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SERIES-1

41)

Explanation Gold salts like Auranofin, Sodium aurothiomalate, aurothioglucose are used to treat rheumatoid arthritis. Additional information: 1) cis platin is used in treatment of cancer. 2) Iron in the form of ferrous sulfate, ferrous gluconate are used in treatment of iron deficiency anemia. Additional questions: 41.1) Give the structure, hybridisation and magnetic moment of cis-platin? 41.2) Write its action on cancer cells. NOTE: Answers to the additional questions are also given at the end. 42) Non-heme iron-sulfur proteins are involved in: 1. Electron transfer. 2. Proton transfer. 3. Both electron and proton transfer 4. Oxygen transfer.

Explanation Iron-sulfur proteins are proteins characterized by the presence of iron-sulfur clusters containing sulfide-linked di-, tri-, and tetrairon centers in variable oxidation states. Eg., Ferredoxins, as well as NADH dehydrogenase, hydrogenases, nitrogenase etc., Iron-sulfur clusters are best known for their role in the oxidation-reduction reactions of mitochondrial electron transport. Additionally some Fe-S proteins regulate gene expression. Fe-S proteins are vulnerable to attack by biogenic nitric oxide. In most iron-sulfur proteins, the clusters function as electron-transfer groups. Additional information: 1) Ferredoxins: are small proteins containing iron and sulfur atoms organized as iron-sulfur

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Complexes of which of the following metals are used in the treatment of rheumatoid arthritis: 1. Gold 2. Ruthenium 3. Iron 4. Copper

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clusters. These biological "capacitors" can accept or discharge electrons, the effect being change in the oxidation states (+2 or +3) of the iron atoms. This way, ferredoxin acts as electron transfer agents in biological redox reactions. The following diagram illustrates the redox scheme between low-potential and high-potential (HiPIP) ferredoxins containing Fe4S4clusters. The formal oxidation numbers of the iron ions can be [2Fe3+, 2Fe2+] or [1Fe3+, 3Fe2+] in low-potential ferredoxins. The oxidation numbers of the iron ions in high-potential ferredoxins can be [3Fe3+, 1Fe2+] or [2Fe3+, 2Fe2+]
S S S S S S S

Fe
S S

Fe
S S

Fe
S S

Fe
S Fe S

1-

+e-e-

Fe
S Fe

2-

+e-e-

Fe
S Fe

3-

Following is Fe2S2 type of ferredoxin.

Cys S

Note: High potential iron-sulfur proteins (HiPIPs) form a unique family of Fe4S4 ferredoxins that function in anaerobic electron transport chains. Additional questions: 42.1) The vitamin riboflavin is part of the ______ molecule. A) ferredoxin B) FAD C) pyridoxal phosphate D) pyrophosphate E) NAD+

42.2) Ferredoxin (Fd) is a sulfur-containing protein which undergoes redox reactions in a variety of microorganisms; Fdox+ + e- -------> Fdred , Eo = 0.439V @pH = 7.0. Will Fd generate hydrogen gas from hydronium ions dissolved in water if the standard potential for the reduction 2H+ + 2e- ---------> H2 is -0.421 at pH=7.0. Show the redox reaction and explain your answer. 42.3) In the following reaction ferredoxin-1 is the oxidised form of ferredoxin. State whether this statement is true or false? 43)
nitrite reductase NO 2 - + ferredoxin-1 NH 3 + ferredoxin-2 Active catalytic species for hydroformylation is 1. RuCl2(PPh3)3 2. HCo(CO)3 3. RhCl(PPh3)3

Explanation Hydroformylation, also known as oxo synthesis, is an important industrial process for the

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Fe
S

Fe

Fe

Cys

Fe

S S

Fe

Cys

Cys

4. K2PtCl6

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production of aldehydes from olefins. In this reaction a formyl group (CHO) and a hydrogen atom are added to a carbon-carbon double bond. H2 + CO + CH3CH=CH2 -----> CH3CH2CH2CHO (normal) --commercially desired product H2 + CO + CH3CH=CH2 -----> (CH3)2CHCHO (iso) The reaction begins with the generation of coordinatively unsaturated metal hydrido carbonyl complex such as HCo(CO)3 and HRh(CO)(PPh3)2. Therefore, Answer is 2 and not 3. Additional information: * It is an example for homogeneous catalysis. * The linear / iso product ratio can be improved by using bulky ligands (see below). * HRh(CO)(PPh3)2 (second generation catalyst) is a better catalyst than HCo(CO)3 (first generation catalyst because i) pressures around 20-30 atm are sufficient. ii) the major product is linear isomer of aldehyde (highly selective). iii) the side reactions like hydrogenation can be minimized. * Third generation water soluble rhodium catalyst uses TPPTS ligands instead of triphenyl phosphine. In this case the water insoluble products can be separated easily from the catalyst. TPPTS = 3,3',3''-Phosphinidynetris(benzenesulfonic acid) trisodium salt

* HCo(CO)3 is generated as follows

Co 2 (CO)8

Octacarbonyl dicobalt

HCo(CO)4

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O S Na O
+ -

O Na O

O
-

O Na

H 2

2HCo(CO) 4

tetracarbonylhydridocobalt(I) (trigonal bipyramidal)

HCo(CO)3

CO

tricarbonylhydridocobalt(I) (tetrahedral)

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Mechanism

H OC Co CO OC R

16 VE (VE = valence electrons)

H OC Co CO OC

OC OC

Co

linear

OC OC OC

Co

OC OC

Co

O H OC OC Co CO H

O H

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18 VE reverse beta elimination
H R H R

16 VE

CO

OC

Co

OC

CO

iso

If bulky groups like tributyl phosphine(PBu3) are used then the formation of iso product is DISFAVORED due to steric and electronic effects. Now a days, HRh(CO)(PPh3)2 is used to achieve this effectively.

CO

OC

18 VE

OC

Co

CO

OC

CO

16 VE

CO

OC

Co

OC

CO

H2 oxidative addition
O R H OC OC Co CO H

reductive elimination
H R O R H

OC Co CO OC

16 VE

to the cycle

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Additional questions: 43.1) Write the IUPAC names of HCo(CO)3 and HRh(CO)(PPh3)2 and mention the oxidation states of Co and Rh. 43.2) Write the mechanism of hydroformylation of propene catalysed by HRh(CO)(PPh3)2. Mention the major product formed during the reaction. 43.3) What is Wilkinsons catalyst? Mention its use. 44) The unit of molar absorptivity is: 1. L mol1 cm1 2. L1 mol cm1

3. L mol cm1

4. L mol cm

Additional information Absorbance (A) = -log10 T = -log10 I /Io (T = transmittance = I /Io ) Where I = intensity of the transmitted light Io = intensity of the initial incident light * Remember transmittance (T) is inversely related to absorbance (A) * is a is a measure of the amount of light absorbed per unit concentration at a given wavelength. * is an intrinsic property of the compound; * The actual absorbance, A, of a sample is dependent on the pathlength l (in cm) and the concentration c (molar conc.) of the species via the Beer-Lambert law, A = cl. * It is a limiting law. It is only valid for dilute solutions. At higher concentrations, the electrostatic interactions between neighbouring molecules distort the energy levels which cause deviation from the law. * Deviations also occur when the molecules undergo chemical change in solutions (this may occur due to change in concentration or pH). eg., Yellow chromate and orange dichromate are in equilibrium with each other in aqueous solution. The equilibrium shifts to the right if pH is decreased (when acid is added) and shifts to the left if pH is increased (when base is added).
2 CrO 4 2- (aq) + 2 H + (aq) Cr2O 7 2- (aq) + H 2O (l) yellow orange

Hence the absorbance for this solution depends on the pH Additional questions: 44.1) What is the concentration of a solution whose absorbance is 0.21 when placed in a tube of path length 10 cm ( max = 245 nm and max = 31,500 M-1cm-1) 44.2) If the visible spectrum of [Ti(OH2)6]3+ has an absorbance maximum at 0.9 at 510 nm and the spectrum was recorded on a 0.20 M solution in a 1.0 cm cell, what would be the value of

510 ?

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Explanation: Beer-Lambert law A = .c.l Where A = absorbance c = molar concentration l = pathlength (in cm) = molar extinction coefficient or molar absorptiviy = A / cl Hence the units are usually in M-1cm-1 or L mol-1cm-1 ( A has no units: see below) As 1 liter = 1000 cm3, the unit may be sometimes cm2 mol-1, especially in old literature. (note: = pronounced as epsilon)

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44.3) Transferrin is an iron-transport protein found in blood. It is colourless in the absence of iron. Desferrioxamine B is an iron chelator used to treat patients suffering from iron overload. It is also colourless in the absence of iron. The following data was obtained in aqueous solution using a 1.00 cm path length cell for both species when fully complexed with iron: ----------------------------------------------------------------------------------

45)

Gelatin is added during polarographic measurements to: 1. reduce streaming motion of falling mercury drop 2. increase Id 3. increase E1/2 4. eliminate residual current

Explanation: When a surfactants like gelatin, Triton X-100 are added to the solution, the streaming effects at the drop surface are minimized, and the polarographic wave approaches the limiting current smoothly. Additional information: * Polarography is the measurement of the current that flows in solution as a function of an applied voltage. The electrode processes are studied by using two electrodes - one polarizable and one unpolarizable * Dropping Mercury Electrode (DME) is an example for polarizable working electrode used in polarography. * A polarogram is a curve visualizing the processes occurring in the course of electrolytic polarization of the DME. * A polarographic wave or polarogram is obtained by applying voltage. This experiment employs usually two methods of applying the voltage, a linear sweep (DC) and a differential pulse. * Nowadays a Static Mercury Drop Electrode (SMDE) is used which provides a more sensitive measurement of the faradaic current than the more traditional DME. * One of the difficulties in evaluating a polarogram is the measured current oscillates permanently between a minimum and maximum value. This behavior is caused by the nonconstant electrode surface area. Usually the current rises as the drop surface area grows, and decreases as the drop falls. * Polarography differs from voltametry in that it employs the electrode (like DME) whose surface is continuously renewed. 46) The element that shows both +3 and +4 oxidation states is: 1. Cerium 2. Promethium 3. Gadolinium 4. Holmium

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max / L mol1 cm1 iron-transferrin iron-desferrioxamine B ----------------------------------------------------------------------------------428 3540 2730 470 4170 2290 ----------------------------------------------------------------------------------Use this information to predict the absorbance at 470 nm of a solution that is 11.0 M in iron-transferrin and 69.5 M in iron-desferrioxamine B, assuming both are fully complexed and that the cell path length is 1.00 cm. 44.4) 1,10-Phenanthroline is added during the quantitative analysis of Fe(II) by UV-visible spectroscopy. Explain why? max / nm

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Explanation: Usually lanthanoids exhibit, +3 oxidations states. (why?) But some of them also exhibit +2 and +4 oxidation states due to stable half filled (4f7) or empty (4f0) or completely filled f-sublevel. Eg., Ce4+ has 4f0 configuration. -very stable Eu2+ has 4f7 configuration. -very stable Yb2+ has 4f14 configuration. - appreciably stable Additional information: * Ce4+ is a good oxidising agent as it can be reduced to Ce3+ easily. It can oxidize water also (Eo of Ce4+ /Ce3+ is +1.74 V), but very slowly. Hence Ce(IV) can be used as a good analytical reagent in aqueous medium. * But Eu2+ is a reductant as it can be oxidized to Eu3+, which is the common oxidation state of lantahnoids. * La3+, Ce4+ with 4f0 and Yb2+, Lu3+ with 4f14 configurations - are colorless and diamagnetic. * Lanthanoids exhibit +3 oxidation states commonly because first three ionization enthalpies are small. * Both Ce and Eu can be separated easily from the rest of the lanthanoids due to their different chemical behaviour. For example, Ce 3+ can be easily oxidised to Ce4+ ion which being less basic than other Ln3+ undergoes hydrolysis easily. Hence Ce3+ (in a mixture of Ln3+) is oxidised by KMnO4 or bleaching powder to Ce4+ which can be precipitated as basic salt or hydroxide. Note: Cation with high charge is smaller in size and more acidic (or less basic).

* Yttrium oxide-sulfide activated with europium is used as the red phosphor(?) in color CRTs(Cathode Ray Tubes used in TVs). A phosphor is a substance that exhibits the phenomenon of phosphorescence (sustained glowing after exposure to energized particles such as electrons or ultraviolet photons). Additional questions: 46.1) Which of the following carbonate-fluoride mineral contains all the lanthanoids? 1) Monazite 2) Bastnasite 3) Pitch blende 4) Zirconite 46.2) What is the difference between lanthanoids and lanthanides? 46.3) Describe the ion exchange method of separation of lanthanoids. 46.4) What is the principle involved in solvent extraction of lanthanoids by using tri-nbutylphosphate? 47) The number of 3c, 2e BHB bonds present in B4H10 is 1. 2 2. 3 3. 4 Explanation: * B4H10 is called tetraborane(10).

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H 2O oxidation Ce3 Ce 4 Ce(OH )4

4. 0

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B B B B

B B B

B4H10

Arachno structure of B4H10 , showing boron atoms at the four vertices of octahedral geometry. Note: In these structures the lines do not represent the actual bonds. Only concentrate on the positions.

There are four BHB bonds and also contains a BB bond. It is an arachno borane. Additional information: * Nomenclature: Boranes are named as follows: a) The Latin prefixes mono-, di-, tri-, etc. are used before "borane" to indicate the number of boron atoms in the compound. b) Immediately following the "e" in "borane" the number of hydrogen atoms is placed in parentheses using Arabic numerals. Example: B5H11 is pentaborane(11). c) Whereas the names of anions end in ate rather thanane. The numbers of both boron and hydrogens are indicated by Latin prefixes Example: B10H102- is decahydrodecaborate(2-) * Structure: Boranes fall into five structure categories. 1) closo BnHn2- --- n vertices of n cornered polyhedron are occupied by boron atoms. 2) nido BnHn+4 --- n vertices of (n+1) cornered polyhedron are occupied by boron atoms. 3) arachno BnHn+6 --- n vertices of (n+2) cornered polyhedron are occupied by boron atoms. 4) hypho BnHn+8 --- n vertices of (n+3) cornered polyhedron are occupied by boron atoms. 5) Conjuncto boranes formed by joining two or more preceding types. Hypho and conjuncto boranes are less common and not discussed here.

Illustrations: 1) closo BnHn2- : Eg., Hexahydrohexaborate(2-) B6H62- has regular octahedron structure. Six boron atoms occupy the vertices of octahedron. It has a closed symmetrical structure.
2-

Note: These anionic closo-BnHn2- are examples for 3D aromaticity. Whereas neutral BnHn+2

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H B H B B B H B B H H H

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are unstable and not known. 2) nido BnHn+4 : Eg., In Pentaborane(9), B5H9 , the boron atoms occupy the five vertices (n) of the regular, six cornered, octahedron (with n+1 corners).
H B H H B B H H B H H B H H

Structural relations between Closo, Nido and Arachno boranes are illustrated below

How to know the type and structure of a borane? Eg., B5H11 - Pentaborane(11) has the BnHn+6 formula and hence an arachno borane. Remember it should have five boron atoms (as n=5) occupying five vertices of polyhedron with seven vertices (as n+2=7) i.e., two vertices are missing. Hence its structure is derived from pentagonal bipyramidal structure.

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H H H B B H H H H B H B H H
B B B

3) arachno BnHn+6 : Eg., In B4H10 ( Tetraborane(10) ), only four vertices are occupied by Boron atoms. (Already illustrated in previous page)

Closo borane - all the vertices are occupied.

Nido borane - one vertex is removed

B B B

Arachno borane - two vertices are removed.

Only the positions of boron atoms are shown. Lines may or may not represent the actual bonds between them.

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B B B B B B B

B B B B

B B B

closo Eg., B7H72-

nido Eg., B6H10

arachno Eg., B5H11

Only the positions of boron atoms are shown. Lines may or may not represent the actual bonds between them.

* The most stable boron hydrido clusters are closo B10H102- and B12H122-. They resemble electron rich aromatic compounds. Additional questions: 47.1) Which one of the following boranes is classified as a nido-borane? 1) B2H6 2) B2H7 3) B4H10 4) B12H122 47.2) Which of the following is an arachno borane? 1) [B6H6]22) [B5H9] 3) [B2H6] 4) [B6H12] 48) In BrF3 as a solvent SnF4 and KF behave as 1. acid and base, respectively 2. base and acid, respectively 3. acids 4. bases

Explanation: KF contains F- ion which can donate electron pairs and hence acts as a Lewis base. BrF4- is the solvent anion formed. F- + BrF3 --------> BrF4SnF4 acts as a Lewis acid as Tin (Sn) can expand its octet (due to presence of available empty d-orbitals) and accepts electron pairs. BrF2+ acts as cation of the solvent. SnF4 + BrF3 --------> BrF2+ +SnF5Additional information: Remember BrF3 auto-dissociates as follows BrF3 --------> BrF4- + BrF2+ And according to solvent system concept, the cation resulting from auto-dissiciation is acid and the anion resulting from auto-dissiociation is a base. Hence the solute which increases concentration of cation (BrF2+)is an acid and which increases the concentration of anion (BrF4-)is a base. Compare this analogy with H2O solvent system. Additional questions: 48.1) The following reaction can be viewed as a Lewis acid base reaction. Explain. 2 K2MnF6 + 4 SbF5 --------> 4 KSbF6 + 2 MnF3 + F2

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48.2) The conductivity of BrF3 is increased by adding either AgF or SnF4. Explain. 48.3) AlF3 is insoluble in liquid HF, but dissolves if NaF is present. When BF3 is added to the solution, AlF3 precipitates. Explain? 48.4) The magic acid HF + SbF5 is a super acid. It is the strongest acid known. It can even protonate methane and alkenes. Explain? 48.5) List the following acids in order of their acid strength in aqueous solutions. 1) H2SO4 2) H3AsO4 3) HMnO4 4) H2SO3 48.6) In the reaction : Cl2 + ClF + SbF5 ---------> [Cl3] [SbF6] the role of chlorine is to 1) stabilize Cl+ 2) fuction as Lewis acid 3) function as Lewis base 4) form the cation 49) The effective nuclear charge (Z*) for the 1s electron of 8O according to Slaters rules is nearly 1. 4.55 2. 3.45 3. 7.65 4. 5.451 Explanation: According to Slaters rules Z* or Zeff = Z - s = 8 - 0.3 = 7.7

Additional Information: Slaters rules: * In multi electron atoms the electrons in the outer shells experience less than the actual nuclear charge owing to shielding or screening of other intervening electrons. * This effective nuclear charge (Z* or Zeff) is calculated by using following equation Effective nuclear charge = Z* = Z - s Where Z = atomic number s = shielding or screening constant ( also represented by S or ) * Slaters rules are used to provide a value to the shielding constant as follows. * Firstly, the electrons are arranged in to a sequence of groups that keep s- and p- orbitals with the same principal quantum number together, but otherwise progresses with the orbital ordering with increasing principal quantum number (ignore filling irregularities): [1s] [2s,2p] [3s,3p] [3d] [4s,4p] [4d] [4f] [5s, 5p] [5d] etc. * Any electrons to the right of the electron of interest contributes no shielding. Only the electrons left to the electron of interest contribute to the shielding constant. * The shielding constant for each group is formed as the sum of the following contributions: 1. An amount of 0.35 from each other electron within the same group except for the [1s] group, where the other electron contributes only 0.30. 2. If the group is of the [s p] type, an amount of 0.85 from each electron with principal quantum number one less and an amount of 1.00 for each electron with an even smaller principal quantum number. 3. If the group is of the [d] or [f], type, an amount of 1.00 for each electron with a smaller principal quantum number. * For example, for the iron atom which has nuclear charge 26 and electronic configuration 1s22s22p63s23p63d64s2 the screening constant, and subsequently the effective nuclear charge for each electron can be deduced as For 4s: s = (1 x 0.35) + (14 x 0.85) + (10 x 1) = 22.25

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Z* = 26 - 22.25 = 3.75

For 3d:

s = (5 x 0.35) + 0 Z* = 26 - 19.75 = 6.25 s = (7 x 0.35) + (8 x 0.85) Z* = 26 - 11.25 = 14.75 s = (7 x 0.35 ) + (2 x 0.85) Z* = 26 - 4.15 = 21.85 s = 1 x 0.30 Z* = 26 - 0.30 = 25.7

(18 x 1) = 19.75

For 3s, 3p:

(2 x 1) = 11.25

For 2s, 2p:

= 4.15

For 1s:

= 0.30

Additonal questions: 49.1) Calculate Z* for a valence electron in fluorine. 49.2) Calculate Z* for a 6s electron in Platinum, given the electronic configuration (1s2)(2s2,2p6)(3s2,3p6) (3d10) (4s2,4p6) (4d10) (4f14) (5s2,5p6) (5d8) (6s2) 49.3) The first ionization energy for hydrogen is 1310 kJ.mol1 while the first ionization energy for lithium is 520 kJ.mol1. Explain. 50) Among the species O2+, O2 and O2, the order of first ionization energy is 1. O2+ < O2 < O2 2. O2 < O2 < O2+ 3. O2 < O2+ < O2 4. O2+ < O2 < O2 Explanation: * Greater the positive charge, greater is the ionization energy. 51) CO bond order is lowest in 1. uncoordinated CO 2. CO bonded to one metal 3. CO bridging two metals 4. CO bridging three metals

52)

Explanation: * The most unstable species among the following is 1. Ti(C2H5)4 2. Ti(CH2Ph)4 3. Pb(CH3)4 4. Pb(C2H5)4

55)

On oxidative addition of O2 to Ir(CO)Cl(PPh3)2, the oxidation state and coordination number of Ir changes, respectively, by 1. 1 and 3 2. 2 and 2 3. 3 and 1 4. 2 and 3

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Explanation:
PPh3 C Ir Cl 179 pm PPh3 O O C 190 pm Cl PPh3 Ir O PPh3 O

+ O2 Oxidative Addition

Ir(CO)Cl(PPh3)2, trans-chloridocarbonylbis(triphenylphosphine) iridium(I)

Ir(CO)Cl(O2)(PPh3)2

* Ir(CO)Cl(PPh3)2 is a square planar complex which is often referred to as Vaskas compound. The oxidation state of Ir is +1. Co-ordination number is 4. (contains 16 VE) * During oxidative addition (not simple addition) of O2 the oxidation state is changed to +3. The compound formed is Ir(CO)Cl(O2)(PPh3)2. It is octahedral (a little bit distorted), and hence C.N is 6. (contains 18 VE) * The Dioxygen added is in peroxidic form (O22-) and not in superoxidic form (O2-). * Therefore both oxidation state and coordination number are changed by 2 (oxidation state from +1 to +3 whereas C.N from 4 to 6). Additional information: * Vaskas complex is said to be co-ordinatively unsaturated as it contains 16 valence electrons in Iridium(I). Hence it can bind to ligands and expand its valence electrons to 18 by undergoing oxidative additions. During this process, the oxidation number of Ir is changed to +3. * The C-O stretching frequency is increased from 1967 cm-1 to greater than 2000 cm-1 during oxidative addition reactions. It is due to reduction of amount of -back bonding from Ir to C and at the same time strengthening of C-O bond. (Refer to Qtn: 51) * Remember, the Ir-C bond length is decreased and C-O bond length is increased during oxidative addition. 57) Among the following molecules, the dipole moment is the highest for 1. NH3 2. trans-[PtCl2(NH3)2] 3. BF3 4. NF3 Explanation:
F
Cl Pt NH3

N H H H
NH3

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B
Cl

N F
F

F F

* Only NH3 and NF3 have dipole moments. NF3 has highest dipole moment, as the magni-

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tude of N-F bond moment is larger. * trans-[PtCl2(NH3)2] and BF3have zero dipole moments due to symmetrical structure and as the individual bond moments are cancelled out by each other. * cis-[PtCl2(NH3)2] has dipole moment. The bond moments are not cancelled out and it is less symmetrical than trans isomer. * Remember, BF3 is trigonal planar whereas, NH3 and NF3 are trigonal pyrimidal. Additional information: * Dipole moment ( ) is defined as the product of magnitude of charge( ) on either of the poles (atoms) and the distance(d) between them. = .d * It is a vector quantity. It is represented by an arrow pointing towards negative pole (as shown in above diagrams). * The dipole moment of a bond is called bond moment. The final dipole moment of a molecule is the vectorial addition of all the bond moments in it. * The unit of dipole moment is Debye (D) = 10-18 e.s.u cm * Dipole moment is used to determine the ionic nature of a polar covalent bond.

* For example, In HCl molecule, the observed dipole moment is 1.03 D and its bond length is 1.275. Assuming 100% ionic character, the charge developed on H and Cl atoms would be 4.8 x 10-10e.s.u. Therefore, the theoretical dipole moment for 100% ionic character will be theoretical = x d = 4.8 x 10-10e.s.u x 1.275 x 10-8cm = 6.12 x 10-18e.s.u.cm = 6.12 D ( 1D = 10-18 e.s.u. cm.)

% ionic character =

* It is also used to determine the shape of a molecule. Usually, the symmetrical molecules have zero dipole moment. For example CO2 has zero dipole moment as it has linear shape, whereas SO2 has net dipole moment as it has angular structure. * Bond angle between two bonds can be calculated if their bond moments and resultant dipole moment are known. Following simplified equation can be used when the two bonds are same. net dipole moment = 2(bond moment) x cos where = bond angle Additional questions: 57.1) The dipole moment of H2S is 0.95 D. If the S-H bond moment is 0.72 D, find the bond angle. 57.2) Naphthalene has zero dipole moment whereas its isomer Azulene has a dipole mo 2

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% ionic character = experimental theoretical x 100

theoretical is calculated by assuming the bond is completely polar (ionic).

experimental theoretical

x 100 =

1.03 x 100 = 16.83% 6.12

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ment of 0.8 Debye. Explain? 135) The major product formed in the reaction, given below, is
CN 1. EtMgBr 2. H3O+

1)

CHO
O

2)

3)

4)

Explanation:

..

C N

140) Sucrose is a disaccharide consisting of 1. glucose and glucose 2. glucose and galactose 3. glucose and fructose 4. glucose and mannose

Explanation: * Sucrose is -D-glucopyranosyl--D-fructofuranoside . * It is a disaccharide containing alpha-D-Glucose and beta-D-Fructose units. * There is a glycosidic linkage (an acetal linkage) between C-1 of alpha-D-glucose and C-2 of beta-D-fructose.

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NH2
CN

- + Et-MgBr

- + N MgBr ..

H+

HOH

An imine salt complex

imine

HOH

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WARANGAL glycosidic linkage

O HO OH OH

OH O

OH - H2O OH OH HO O OH O OH HO HO O OH OH

+ HO
OH

HO HO

-D-Glucose

-D-Fructose

-D-Glucopyranosyl--D-Fructofuranoside

* It is a non-reducing sugar as both the reducing ends of glucose and fructose are linked. It does not give silver mirror with Tollens reagent. * In sucrose, there are no anomeric hydroxy groups, as the rings at the reducing parts are not free to open, and hence does not show mutarotation. Additional information: *

41.1)

Note: chlorido is very recent IUPAC usage instead of chloro. Pt (Z=78). Belongs to Nickel group. with e.c - [Xe] 4f14 5d8 6s2 For Pt2+ -- [Xe] 4f14 5d8 . Hybridization of Pt2+ is dsp2 . It is a square planar and low spin complex with zero magnetic moment. The crystal field splitting of square planar complexes is shown below.

41.2) Action: Upon administration to the cancer patient, the chloride ligands are displaced by water and thus aqua platinum complexes are formed in cells, which bind and cause crosslinking of DNA---- ultimately triggers apoptosis - programmed cell death. 42.1) B 42.2) L: R:

2H+(aq) + 2e- -----------> H2(g), Eo = -0.421V Fdox+ + e-----------> Fdred , Eo = 0.439V

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SOLUTIONS TO ADDITIONAL QUESTIONS cis-Diamminedichloridoplatinum(II)

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WARANGAL

Overall cell reaction Fdox+ + H2(g) + -----------> Fdred + 2H+(aq) Ecell = ER - EL = 0.439 - (-0.421)V = 0.86V ------- which is > 0 This means that rG < 0 (why? see the note). Hence reduction of Fdox+ is spontaneous and NOT the liberation of hydrogen. Therefore H2 gas is consumed, and not produced in this reaction. Note: G = -nFE 42.3) False. This is a reduction reaction. Hence only reduced form of ferredoxin can reduce NO2to ammonia.
nitrite reductase NO 2 - + reduced ferredoxin NH 3 + oxidised ferredoxin

43.1) HCo(CO)3 -- Tricarbonylhydridocobalt(I) HRh(CO)(PPh3)2 -- Carbonylhydridobis(triphenylphosphine)rhodium(I) 43.2) Mechanism:

HRh(CO)(PPh)3 18e

H Butyraldehyde (major product)

reductive elimination O H Rh OC H CH3

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-(PPh) HRh(CO)(PPh)2 16e H Rh CO 18e

PPh

PPh

HRh(CO)(PPh)2 16e to the cycle

Rh

OC

PPh PPh

16e

H2

O Rh OC PPh PPh

CH3 CO insertion OC Rh CO PPh PPh

CH3

PPh PPh

16e

18e

43.3) RhCl(PPh3)3 - chlorotris(triphenylphosphine)rhodium(I), is called Wilkinsons catalyst and used in the selective hydrogenation of alkenes. It is a square planar 16 electron complex. * exocyclic double bonds are selectively hydrogenated over endocyclic double bonds. * cis alkenes are reduced rapidly than trans alkenes. * Functional groups like C=O, C=N, NO2, Ar, CO2R etc., are unaffected.

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WARANGAL

RhCl(PPh3)3
O

H2, benzene

sterically less hindered double bond is hydrogenated selectively

44.1) c=

A l

0.21 31500 x 10

= 6.67 x 10-7 M

44.2) 510 = 4.5 cm-1M-1 44.3) M = 10-6 M For iron transferrin, A = 4.6 x 10-2 For iron-desferrioxamine B, A = 1.6 x 10-1

44.4) The absorption bands of many transition metal ions in aqueous solutions are broad & strongly influenced by the chemical environment, because of the spatial shape & orientation of the d-orbitals. Such bands are rarely intense enough (low molar absorptivity) to use directly for quantitative analysis. Hence the molar absorptivity is greatly augmented by complexing the metal ion with some suitable organic chelating agent to produce a chargetransfer complex. Eg., 1,10-phenanthroline improves the molar absorptivity of Fe(II).

Above complex is commonly known as ferroin and also used as 1) redox indicator (reduced ferrous form is deep red, oxidised ferric form is light blue) 2) used as a cell permeable inhibitor for metalloproteases in cell biology. Wait! Lanthanides & actinides having incomplete f-levels & give rise to absorption bands in a similar fashion to transition metals. In contrast to transition metal ion spectra, those of the lanthanides/actinides contain narrow, well-defined bands which are little affected by ligands & the local chemical environment. But still the peaks are less intense.(Ofcourse 4f-4f transitions are sharp and not of 4f-5d.) 46.1) Bastnasite mainly represented by (Ce,La,Y)CO3F contains all the lanthanoids, whereas Monazite(Phosphate mineral of Thorium and other rare earths) contains lighter ones. 46.2) Fifteen elements from La-Lu are lanthanoids. Whereas fourteen elements Ce-Lu without lanthanum are lanthanides (meaning the elements similar to lanthanum). 46.3) The ore (monazite or bastnasite) is dissolved in HCl and converted to a solution of LnCl3. Lanthanoids in this solution are separated by ion exchange as follows.

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N N Fe
2+

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WARANGAL

Ion Exchange -first the solution is eluted onto the cation exchange column to replace the resin bound Na+ ions in a band at the top of the column
Ln 3+ (aq) + 3Na + (resin) Ln 3+ (resin) + 3Na + (aq)

-then elute with a complexing agent such as EDTA4- and adjust pH -the Ln3+ with the smallest radii are most strongly bound to the anionic ligand(EDTA4-) and so are eluted first.
Ln 3+ (resin) + 3Na + (aq) + [EDTA-H]3 (aq) Ln[EDTA-H](aq) + 3Na + (resin)

Note: Ln3+ = trivalent lanthanoid ion. 46.4) The solubility of Ln3+ ions in tri-n-butylphosphate, (BunO)3PO , solvent increases with increase in atomic weight of Ln. Thus the separation of lanthanoids is achieved on large scale by extracting an aqueous solution containing mixture of nitrates of lanthanoids with the solvent tri-n-butylphosphate. 47.1) B2H6 is a nido-borane as it has BnHn+4 formula.

47.2) [B6H12] is an arachno-borane as it has BnHn+6 formula.

48.1) MnF62- acts as a Lewis base, donating two F- to SbF5 molecules. MnF62- + 2 SbF5 --------> 2 SbF6- + MnF4 Thus formed MnF4 lose F atoms which form F2 by combining. 2 MnF4 --------> MnF3 + F2

48.2) Conductivity is increased due to formation of following ions BrF3 + AgF <--------> BrF4- + Ag+ (AgF is acting as a base) BrF3 + SnF4 <--------> BrF2+ + SnF52BrF3 + SnF4 <--------> 2 BrF2+ + SnF6-

48.3) AlF3 is a Lewis acid. It reacts with F- ion and thus by forming salt containing Na+ and AlF4-. AlF3 + NaF ----------> Na+ + AlF4When BF3 is added, it has stronger affinity for the F- ions and precipitates out AlF3 AlF4- + BF3 -----------> AlF3 + BF4(Which is stronger acid among AlF3 and BF3?) 48.4) SbF5 reacts with HF and increases the concentration of H+ ions. 2SbF5 + 2HF ------------> Sb2F11- + H2F+ H2F+ -------------> HF + H+ This mixture can protonate methane and alkenes.

48.5) H3AsO4 < H3SO4 < H2SO3< HMnO4 Hints: 1) Greater the oxidation number of the central atom, greater is the acidic strength. 2) Sulfur is a stronger non-metal than Arsenic. 48.6) Cl2 donates lone pair of electrons to Cl+ and forms [Cl3]+ ion. Hence it acts as a Lewis base.

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(SnF4 is acting as an acid)

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+

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WARANGAL

Cl

Cl

+ Cl

Cl

Cl

Cl

49.1) e.c of Fluorine is (1s2)(2s2,2p5) shielding constant = s = (6 x 0.35) + (2 x 0.85) = 3.8 Z* = 9 - 3.8 = 5.2 49.2) From the electronic configuration (1s2)(2s2,2p6)(3s2,3p6) (3d10) (4s2,4p6) (4d10) (4f14) (5s2,5p6) (5d8) (6s2) s= 60 x 1.00 + 16 x 0.85 + 1 x 0.35 = 3.95 Z* = 78 - 73.95 = 4.15 49.3) The IE for lithium is lower for two reasons; 1) The average distance from the nucleus for a 2s electron is greater than that of a 1s electron; 2) The 2s1 electron in lithium is shielded from the nuclear attraction (as well as repelled) by the inner core electrons, so the valence electron is easily removed. 57.1)
net dipole moment = 2(bond moment) x cos

57.2) The resonance hybrid of Azulene is contributed by stable zwitter ionic resonance forms(II & III). Hence it has dipole moment. Resonance forms (II & III) are aromatic as they contain six -electrons in both the rings and hence are stable.

Whereas naphthalene cannot be stable in this type of zwitter ionic form with charge separation. Only non polar neutral forms are aromatic and stable. Hence it is non polar. Note: Remember, in writing resonace structures, the structure with charge separation is considered to be less stable. And more over, in case of Naphthalene, this form will not satisfy Huckels rule and anti-aromatic and hence with least stability. But in case of azulene, resonance form with charge separation becomes more important as the aromatic nature out weighs this factor.

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2
0.95 = 2(0.72) x cos 2 cos = 0.6597 2 bond angle = = 97 0

II

III

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WARANGAL

2px 2py 2pz

2px 2py sp

2s

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2px 2py sp 2pz 2px 2py sp sp 2s CO O

Energy

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WARANGAL

2px 2py 2pz

2px 2py sp

Energy

2px 2py sp 2s sp

2pz 2px 2py

sp

2s

CO