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CSIR

CSIR

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01/06/2011

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Prepared by V. Aditya vardhan adichemadi(at)gmail.com
WARANGAL
   V .  A   D   I   T   Y  A    V  A   R   D   H  A   N  a  d   i  c   h  e  m  a  d   i   @   g   m  a   i   l .  c  o  m
39
This part(Series-2 from Q.no 61 - 80)is updated on13th July, 2009and going to be updated constantly. For recent updates and other parts, join the following group
http://groups.google.com/group/adichemadi
or view them athttp://www.scribd.com/adichemadiSOLVEDCSIR UGC JRF NETCHEMICAL SCIENCES
PAPER 1 (PART-B)
SERIES-2
NOTE: Related and additional questions appeared in previous GATE exams are alsosolved.
61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80
61)The polymeric species (SN)
n
is a / an1. three dimensional conductor2. two dimensional conductor3. insulator4. one dimensional conductorExplanation:
* (SN)
n
, known as polythiazyl, is a linear polymeric sulfur nitride. It is a one dimensionalconductor. It was found to be a superconductor at very low temperatures (below 0.26 K).* It is used as barrier electrode in ZnS junctions.* It increases the quantum efficiency of blue emission by a factor of 100 compared to gold.* It increases the efficiency of 
GaAs
solar cells by up to 35%.
Additional information:Structure of (SN)
n
NSNSNSNSNSNS
120
0
106
0
It is a linear polymer (n = up to 2000). It exists in several resonance forms.
Preparation:
Polythiazyl is synthesized by passing Tetrasulfur tetranitride (S
4
N
4
) over silver metal. In thisconversion, silver is sulfided to silver sulfide which catalyses the conve
 
rsion of S
4
N
4
toDisulfur dinitride (S
2
N
2
), which readily polymerized to (SN)
n
.S
4
N
4
+ 8AgAg
2
S + 2N
2
S
4
N
4
 Ag
2
S (as catalyst)77 K2S
2
N
2
 2S
2
N
2
 (SN)
n
1) sublimes to surface at 0
o
C2) then undergoes thermal polymerization
Additional questions:61.1) Draw the structure of S
4
N
4
.
 
Prepared by V. Aditya vardhan adichemadi(at)gmail.com
WARANGAL
   V .  A   D   I   T   Y  A    V  A   R   D   H  A   N  a  d   i  c   h  e  m  a  d   i   @   g   m  a   i   l .  c  o  m
40
Ans:-
SSSNNNNS
61.2) Write the equations for preparation of S
4
N
4
from SCl
2
.
Ans:- S
4
N
4
was prepared by the reaction of ammonia with SCl
2
in carbon tetrachloride followedby extraction into dioxane.24 SCl
2
+ 64 NH
3
--------------> 4 S
4
N
4
+ S
8
+ 48 NH
4
Cl
63) The molar absorptivity at
max
 
is minimum for1. [Mn(H
2
O)
6
]
2+
2. [Cr(H
2
O)
6
]
2+
3. [Co(H
2
O)
6
]
2+
4. [Fe(H
2
O)
6
]
2+
Explanation:
* The molar absorptivity or extinction coefficient (
 
) indicates the intensity of absorption of light radiation during the excitation of electrons. If this value is large then the the complexhave intense color and otherwise it will have pale color.* The intensity can be determined from the following quantum mechanical selection rules thatstate whether the transitions are allowed (intense color) or not allowed (pale color)a) Symmetry forbidden or Laporte forbidden (
Δ = 1
l
): If the molecule has centre of symmetry, the transitions from one centrosymmetric orbital (that with centre of inversion) toanother are forbidden. i.e., transitions within a given set of p or d orbitals (i.e. those whichonly involve a redistribution of electrons within a given subshell) are forbidden.In other words, g-->g or u-->u transitions are not allowed.b) Spin forbidden (
ΔS = 0
): The number of unpaired electrons cannot change uponexcitation i.e., no electron spin-flip is allowed.* All the molecules are octahedral with centre of symmetry and hence the excitations aresymmetry forbidden. (In case of Cr
2+
there is Jahn-Teller distortion)* Check for whether spin forbidden or not?The electron distributions are shown below (remember H
2
O is a
 
weak field ligand)Mn
2+
-3d
5
ort
2g3
e
g2
spin forbiddenCr
2+
-3d
4
ort
2g3
e
g1
one spin allowed transitionCo
2+
-3d
7
ort
2g5
e
g2
three spin allowed transitionsFe
2+
-3d
6
ort
2g4
e
g2
one spin allowed transition* As the transitions in Mn
2+
are both symmetry and spin forbidden, the molar absorptivity isminimum for first complex, [Mn(H
2
O)
6
]
2+
. Hence it is pale pink in color.Note: Extinction coefficients for tetrahedral complexes are expected to be around 50-100
 
Prepared by V. Aditya vardhan adichemadi(at)gmail.com
WARANGAL
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41
times larger than for octrahedral complexes. Why? Ans: Do not possess centre of inversion.
Additional questions63.1) KMnO
4
shows an intense pink colour, while KReO
4
is colourless.Explain.
Ans:- KMnO
4
shows an intense pink colour, while KReO
4
is colourless.Explanation: Mn
7+
in MnO
4-
has d
0
configuration. Hence no d-d transition. Still it shows colordue to ligand to metal charge transfer (LMCT) phenomenon. MnO
4-
absorbs yellow andtransmits violet part of light.
Charge transfer spectra:
Charge transfer is of two types viz.,i) Ligand to Metal Charge Transfer (LMCT)ii) Metal to Ligand Charge Transfer (MLCT)
LMCT:
In LMCT, an electron is transferred from ligand to the metal, which is thereforereduced in the excited state. Charge transfer is analogous to an
internal redox reaction
, andhence absorption energies can be correlated with trends in redox properties. The more posi-tive the redox potential concerned, the easier such reduction will be, and so the lower theLMCT energy. LMCT transitions in the visible region of the spectrum give intense color as incase of permanganate ion (MnO
4-
).The general LMCT energy trends in some d
0
species are:i) LMCT energy decreases towards the right in the 3d series.e.g. VO
43-
> CrO
42-
> MnO
4-
ii) LMCT energy increases down the transition metal group.e.g. MnO
4-
< TcO
4-
< ReO
4-
The above orders of LMCT energy are reflected in the changing colors of the ions and asthe transition moves progressively to higher energy out of the visible spectrum into the UV.e.g.i) MnO
4-
deep purple(absorbs yellow color (low energy) and transmits violet)ii) CrO
42-
deep yellow(absorbs violet (high energy) and transmits yellow)iii) VO
43-
pale yellow(as in above case)Now the answer to final part of the question. As the energy required for the charge trans-fer in case of ReO
4-
is in the UV region, it does not show any color. It absorbs UV and trans-mits entire VIBGYOR (= white).Other examples:i) CdS: The color of artist’s pigment cadmium yellow is due to t
 
ransition from S
2-
(porbital) to Cd
2+
(empty 5s orbital).ii) HgS: It is red due to S
2-
(p) to Hg
2+
(6s) transition.Actually in Cd
2+
and Hg
2+
d-d transitions are not possible due to d
10
configuration.
MLCT:
The less common, MLCT results in the reduction of the metal center. The chargetransfer occurs from metal to ligand with emty orbital especially low lying
*
 
orbital.e.g.Tris(2,2’-bipyridyl)ruthenium(II),[Fe(phen)
3
]
2+
-- ferroinNote: phen = 1,10-phenanthrolineOptical spectroscopy is a powerful technique to assign and characterize charge transferbands in these complexes.

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