with H-bonding but methoxy methane does not .
ANS-9--The method is suitable for the preparation of ethers having primary alkyl groups only. The alkyl group should be unhindered and the temperature be kept low. Otherwise the reaction favours the formation of alkene. The reaction follows SN1 pathway when the alcohol is secondary or tertiary. However, the dehydration of secondary and tertiary alcohols to give corresponding ethers is unsuccessful as elimination competes over substitution and as a consequence, alkenes are easily formed. Answer-10-H2SO4 cannot be used along with KI in the conversion of an alcohol to an alkyl iodide as it converts KI to corresponding HI and then oxidizes it to I2.

Organic CONVERSION With Word Problems (5 Marks) FOR PRACTICE IDENTIFY THE COMPOUNDS A,B,C etc. by akp Q.1# An organic compound (A) with molecular formula C8H8O forms an orange-red precipitate(B) with 2,4-DNP reagent and gives yellow precipitate( C ) on heating with iodine in the presence of sodium hydroxide along with a colourless compound( D ) . ( A ) neither reduces Tollens or Fehlings reagent, nor does it decolourise bromine water or Baeyers reagent. On drastic oxidation of ( A ) with chromic acid, it gives a carboxylic acid (E) having molecular formula C7H6O2. Deduce the structures of organic compounds (A) to (E) and explain the reactions involved. (TBQ and Sample Paper-1) Q.2# An organic compound with the molecular formula C9H10O forms 2,4-DNP derivative, reduces Tollens reagent and undergoes Cannizzaro reaction. On vigorous oxidation, it gives 1,2-benzenedicarboxylic acid. Identify the compound. (TBQ) Q.3# An organic compound (A) (molecular formula C8H16O2) was hydrolysed with dilute sulphuric acid to give a carboxylic acid (B) and an alcohol (C). Oxidation of (C) with chromic acid produced (B). (C) on dehydration gives but-1-ene. Write equations for the reactions involved. (TBQ) Q.4# An organic compound contains 69.77% carbon, 11.63% hydrogen and rest oxygen. The molecular mass of the compound is 86. It does not reduce Tollens reagent but forms an addition compound with sodium hydrogensulphite and give positive iodoform test. On vigorous oxidation it gives ethanoic and propanoic acid. Write the possible structure of the compound. (TBQ) Q.5# Primary alkyl halide C4H9Br (a) reacted with alcoholic KOH to give compound (b). Compound (b) is reacted with HBr to give (c) which is an isomer of (a). When (a) is reacted with sodium metal it gives compound (d), C8H18 which is different from the compound formed when n-butyl bromide is reacted with sodium. Give the structural formula of (a) and write the equations for all the reactions. (TBQ) Q.6# An organic compound (A) with molecular formula C5H8O2 is reduced to n-pentane on treatment with Zn-Hg/ HCl . A forms a dioxime with hydroxylamine and gives a positive iodoform test and Tollens test.Identify the compound A and deduce its structure.( SP-2) (2 Marks) Q.7# An organic compound (A) with molecular formula C8H8O gives a positive DNP and iodoform test . It does not reduce Tollens or Fehlings reagent and does not decolourise bromine water also. On oxidation with Chromic acid(H2CrO4) , It gives carboxylic acid (B) with a molecular formula C7H6O2 . Deduce the structures of organic compounds (A) and (B). (SP-2)(3 M) Q.8 # An unknown aldehyde A on reacting with alkali gives a -hydroxy aldehyde , which losses water to form an unsaturated aldehyde , 2-butenal . Another aldehyde B undergoes disproportionation reaction in the presencence of conc.alkali to form products C and D . C is an aryl alocohol with a formula C7H8O. (i) Identify A and B (ii) Write the sequence of reactions involved (iii) Name the product , when B reacts with Zinc amalgam and hydrochloric acid . (SP-3) ( 5 Marks) Q.9# A compound X (C2H4O ) on oxidation gives Y (C2H4O2) . X undergoes haloform reaction.On treatment with HCN X forms a product Z which on hydrolysis gives 2-hydroxy propanoic acid . (i) Write down structures of X and Y (ii) Name the product when X reacts with dil NaOH (iii) Write down the equations for the reactions involved. (SP-3) ( 5 Marks) Q.10 # An optically active compound having molecular formula C7H15Br reacts with aqueous KOH to give a racemic mixture of products .Write the structures of the compounds . Additional Questions for practice Q.11# A compound (A) with molecular formula C5H12O , on oxidation forms compound (B) with molecular formula C5H10O .The compound (B) gives iodoform test ,but does not reduce ammoniacal silver nitrate solution.(B) on reduction with amalgamated zinc and conc.HCl gives compound (C)with molecular formula C5H12. Identify (A),(B),(C), write down the chemical reaction involved . (3) Q.12# An organic compound (A) with a molecular formula C3H6O2 when treated wit h excess of NH3 and then heated formed B (C3H7ON). B on treatment with P2O5 formed C with molecular formula C3H5N. C on complete acid hydrolysis formed A . C on reduction with complex metal hydride formed a basic nitrogeneous compound D with molecular formula C3H9N . D on treatment with HNO2 formed an alcohol E (C3H8O).E on oxidation gave A . Give structures of A to E and write reactions . ( 5 Marks) Q.13# An organic compound A has a molecular formula C3H7O2N on reaction with Fe and Conc.HCl give a compound B of molecular formula C3H9N . Compound B on treatment with NaNO2 and HCl give another compound C of molecular formula C3H8O.The compound C gives effervescence with Na.On oxidation with CrO3, the compound C gives a saturated aldehyde containing three carbon atoms .Deduce the structures of A, B and C and write the chemical equations for the reactions involved. Q.14# A compound A of molecular formula C7H7NO. On treatment with Br2 and NaOH it gives B .B gives a foul smelling substance C on treatment with CHCl3 and KOH . B on treatment with NaNO2 and HCl at 00C and mixing with alkaline phenol give a red dye D.Identify A to D Q.15 # An organic compound A which has characteristic odour, on treatment with NaOH forms two compounds B and C .Compound B has a molecular formula C7H8O which on oxidation gives back compound A.Compound C is the sodium salt of an acid .C when heated with sodalime yields an aromatic hydrocarbonD.Deduce the structure A,B,C,D . Q.16# An organic compound A has a molecular formula C5H10O.It does not reduce Fehlings Solution but forms a bisulphite compound .It also positive iodoform test.What is the possible structure of A? Explain your reasoning which helped to arrive at the structure. Q.17 # A compound A has a molecular formula C5H10O gave a positive 2,4-DNP test but a negative Tollens test. It was oxidized to carboxylic acid B with molecular formula C3H6O2 when treated with alkaline KMnO4 under vigorous condition .Sodium salt of B gave a hydrocarbon C on Kolbes electrolytic reduction Identify A,B and C and write chemical equations for the reaction.

Q.18 # An organic compound A having molecular formula ,C6H6O gives a characteristic colour with aqueous FeCl3 solution.Aon treatment with CO2 and NaOH at 400K under pressure gives B which on acidification gives a compound C . C reacts with acetyl chloride to give D which is a popular pain killer .Deduce the structures of A,B,C and D . .

ORGANIC DISTINGUISH BETWEEN PAIRS OF COMPOUNDS FOR CBSE (2 MARKS)

GIVE SIMPLE CHEMICAL TEST TO DISTINGUISH BETWEEN FOLLOWING PAIRS OF COMPOUNDS PRIORITY-I 1# Benzyl chloride and Chlorobenzene 2# Methanol and Ethanol 3# Phenol and Benzoic acid 4# Ethanol and Ethoxyethane 5# Propanal and Propanone 6# Ethylamine and Aniline. PRIORITY-II 1 # Vinyl Chloride and Allyl Chloride 2# Formic acid and Acetic acid . 3# Phenol and Ethanol 4# Phenol and cyclohexanol 5# Propanoyl chloride and Propanoic acid. 6# Benzamide and p-Aminobenzoic acid . 7# Propanal and Diethyl ether. 8# Acetaldehyde and Benzaldehyde. 9# Propanol-1 and Propanol-2 10# Butanol and 2-methyl propan-2-ol 11# Propanal and butanone 12# Isopropyl alcohol and propanol

7# Ethylamine and Nethylaniline. 8# t-butylalcohol and Butan-2ol . 9# Ethanenitrile and Methylcarbylamine 10# Nitromethane and Methyl nitrite 11# Benzoic acid and Ethyl benzoate . 12# Acetophenone and Benzophenone. 13# Benzalehyde and Acetophenone. 14# Pentanone -2 and Pentanone-3. 15# Ethanal and Propanal 16# Methylamine and dimethylamine 17# Aniline and benzylamine 18# Aniline and N-methylaniline 19# Methyl acetate and Ethyl acetate. 20# Formaldehyde and Acetaldehyde REAGENTS TO BE USED ***********

1# Iodoform test [POSITIVE TEST for ethanal, ethanol, --2one , -2-ol , terminal CH3CO group, acetophenone ] ( NaOH + I2 ) OR (Na 2CO3 + I2 ) OR NaOI (Iodoform tests )--- yellow ppt. of iodoform forms. 2# Test for phenol (a)Neutral Ferric Chloride solution Phenol gives violet colour complex with neutral FeCl3. (b) Bromine water test:Phenol and Aniline readily decolourises bromine water giving a white ppt. of 2,4,6-tribromophenol /2,4,6tribromoaniline 3# Test for Aldehydes and Formic acid (a)Tollens Reagent (ammoniacal AgNO 3 solution)--- silver mirror appears. (b) Fehlings solution(alkaline sol. Of CuSO4 + sod.pot.tartarate)---- redish brown ppt. of cuprous oxide forms. 4# TEST FOR ALCOHOLS[ Na metal test] -- hydrogen gas evolved (effervescence) [ether does not responds this test] 5# TEST FOR CARBOXYLIC ACIDS [NaHCO3 solution ]----carbon dioxide evolves with acids. (effervescence) 6# ISOCYANIDE TEST OR CARBYLAMINE TEST ( test for primary amine) CHCl3 + alcoholic KOH solution----an offensive smell of isocyanide results when treated with primary amine . 7# AZODYE TEST [Test for primary aromatic amines] ( NaNO2 +HCl) and beta-napthol (diazo test)----an orange or red dye will appear with primary aromatic amine 8# Hinsbergs reagent ( benzene sulphonyl chloride and KOH ) ----To distinguish p-,s-,t- amines Both 10 and 20 Amine reacts with benzene sulphonyl chloride ,the reaction product of 10 amine soluble in KOH due to presence of acidic hydrogen but 20 Amine does not. 30 Amine does not react at all with benzene sulphonyl chloride 09# TEST FOR CHLORIDE ION [aq.NaOH and AgNO3 test ] -- white ppt. of AgCl forms due to free chloride ion

[ In a compound when Cl attached with SP3 carbon responds this testeasy for SN reaction] 10# Lucas Test ( anh. ZnCl2 + conc.HCl )---( turbidity appears immediately for tert-alcohol, after 5 minutes for sec alcohol , after heating with primary alcohol ) 11# Acidic hydrolysis of ester + Iodoform test. ( to distinguish methyl acetate and ethyl acetate ) 12 # Reduction ( LiAlH4 ) and carbylamine test . (for nitrile and isonitrile)

JUST FOR PRACTICE ---- ORGNIC CHEMISTRY ( EXAM SPECIAL) 1# Explain why ? Give reason

by A.K.Panda

(i) Treatment of C6H5CHO and HCN gives a mixture of two isomers which cannot be separated even by very careful fractional distillation .Why ? (1) (ii) Why is vinyl chloride less reactive than ethyl chloride towards nucleophile ? (1) (iii)Why formaldehyde does not respond Aldol condensation reaction ? (1) (iv) Why CF3C+HCH3 is much less stable than isopropyl cation? (1) (v) Explain why this takes place with anti-Markownikoffs regiochemistry (1) CF3CH=CH2 + HCl CF3CH2CH2Cl (vi) Why does the reactivity of NH2 get reduced in acetanilide ? (1) (vii) Amino group is o,p-directing for aromatic electrophilic substitution . Why does aniline on nitration gives a substantial amount of meta-nitroaniline ? (1) (viii) There are two NH2 groups in semicarbazide. However, only one is involved in the formation of semicarbazones. (1) (ix) Haloalkanes react with KCN to form alkyl cyanides as main product while AgCN forms isocyanides as the chief product. Explain. (1) (x) Why sec- & tert- alkyl halides are not used during Williamsons Synthesis . (1) (xi) Why N,N-Diethylbenzenesulphonamide is not soluble in alkali . (1) (xii) Which compound will react faster in SN2 reaction with OH and why ? (CH2=CHBr and CH2=CHCH2Br ) (1) (xiii) Although phenoxide ion has more number of resonating structures than carboxylate ion , carboxylic acid is a stronger acid than phenol . Why? (1)

2#(A) Give the structures of the major product(s) which are obtained when

(i) 2-methyl-2-methoxypropane is treated with hydroiodic acid . (ii) Methyl magnesium bromide is treated with CO2 and subsequently hydrolysed . (iii) Salicylic acid is acetylated (iv) butan-1-ol is treated with Jones reagent (v) Hex-4-ene-nitrile is treated with DIBAL-H (vi) ethanoyl chloride is treated with diethyl cadmium . (vii) benzene diazonium chloride treated with DMA in presence of a base . (viii) Methanamine treated with benzoyl chloride . (ix) Propanoic acid is treated with NABH4 . (x) 1-bromo-1-methylcyclohexane is treated with alcoholic KOH (xi) Cyclohexene is treated with hot acidified KMnO4 . (xii) Cyclohehanone is treated with semicarbazide . (xiii) Benzaldehyde is treated with Acetophenone in presence of dilute NaOH . (B) How do products differ when ethyl bromide reacts separately with (i) aq . KOH and alc. KOH (ii) KNO2 and AgNO2 (iii) KCN and AgCN 3# Write chemical test to distinguish between (i) Formic acid and acetic acid (ii) C6H5CH2NH2 and C6H5NH2 ( iii) Propanoyl chloride and Propanoic acid. (iv) Vinyl Chloride and Allyl Chloride 4# Write the mechanism of (i) Hydration of propene to yield propanol . (ii) Ethanamine is converted into N-Ethylethanamide . (iii) 1-propoxypropane from propan-1-ol (iv) Reaction of HI with methoxy ethane 5 # Give the IUPAC Name of (i) Methyl vinyl ketone . (ii) Benzophenone (iii) Sulphanilic caid (iv) Aspirin (v) Terepthalic acid (vi) Adipic acid (vii) Phenetole (viii) Propiophenone (ix) DDT (x) Freon

UNIT-14# BIOMOLECULES
PART-I : Answer the following : 1# An optically active compound having molecular formula C6H12O6 is found in two isomeric forms(A) and (B) .When (A) and (B) are dissolved in water they show the following equilibrium: (A)-------------- equilibrium mixture --------------(B) [] = 1110 52.20 19.20 (i) What are such isomers called ? (ii) Can they be called enantiomers ? Justify your answer . (iii) Draw the cyclic structure of isomer (A) . 2# An optically active amino acid (A) can exist in three forms depending on the PH of the medium.If the molecular formula of (A) is C3H7NO2 then write (i) Structure of compound (A) in aqueous medium. What are such ions called ? (ii) In which medium will the cationic form of compound (A) exist ? (iii) In alkaline medium, towards which electrode will the compound (A) migrate in electric field ? 3 # When RNA is hydrolysed, there is no relationship among the quantities of different bases obtained unlike DNA ? What does this fact suggest about the structure of RNA? 4# What are reducing and non-reducing sugars ? Give two examples. .What is the structural feature characterizing reducing sugars ? 5# Write down the structures and names of the products obtained when D-Glucose is treated with (a) HI (b) Br2 Water (c) HNO3 (d) NH2OH (e) Acetic Anhydride (f) HCN (g) ammoniacal AgNO3 6# What is the significance of D and (+) in -D(+)-glucopyranose 7 # What are the expected products hydrolysis of (i) Lactose (ii) sucrose (iii) Maltose 8# What type of bonding helps in stabilising the -helix structure of proteins? 9#What is the effect of denaturation on the structure of proteins? 10# The two strands in DNA are not identical but are complementary . 11# Enumerate the reactions of D-glucose which cannot be explained by its open chain structure. 12# How do you explain the absence of aldehyde group in the pentaacetate of D-glucose?
Ans-1-(i) Anomers (ii) No, they are not enantiomers . - and -anomers are not mirror images of each other . They are not having nonsuper imposable mirror images ( which is the conditions of showing enantiomerism)

ANSWERS TO (I)

(iii) ANS-2-(i) they are called Zwitter ions (ii) In acidic medium ,the cationic form of compound will exist (iii) In alkaline medium , it will behave as anion and migrates towards anode in electric field ANS-3- This indicates that RNA does not exist as double strand but exist as single strand. DNA exist as double strand . The sequence of bases on one strand of DNA is complimentary to the sequence of bases on the other strand . Therefore , the quantities of four bases obtained on hydrolysis of DNA have relationships . Since in case of RNA there is no relationship among the quantities of bases it indicates that RNA exists in the form of single strand and not double strand ANS-4- Reducing Sugars:- All those carbohydrates which contain free aldehydic or ketonic groups

which reduce Fehlings solution and Tollens reagent are referred to as reducing sugars. Eg. Glucose, fructose, maltose, lactose. Non- Reducing Sugars :- All those carbohydrates which do not contain free aldehydic or ketonic groups cannot reduce Fehlings solution and Tollens reagent are referred to as reducing sugars .e.g sucrose . These two monosaccharides are held together by a glycosidic linkage between C1 of -glucose and C2 of -fructose. Since the reducing groups of glucose and fructose are involved in glycosidic bond formation, sucrose is a non reducing sugar.

ANS-5-

(a) n-hexane (b) Gluconic acid (c) Saccharic acid or glucaric acid (d) Glucose monooxime (e) Glucose Pentaacetate (f) Glucose cyanohydrin (g) Gluconic acid

ANS-6- D before the name of glucose represents the configuration whereas (+) represents

dextrorotatory nature of the molecule. [*** It may be remembered that D and L have no relation with the optical activity of the compound.] ANS-7 : (i) -D-Galactose and -D-Glucose (C-1 and C-4 glycosidic linkage) (ii) - D(+)-Glucose and -fructose (C1C2 glycosidic linkage) (iii) -D Glucose and -D- Glucose (C-1 and C-4 glycosidic linkage) Ans-8:-Due all possible hydrogen bonds, by twisting into a right handed screw (helix) with the NH group of each amino acid residue hydrogen bonded to the >C= O of an adjacent turn of the helix . Ans-9:- During denaturation 2 and 3 structures are destroyed but 1 structure remains intact . Due to this, globules unfold and helix get uncoiled and protein loses its biological activity Ans-10: Two nucleic acid chains are wound about each other and held together by hydrogen bonds between pairs of bases. The two strands are complementary to each other because the hydrogen bonds are formed between specific pairs of bases. Adenine forms hydrogen bonds with thymine whereas cytosine forms hydrogen bonds with guanine. Ans-11# The following experimental facts could not be explained by its open chain structure (i) Despite having the aldehyde group, glucose does not give 2,4-DNP test, Schiffs test and it does not form the hydrogensulphite addition product with NaHSO3. (ii). The pentaacetate of glucose does not react with hydroxylamine indicating the absence of free CHO group. (iii) Glucose is found to exist in two different crystalline forms which are named as and -form. Ans-12# Pentaacetate of D-glucose does not react with hydroxylamine indicating the absence of free CHO group .

1. 2. 3. 4. 5. 6. 7.

PART-II Cellulose in the form of plants is a food for cattles but not for human beings.Explain. Upon heating glucose with tollens reagent, a shining mirror is obtained.Explain why? Name a water soluble vitamin which is a powerful antioxidant. Except for B12, all other vitamins of this group B should be supplied regularily in diet, why? Name the protein responsible for blood clotting . Glucose form an oxime but glucose pentaacetate does not why? Name the following a) A water soluble vitamin b) A vitamin which is neither water soluble nor fat soluble c) What is meant by avitaminosis? d) Vitamin which prevent loss of hairs e) The disease caused by deficiency of B12

1. 2.

3. 4. 5. 6. 7.

ANSWER KEY PART-II: UNIT 14 Due to absence of enzymes needed for breakdown of glucose in human beings. CHO COOH (CHOH) 4 + 2[Ag(NH3) 2]OH (CHOH) 4 + 2Ag +4NH3 + 2H2O CH2OH CH4OH Vitamin C Because it can be stored in liver while others could not. Fibrinogen Due to absence of free aldehyde group on glucose pentaacetate. a) Vitamin B or C b) Vitamin H c) Deficiency of more than one vitamin in human body d) Vitamin H (Biotin) e) Anaemia

Q.I# Answer the following: (1) How double bonds in rubber molecules influence their structure and reactivity ? (2) Write the free radical mechanism for the polymerization of ethene (3) Write the name and structure of one of the common initiators used in free radical addition polymerisation. (4) Is ( NH-CHR-CO )n, a homopolymer or copolymer? (5) Explain the term copolymerisation and give two examples. (6) Discuss the main purpose of vulcanisation of rubber. Or Mention advantages of Vulcanised rubber over natural rubber . OR , How does vulcanization change the character of natural rubber ? (7) Can a copolymer be formed in both addition and condensation polymerization ? Explain with examples. (8) What are biodegradable polymers?Give two examples. (9)(a) What is the role of Benzoyl peroxide in polymerization of ethane .(b)How do you explain the functionality of a monomer (10) What are LDPE and HDPE ? How are they prepared

UNIT-15: POLYMERS

11). Give two examples of biodegradable polymers. 12). What is plastisizer? 13).. What is the commercial name of PMMA? What is its use? 14).the monomers for the following a) Teflon b) Cellulose c) Neoprene 16)What is the main constituent of bubble gum? 17) Why are the numbers 66 and 6 put in the names of nylon66 and nylon 6?

d) Polythene

Q.II # Arrange the following polymers in increasing order of Intermolecular Forces ? (a) Nylon-66 , Buna-S , Polythene (b) Polyisoprene , PTFE , Decron (c) Nylon-6 , PVC , Neoprene

UNIT 15:

1# How double bonds in rubber molecules influence their structure and reactivity ? Ans-From the structural point of view, the natural rubber is a linear cis-1,4- polyisoprene(2-methyl-1, 3-butadiene). In this polymer the double bonds are located between C2 and C3 of isoprene units. This cis-configuration about double bonds do not allow the chains to come closer for effective attraction due to weak intermolecular attractions. Hence, the natural rubber has a coiled structure and it can be stretched like a spring and exhibits elastic properties. The double bonds in the rubber molecules, in additions to determining their configurations act as reactive sites. The allylic --CH2- - .On vulcanization, sulphur establishes cross links at these reactive sites .Thus ,the rubber gets stiffened and intermolecular movement of rubber springs is prevented resulting in change of physical character of rubber

ANSWER KEY Answers

2# FREE RADICAL MECHANISM-(P.N-329) 3# Free radical generating initiator (catalyst) like benzoyl peroxide, acetyl peroxide, tert-butyl peroxide

4# Homopolymer because of similar type of monomer 5# Copolymerisation is a polymerisation reaction in which a mixture of more than one monomeric species is allowed to polymerise and form a copolymer. For example, (1) Buna-S, a mixture of 1, 3 butadiene and styrene can form a copolymer.(chain growth) (2) Nylon-66 , a mixture of Adipic acid and hexamethylene diammine (step growth) 6# Vulcanised rubber Raw rubber + Sulphur + additive(ZnO) at 373K to 415 K Vulcanised rubber On vulcanization sulphur forms cross links at the reactive sites of double bonds and thus the rubber gets stiffened .Excellent elasticity, Low water absorption tendency, resistance to oxidation and organic solvents , Hard ,non-sticky ,high tensile strength ,insoluble in all common solvents , works at higher temperature range from -400C to 1000 C . High abrasion resistance 7# Yes. addition polymerization--- Buna-S, a mixture of 1, 3 butadiene and styrene can form a copolymer.(chain growth) and condensation polymerization--- Nylon-66 , a mixture of Adipic acid and hexamethylene diammine (step growth) 8# Synthetic biodegradable polymers contain functional groups similar to the functional groups present in biopolymers which can be easily degraded through environmental process by microorganisms. Aliphatic polyesters are one of the important classes of biodegradable polymers e.g. PHBV 1. Poly- -hydroxybutyrate co--hydroxy valerate (PHB ) [ 3-hydroxybutanoic acid and 3-hydroxypentanoic acid] and

PHBV undergoes bacterial degradation in the environment. 2. Nylon 2nylon 6 . It is an alternating polyamide copolymer of glycine (H2NCH2COOH) and amino caproic acid [H2N (CH2)5 COOH] 9# (a)Benzoyl peroxide acts as a free radical generating initiator (catalyst) in free radical polymerization reaction (b) Functionality is the number of bonding sites in a monomer . 10# Low Density PolyeheneIt is obtained by the polymerization of ethene under high pressure of 1000 to 2000 atmospheres at a temperature of 350 K to 570 K in the presence of traces of dioxygen or a peroxide initiator (catalyst). The low density polythene (LDP) obtained through the free radical addition and H-atom abstraction has highly branched structure. High Density PolyeheneIt is formed when addition polymerisation of ethene takes place in a hydrocarbon solvent in the presence of a catalyst such as triethylaluminium and titanium tetrachloride (Ziegler-Natta catalyst) at a temperature of 333 K to 343 K and under a pressure of 6-7 atm 11# PHBV Poly- beta- hydroxybutyrate- Co beta hydroxyl valerate and Polyglycolic acid and Polylactic acid 12# Those plastics which do not soften on heating can be made sof by addition of certain organic compounds called plasticizers. 13# Polymethyl methacrylate 14# a) Tetrafluoro ethane (b) Beta D-Glucose (c) 2 chloro 1,3 butadiene (d) Ethene 15# Styrene- Butadiene 16# In nylon 66 both monomers have 6 numbered carbon chain and in nylon 6 only one monomer is present which has six membered carbon chain. ANSWER-II:- (a) Buna-S < Polythene < Nylon-66 (c) Neoprene < PVC < Nylon-6 (b) Polyisoprene < PTFE < Decron (d) SBR < Polystryne < Terylene

UNIT-16 : Chem in everyday life

1# Why are cimetidine and ranitidine better antacids than sodium hydrogencarbonate or magnesium or aluminium hydroxide ? (TBQ) 2#(a) While antacids and antiallergic drugs interfere with the function of histamines, why do

these not interfere with the function of each other ?

(b) Metal hydroxides are better alternatives than Sodium bicarbonates for treating acidity. 3# Sleeping pills are recommended by doctors to the patients suffering from sleeplessness but it is not advisable to take its doses without consultation with the doctor. Why ? (TBQ) 4# Explain the term, target molecules or drug targets as used in medicinal chemistry. 5 # Account for the following:(i) aspirin drug helps in the prevention of heart attack (ii) Detergents are non-biodegradable while soaps are biodegradable (iii) Diabetic patients are advised to take artificial sweeteners instead of natural sweeteners 6# Low level of noradrenaline is the cause of depression. What type of drugs are needed to cure this problem ? Name two drugs. 7# Define the term chemotherapy. What are the criteria of classification of drugs. 8# With reference to which classification has the statement, ranitidine is an antacid been given? (TBQ) 9# Differentiate between (i)Antiseptic and disinfectant (ii)Soaps and Detergents (iii)Antagonist and agonists (iv) Enzymes and Receptors

10#Name a drug used for treatment of tuberculosis. What type of drug it is? 11# What are sulpha drugs? Give two examples. 12# Which of the following is hypnotic? Whats its function? a) Luminal b) Catechol c) salol d) Paracetamol 13# What is the use of a) Benadryl b) BHA c) Sodium Benzoate d) Progesetrone 14# Name the drugs which are used to control allergy. 15# Classify synthetic detergents giving an example in each case. UNIT 16 : ANSWER KEY 1# Sodium hydrogencarbonate or magnesium or aluminium hydroxide used as antacids These treatments control only symptoms, and not the cause. Therefore, with these metal salts, the patients cannot be treated easily. Histamine, stimulates the secretion of pepsin and hydrochloric acid in the stomach. cimetidine (Tegamet) prevent the interaction of histamine with the receptors present in the stomach wall. This resulted in release of lesser amount of acid. 2# (a) Antiallergic and antacid drugs work on different receptors. Antihistamines (antiallergic drugs) do not affect the secretion of acid in stomach because they do not interact with receptors present in the stomach wall.

(b) Excessive hydrogencarbonate can make the stomach alkaline and trigger the production of even
more acid. Metal hydroxides are better alternatives because of being insoluble, these do not increase the pH above neutrality.

3 # Most of the drugs taken in doses higher than recommended may cause harmful effect and act as poison. Therefore, a doctor should always be consulted before taking medicine. 4# Target molecules or drug targets are the macromolecules such as carbohydrates , proteins,lipids,nucleic acids with which the drug interacts in our body to produce therapeutic
effect

5 #(a)Aspirin prevents platelet coagulation. Because of its anti blood clotting action, aspirin finds use
in prevention of heart attacks. (b) Main problem that appears in the use of detergents is that if their hydrocarbon chain is highly branched, then bacteria cannot degradethis easily. Slow degradation of detergents leads to their accumulation. Effluents containing such detergents reach the rivers, ponds, etc. These persist in water even after sewage treatment and cause foaming in rivers, ponds and streams and their water gets polluted. (c) natural sweeteners contains calorie i.e sugars which cannot be metabolized by diabetic patients as they do not have the insulin to metabolise them

6# Antidepressant drugs. E.g.- Iproniazid and Phenelzine. 7# Use of chemicals for therapeutic effect is called chemotherapy. Drugs can be classified mainly on
criteria outlined as follows: (a) On the basis of pharmacological effect (d) On the basis of molecular targets (b) On the basis of drug action (c) On the basis of chemical structure

8# This statement refers to the classification according to pharmacological effect of the drug because any drug which will be used to counteract the effect of excess acid in the Antiseptics
*Antiseptics are chemical substances which prevent the growth or kill the microorganisms and not harmful to the living human tissues *Antiseptics are applied to the living tissues such as wounds, cuts,ulcers and diseased skin surfaces. *Examples are furacine,soframicine, etc. These are not ingested like antibiotics.

Disinfectants
*Disinfectants are chemical substances which kill the microorganismsor stop their growthbut are harmful to human tissues *Disinfectants are applied to inanimate objects such as floors, drainage system, instruments, etc. * 1% Phenol , 0.2 0.4 ppm Chlorine in aqeous solution etc

stomach will be called antacid.

9# (i)

(ii) Soaps 1.Soaps are sodium salts of higher fatty acids 2.Soaps are prepared from natural oils and fats 3 .Soaps forms insoluble salts(curdy white ppt) with calcium and magnesium which are presenting hard water and hence cannot be used in hard water 4.Soaps cannot be used in acidic medium as they are decomposed into carboxylic acids in acidic medium 5.Soaps are biodegradable

Detergents 1.Synthetic detergents are sodium alkyl sulphates or sodium alkyl benzene sulphonates with alkyl groups having more than 10 carbon atoms 2.Synthetic detergents are prepared from the hydrocarbon of petroleum 3.Calsium and magnesium salts of detergents are soluble in water and, therefore ,no curdy white ppt. are obtained in hard water and hence ,can be used even in hard water 4.They can be used in acidic medium as they are the salts of strong acids and are not decomposed in acidic medium 5.Some of the synthetic detergents are not biodegradable

(iii) Antagonists. Drugs that bind to the receptor site and inhibit its natural function are called antagonists. These are useful when blocking of message is required.

Agonists. There are other types of drugs that mimic the natural messenger by switching on the receptor, these are called agonists

(iv) Enzymes proteins which perform the role of biological catalysts in the body are called enzymes

Receptors Proteins which are crucial to communication system in the body are called receptors

10# Streptomycin and it is narrow spectrum antibiotic 11# A group of drugs which are derivatives of sulphanilamide and are used in place of antibiotics. Examples Sulphadiazine and Sulphanilamide 12# Luminal is sleep inducing drug 13# a) Antihistamine b) Antioxidant c) Preservative d) Antifertility drug 14# Antihistamines 15# These are cleansing agents which have all the properties of soap but actually contain no soap. They are a) Anionic Detergents e.g. sodium lauryl sulphonate b) Cationic detergent e.g. Cetyltrimethylammonium Bromide c) Non Ionic detergents e.g. Detergent formed when stearic acid reacts with polyethylene glycol