Csir Net Gate

Prepared by V. Aditya vardhan - i - mail id: adichemadi@gmail.
com
Original & Accurate copy of AdiChemistry CSIR NET & GATE study material is available only from the Author at www.adichemistry.com
Updates & keys with explanation are only available to those who purchased this material from the Author at www.adichemistry.com
SELECTED TOPICS FOR CSIR NET & GATE CHEMISTRY
(NEW EDITION 2017)
ACi hem stry Study material by V. Aditya vardhan

(AdiChemistry / AdiChemAdi)
Released on: 01st, May 2017
Last updated on: 10th, June 2017
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V. Aditya Vardhan SALIENT FEATURES

* Important selected topics for CSIR NET & GATE as well as other equivalent exams like SET/
SLET, TIFR etc. Also useful for UG & PG exams.
* Written in a simple langualge but with very effective tone and helps you in improving your
score.
* Most of the topics are provided with illustrated notes as well as worksheets/practice problems.
Note: The length of topics may range from large to small. Some topics are provided with either notes or
question bank only. Missing parts will be appended in future updates.
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ACi
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hem stry
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Selected Topics for CSIR NET & GATE chemistry 2017
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Prepared by V. Aditya vardhan - ii - mail id: adichemadi@gmail.com
LIST OF TOPICS
# ACi hem stry

PART-1
Topic Name
1 Bioinorganic chemistry: * Distribution of elements - Bulk & Trace

from
page
to
page
metals ; non metals - biological functions * Porphyrins * Oxygen

transport * Hemoglobin & Myoglobin (Updated again) * Hemerythrin
* Hemocyanin * Electron transport * Cytochromes - Cytochrome C
oxidase - Cytochrome P450 * Iron sulfur proteins - Ferridoxins -
Reiske protein * Rubredoxin * Photosystems * PSII - OEC * PSI *
Metalloenzymes * Carboxy peptidase * Carboxy anhydrase * Liver 1 36
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alcohol dehydrogenase * Superoxide dismutase * Nitrogen fixation
* Copper proteins * Siderophores * Ionophores * Ferritin, Apoferritin
& Tranferrin * Application of metals in medicine * Practice questions
V. Aditya Vardhan
(level 1) * Advanced questions (level 2)
2 Analytical chemistry: * Chromatography * Basic concepts &

terminology * Theory of Band broadening and Van deemter equation
* Gas Chromatography * HPLC * Practice questions * Advanced
questions * Spectrochemical methods * Beer-Lambert’s law *
Practice questions * Advanced questions * Electroanalytical 37 82
methods * Polarography* Amperometry * Cyclic Voltammetry *
Stripping Voltammetry * Potentiometry * Practice questions *
Advanced questions * Gravimetry * Iodometry * Practice questions
3 Nuclear chemistry: Terminology, Concepts, Formulae * Stability of

nucleus * Mass defect * Binding energy * magic numbers * 83 97
Radioactive disintegration series * Solved questions * Practice
4 Solid state (explained through problems) 98 119
5 Pericyclic reactions: 1) Cycloaddition reactions 2) Electrocyclic
reactions
3) Sigmatropic rearrangements 4) Group transfer reactions 5) 120 142
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Cheletropic reactions 6) Dyotropic rearrangements ; * Frontier
Molecular Orbital (FMO) Theory * Woodward Hoffmann rules *
6 Mossbauer Spectroscopy: Introduction; Natural line width; Doppler
effect; Recoiling effect; 57 Fe Mossbauer spectroscopy; Isomeric shift;
143 155
Electric quadrupole splitting; Magnetic interactions; selection rules,
Chemical applications; Practice problems hem stry

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7 Thermodynamics (through problems) 156 177
Electron spin resonance (ESR) Spectroscopy: Introduction; Spin states
of electron, Presentation of spectrum, Characteristics of 'g', Hyperfine
8 splitting, Selection rules, EPR transitions in metal complexes & organic 178 189
ACi
molecules, Practice problems
9 Electronic Spectroscopy
hem stry of Transition metal complexes: Selection
rules (Laporte and spin); LMCT, MLCT, calculation of CFSE , Term
symbols for ground state, Russel Saunder's coupling are explained
190 207
through solved problems.
PART-2
In the following topics, explanations arePrepared by
followed by practice questions.
1 Aldol reaction 1 11
2 Jahn Teller Theorem 12 22
3
4
5
6
V. Aditya Vardhan
Kohlrausch law
Wittig reaction
Hard Soft Acid Base theory (HSAB)
Miller indices
23
38
47
52
37
46
51
60
7 Beckmann reaction 61 65
8 Wilkinson catalyst 66 74
9 Rate laws 75 94
10
11
12
Birch reduction
Spinels
van der Waals equation
95
103
108
102
107
123
13 SeO2 124 129
14 18E Rule 130 143
15 Phase rule 144 149
16 Hammett equation 150 151
17 Trans Effect 152 156
18 le Chatelier's Principle 157 168
19 Favoroskii reaction 169 173
20 Silicates 174 178
21 Jablonskii diagram 179 181
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22 Inductive effect 182 187
23 Boranes & Wades rules 188 199
24 Adsorption isotherms - Langmuir theorem 200 208
25 Corey-Chaykovsky reaction 209 217
26 f-block hem 218stry 232
27 Band Theory 233 241
28 DIBAL 242 249
29 Catalysis using organometallics-Hydroformylation-Wacker oxidation 250 263

MORE TOPICS WILL BE ADDED FROM TIME TO TIME
Original & Accurate copy of AdiChemistry CSIR NET & GATE study material is available only from the Author at www.adichemistry.com HEMOGLOBIN AND MYOGLOBIN
Hemoglobin (denoted as Hb) and Myoglobin (Mb) are dioxygen (O2) binding metalloproteins containing
an iron porphyrin system, heme. Both of them contain Fe(II) ion. Hemoglobin is present in Red Blood
Cells (RBC) and helps in transport of dioxygen from lungs to tissues. Whereas, myoglobin stores dioxygen
and is present in muscles.
ACi hem stry

Hemoglobin contains
STRUCTURE
four heme units each embedded in a globular protein sub-unit. There are two
types of protein sub-units i.e., a and ß. Myoglobin contains only one heme unit surrounded by a globular
protein, containing seven -helical and six non helical segments, made up of 153 amino acids .
Prepared by
V. Aditya Vardhan
Note: Heme moieties are shown in green color in above diagram. Fe(II) ion is shown in red color.
Heme is a porphyrin ring system made up of four pyrrole rings with an Fe(II) ion coordinated to nitrogens
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of pyrrole rings.
Globin part prevents irreversible oxidation of Fe(II) ion by providing hydrophobic environment. It enhances
the selectivity for O2 binding. In hemoglobin, the tetramer arrangement allows for co-operativity by making
it more efficient in binding to dioxygen.
Hemoglobin and Myoglobin exist in two forms i.e.,
1) deoxy form: No oxygen is bound to iron. hem stry
2) oxy form: dioxygen is bound to iron.
In deoxy-hemoglobin, four of the coordinated sites of iron are occupied by nitrogens of porphyrin ring.
The fifth site is occupied by Histidine residue (called proximal histidine) of globin. The sixth position is
occupied by weakly bonded water molecule. Hence some authors tend to report Fe(II) ion in deoxy form
as pentacoordinated. Deoxy-hemoglobin is said to be in T-state (tense).
On the opposite side of the proximal histidine, there is one more histidine group (called distal histidine)
placed near the iron ion. It forces the binding of dioxygen in "end on bent" confirmation.
A careful balance between Science and Silence brings peace, happiness and prosperity in our life.
Note: The bent confirmation discourages the binding of CO to heme iron. Otherwise, CO may have
even more affinity with the iron ion. It is observed that CO binds to hemoglobin 200X stronger than
dioxygen but binds 20,000X stronger with unprotected heme.
ACi hem stry
Prepared by
V. Aditya Vardhan
Hemoglobin coordinated to dioxygen is called oxy-hemoglobin. It is also referred to as R-state
(relaxed). In oxy-hemoglobin the sixth coordinated position of iron is occupied by dioxygen in "end on
bent" geometry.
Hemoglobin is sometimes referred to as dimer of dimers since it contains two alpha and two
beta subunits.
FUNCTIONING OF HEMOGLOBIN - A BIOINORGANIC PERSPECTIVE

In deoxy-Hemoglobin, the porphyring ring is dome shaped. The Fe(II) is in high spin state and is
paramagnetic. Its size is 0.78 Ao and is positioned above the plane of the porphyrin ring.
However, in oxy-Hemoglobin, the size of iron ion is reduced to 0.61 Ao and can fit into the cavity of
planar porphyrin ring and hence moves into the cavity of porphyrin ring with concomitant dragging of
proximal histidine that triggers the conformational changes in other globin subunits and thus by opening
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other heme sites. As a result, the binding capacity of other heme irons with dioxygen is enhanced. This is
best example for co-operativity through allostery.
hem stry
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N N
N N
ACi
H H
H-bond
CH3
com O
O
ry.
H 3C hem stry CH3
N N H 3C
H 3C N N CH3
i st N
FeIII
N
m
II
Fe N N
e
- -
O OC-H 2 C-H 2 C CH 2 -CH 2 -COO H 3C CH3
ich -
O OC-H 2 C-H 2 C
N
CH 2 -CH 2 -COO
-
A
N
d N
H
N
H
Oxy Hb
Deoxy Hb
Domed porphyrin Prepared by Planar porphyrin
Fe ion moves into the ring
High spin Fe(II) - out of ring
Bent O2
V. Aditya Vardhan
The nature of Fe in oxy-Hemoglobin or in oxy-Myoglobin is controversial.
According to old Pauling model, there is a low spin Fe(II) ion that is bound to singlet O2 in oxy-Hb. Both
are diamagnetic.
However, according to Weiss model, there is Fe(III) ion bound to superoxide radical anion (O2-).
Though both are paramagnetic, a strong paramagnetic coupling between them ensues diamagnetic behavior
. This model is supported by the O-O stretching frequency at 1105 cm-1 in resonance Raman spectrum
that is consistent with the fact that O2 is in superoxide form. This deems to be more accurate and modern
explanation.
More information..............
* Bisphosphoglycerate (BPG) reduces the affinity of Hb with oxygen. It binds at the centre of cavity
between two beta-Hb units and stabilizes the T-state. It is observed that at high altitudes (on moun-
tains), the amount of BPG increases in the blood. This won’t affect the affinity of Hb with oxygen in
lungs where the pO2 is very high but decreases the affinity in tissues and helps in release of dioxygen by
stabilising the T-state of Hb.
* Bohr effect: The affinity of Hemoglobin with dioxygen decreases with decrease in the pH of
blood. Hence oxygen is released more efficiently in the tissues where CO2 concentration is high. The
response of hemoglobin to changes in pH is called the Bohr effect.
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* Increase in the temperature decreases the affinity with O2.
* The percent saturation with O2 curve of Hb against pO2 is sigmoidal whereas that of Mb is hyper-
bolic. This shows greater affinity of Mb with dioxygen even at low pO2 values.
* Deoxyhemoglobin is the form of hemoglobin without the bound oxygen.The oxyhemoglobin has
significantly lower absorption (660 nm) than deoxyhemoglobin (940 nm). This hem stry
difference is used for
measurement of the amount of oxygen in patient's blood by pulse oximeter.

Mb - Hyperbolic curve
% saturation with O2
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Hb - Sigmoidal curve
pO2
Why are all the oxygen carriers that contain iron and porphyrins are found inside the cells?
The inside cell environment is reducing and sustains Fe(II), whereas outside the cell the O2 concentration
is high and hence the probability of the oxidation
Prepared of Fe(II) ions
byto Fe(III) increases.
What prevents synthetic (simple) iron porphyrins from functioning as O2 carriers?
In the naturally occuring porphyrins, like Hemoglobin, there is a globular protein around the heme
V. Aditya Vardhan
groups. I t prevents the irreversible oxidation of Fe(II) to Fe(III) and solvolysis of Fe(II)-O2 complex by
providing hydrophobic environment around iron. It stops the formation of Fe-O2-Fe dimer.
However in synthetic porphyrins, protein part is absent. As a result, Fe(II) is oxidized to Fe(III) and Fe-
porphyrins easily dimerize to Fe-O2-Fe and then Fe-O-Fe (a  -oxo dimer) and hence cannot function as
oxygen carriers.
The steps, involved in conversion of free heme in aqueous solutions to hematin, a  -oxo dimer, when
exposed to dioxygen, are summarized below.
2+ 2+
Fe + O2 Fe O Binding of dioxygen molecule
O
3+
2+ Fe O
Fe O
O
+ 2+ O Fe
3+ Formation of  peroxo complex
Fe
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Fe
3+
O 4+ 4+ Formation of ferryl complexes in which
Fe O O Fe
O Fe
3+ iron is in +4 formal oxidation state
4+ 2+ Fe
3+
O Hematin formation hem stry
Fe O + Fe
Fe
3+
Note: This  -oxodiiron(III) moiety has a distinctive fingerprint that has made it easy to identify this
motif in proteins regardless of the geometry, type and number of ligands. Selected Topics for CSIR NET & GATE chemistry 2017
Magnetic susceptibility = 1.5 to 2.0 Bohr magnetons, indicating one unpaired electron. It is due to
strong antiferromagnetic coupling of iron centres through oxygen. (Actually the value should be more)
Asymmetric Fe-O stretching frequency at 730 - 880 cm-1
What is the "Cooperative effect" in hemoglobin?
Coordination of one O2 leads to conformational changes in the protein chain leading to facilitated
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coordination of O2 by the other 3 sub-units in hemoglobin.
Why does carbonhem stry

monoxide binds strongly to iron(II) porphyrin complexes but not iron(III)
porphyrins. Compare the infrared frequency of CO in this complex to that of free CO.
Ans:- The Fe(II)-CO bond is strong because there are strong d  -p  * backbonding interactions which
strengthen the Fe-C bond. This is much less important for Fe(III)-CO because of higher positive charge
on the metal.
The IR frequency of free CO is higher than that of CO in a porphyrin complex because backbonding
adds electron density to the  * antibonding orbital of the CO bond, decreasing its strength.
PRACTICE QUESTIONS
Prepared
FROM
by
BIOINORGANIC CHEMISTRY
V. Aditya Vardhan
Keys/Solutions along with extra problems (updates) are available at
http://www.adichemistry.com/csir-net/chemistry/key.html
1) Complexes of which of the following metals are used in the treatment of rheumatoid arthritis:
1. Gold 2. Ruthenium 3. Iron 4. Copper
2) In biological systems, the metal ion involved in the dioxygen transport besides Fe is
a) Co b) Zn c) Mg d) Cu
3) In photosynthesis, the predominant metal present in the reaction centre of photosystem II is:
(a) Zn (b) Cu (c) Mn (d) Fe (GATE 2009)
4) Zn in carbonic anhydrase is coordinated by three histidine and one water molecule. The reaction of CO2
with this enzyme is an example of
(a) electrophilic addition (b) electron transfer
(c) nucleophilic addition (d) electrophilic substitution.
5) The metals present in nitrogenase are
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(a) Fe and Mg (b) Mo and K (c) Mo and Fe (d) Fe and K
6) The transition metal present in vitamin B12 is_______
7) The trivalent ion of lanthanoid element which is used as NMR contrasting agent is
1) Gadolinium 2) Technetium 3) Cerium hem4) Lutetium
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8) Match the following
1) Li+ A) Ulcer treatment
2) Bi3+ B) Eczema
3) Sb3+
4) Fe2+
C) Anemia
D) Depression
Original & Accurate copy of AdiChemistry CSIR NET & GATE study material is available only from the Author at www.adichemistry.com 9) The enzyme which removes C-terminal amino acid from a peptide is
1) Carbonic anhydrase 2) Carboxy peptidase 3) Zymase 4) All
10) Which of the following metal is stored by metallothionein in biological systems?
1) Fe 2) Cu 3) Zn 4) Co
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11) The metals present in superoxide dismutase are:
a) Zn & Fe hem stry
2) Cu & Fe 3) Mo & Cu
(CSIR NET DEC 2011)
4) Cu & Zn
12) In human body, by mass, the most abundant nonmetal is ____ and most abundant metal is ____.
13) The copper containing non heme respiratory protein is

1) Cytochrome-c 2) Hemerythrin 3) Hemocyanin 4) Myoglobin
14) The oxidation state of iron stored in ferritin is

1) +2 2) +1 3) +3 4) 0
Prepared by
15) The enzyme which catalyzes the conversion of carbondioxide to bicarbonate is
1) Carboxy peptidase 2) Superoxide dismutase
V. Aditya Vardhan
3) Carboxy anhydrase 4) Hydrogenase
16) The number of methine bridges present in porphyrin is _______ and in corrin is _____ .
17) The ionophore used in the cattle feed to improve the permeability of Na+ and H+ ions is
1) Crown ethers 2) Monensin 3) Ionomycin 4) Nonactin
18) Match the following
A) Silver sulfadiazine 1) Anti copper agent
B) Selenium sulfide 2) Skin fungal infections
C) tetrathiomolybdate 3) Radiodiagnosis
D) Cardiolyte 4) Seborrheic dermatitis
19) The function of Na+ and K+ in biological systems is

1) To maintain osmotic balance in the cells 2) Help in active & passive transport
3) As charge carriers 4) All
20) Fluoride is present in the teeth in the form of
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1) CaF2 2) Na3AlF6 3) Ca5(PO4)3F 4) CaF2.CaCO3
21) Which of the following is a channel forming ionophore?

1) Valinomycin 2) Salinomycin 3) Gramicidin 4) All
22) The porphin system in chlorophyll is called as hem stry

1) porphyrin 2) chlorin 3) corrin 4) heme
23) The metal present in both superoxide dismutase and hemocyanin is

a) Zn b) Fe c) Cu d) Ni
24) The metal ion present in urease is____ . Selected Topics for CSIR NET & GATE chemistry 2017
25) The ionophore valinomycin is highly selective for:
a) K + b) Na+ c) Mg2+ d) Ca2+
26) The metal ions that have highest mobility in biological media are:
a) Mg(II) & Ca(II) b) Zn(II) & Fe(II) c) Na(I) & K(I) d) Ni(II) & Cu(II)
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27) Cisplatin is:
a) diamagnetic hem stry
b) paramagnetic
28) Hemerythrin belongs to the group of:

c) ferromagnetic d) anti-ferromagnetic
a) non-heme iron protein b) heme-iron protein

c) binuclear copper protein d) non heme non iron protein
29) Which of the following is correct concerning the differences between hemoglobin and myoglobin?
A) Hemoglobin is a monomeric protein and myoglobin is a tetrameric protein.
B) Hemoglobin exhibits a hyperbolic O2 saturation curve while myoglobin exhibits a sigmoid shaped
curve.
Prepared by
C) Hemoglobin exhibits cooperative binding of O2 while myoglobin does not.
V. Aditya Vardhan
BEER-LAMBERT LAW
BEER-LAMBERT LAW: The actual absorbance, A, of a sample is dependent on the pathlength l (in
cm) and the concentration c (molar conc.) of the species.
Mathematically: A =  .c.l
*  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;
Limitations:
* Beer-Lambert law 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.
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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).
 Cr2O 7 2- (aq) + H 2O (l)
2 CrO 4 2- (aq) + 2 H + (aq) 
yellow orange hem stry
Hence the absorbance for this solution depends on the pH .
* There should be no scattering of light.
* There should be no fluorescence or phosphorescence
INTERESTING
Guess the molar absorbtivity of Cu2+ ions in an aqueous solution of CuSO4. Whether 20 or 100,000
L mol-1 cm-1?
You may prefer higher value as the copper sulphate solutions you have seen are usually a beautiful
bright blue in colour. However, its molar absorbtivity value is 20 L.mol-1.cm-1! The bright blue colour is
seen because the concentration of the solution is very high.
Now consider the beta-carotene which is responsible for the colour of carrots. It is found at exceedingly
.
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low concentrations and still imparts beautiful orange color as its molar absorbtivity is 100,000 L.mol-1.cm-
1
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SOLVED QUESTIONS
44) The unit of molar absorptivity is:
1. L mol–1 cm–1 2. L–1 mol cm–1 3. L mol cm–1 4. L mol cm
Explanation:
Beer-Lambert law A =  .c.l
Where A = absorbance
c = molar concentration
Prepared by
l = pathlength (in cm)
A
V. Aditya Vardhan
 = molar extinction coefficient or molar absorptiviy =
(note:  is pronounced as epsilon)
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.
Additional information
Absorbance (A) = log10(1/T)
= -log10 T
= -log10 (I /Io)
Where T = transmittance = I /Io
I = intensity of the transmitted light
Io = intensity of the initial incident light
* Remember transmittance (T) is inversely related to absorbance (A)
Other equations to remember:
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100
A = log10 ( ) = 2 - log10(%T)
%T
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)
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A 0.21
Ans:- c= = = 6.67 x 10-7 M
l 31500 x 10
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 ?
Ans:-  510 = 4.5 cm-1M-1
44.3) Transferrin is an iron-transport protein found in blood. Desferrioxamine B is an iron chelator
used to treat patients suffering from iron overload. Both are 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:
ACi
----------------------------------------------------------------------------------
max / nm
hem stry
iron-transferrin
 max / L mol–1 cm–1
iron-desferrioxamine B
-----------------------------------------------------------------------------------
428 3540 2730
470 4170 2290
-----------------------------------------------------------------------------------
Calculate 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.
Prepared by
Ans:-  M = 10 M -6
For iron transferrin, A = 4.6 x 10-2
V. Aditya Vardhan
For iron-desferrioxamine B, A = 1.6 x 10-1 = 16 x 10-2
Total = 4.6 x 10-2 + 16 x 10-2 = 2.06 x 10-1
44.4) The percentage transmittance of a transition metal complex at 360 nm and at 250C is 25%
for a 6 x 10-4 mol L -1 solution in a 1 cm cell. The molar absorption coefficient in the unit of L mol-1 cm-
1
is
(a)  1.0 x10-3 (b)  1.0 x103 (c)  2.0 x103 (d)  1.0 x104
Ans:- A = log10 (
100
%T
) = 2 - log10(%T)
= 2 - log25
= 2 - 2log5
= 2 - (2 x 0.6990)  0.6
A 0.6
 = = = 1 x 103 L mol-1cm -1
cl 6 x 10-4 x 1
44.5) A solution of a compound shows a transmittance of 0.800 in a 1.0 cm cell at 525 nm. The
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transmittance in a 5.0 cm cell at the same wavelength would be
(a) 0.160 (b) 0.654 (c) 0.240 (d) 0.317
hem stry

Ans:-
A1  log10 T1

A2  log10 T2
A1 l1
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But 
A2 l2
l1  hem
log10 Tstry
1
 =
l2  log10 T2
1  log10 0.800
or =
5  log10 T2
Hence -logT2  5 x -log0.8 = 5 x -(3log2 + log10-1 ) =5 x(-0.9 +1) = 0.5
or T2 =antilog(- 0.5) = antilog ( 1.5)  0.316

Prepared by
44.6) A solution containing 5 ppm of KMnO4 (F.W = 158) has a transmittance of 0.360 measured
in a 1cm cell at 500nm. The molar absorptivity of KMnO4 in L mol-1 cm-1 is
(a) 1.1 x 104 (b) 1.4 x 104 (c) 1.9 x 104 (d) 2.7 x 104
V. Aditya Vardhan
Hence the conc. = molarity(M) =
6
x =
6
Ans:- 5 ppm = = = 5 grams of KMnO4 is present in 10 grams (=10 mL) of water.
w 1000 5 1000
x = 3.16 x 10 -5 mol L-1
FW V(in mL) 158 10 6
A -logT -log0.36 0.444
Now  = =  = = 1.4 x 104 L mol-1cm -1
cl cl 3.16 x 10-5 x 1 3.16 x 10 -5 x 1
ACi hem stry
Original & Accurate copy of AdiChemistry CSIR NET & GATE study material is available only from the Author at www.adichemistry.com MILLER INDICES
What are Miller indices?
Miller indices are a notation for describing directions and labelling planes in lattices and crystals.
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Miller indices for directions in crystals
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A direction is expressed in terms of its ratio of unit vectors in the form [uvw] where u, v and w are
integers. A family of crystallographically equivalent directions is expressed as <uvw>.
Miller indices for crystal planes

A Miller indices for a plane are expressed as (hkl), where h, k and l are integers. A family of
crystallographically equivalent planes is expressed as {hkl}.
The orientation of a surface or a crystal plane may be defined by considering how the plane intersects
the main crystallographic axes of the solid.
How to assign Miller indices?

Prepared by
The following procedure is used to assign the Miller indices for crystal planes. To simplify the concept,
cubic crystal systems (with equal unit cell dimensions) are considered.
V. Aditya Vardhan z
www.adichemistry.com a
b
y
x
Cubic system
a=b=c
Step-1:
Identify the intercepts of the plane along the crystallographic axes (x, y & z), in terms of unit cell
dimensions.
Step-2:
Specify the intercepts in fractional coordinates by dividing by the respective cell-dimension i.e. a, b &
ACi
c.
Step-3:
Take the reciprocals of fractional coordinates.
Step-4:
Clear fractions either by multiplying or dividing through by a common number
hem in order to simplify them.
stry
Step-5:
Reduce to lowest terms wherever possible.
Finally, the numbers obtained are written in the brackets without using commas. The negative number is
denoted by a bar above it. The numbers are separated by gaps if they have two digits.
Original & Accurate copy of AdiChemistry CSIR NET & GATE study material is available only from the Author at www.adichemistry.com ILLUSTRATIONS
Example-1
For the plane shown below, the intercepts on x, y and z axes are a,  &  respectively..
Remember that if any plane is parallel to an axis, the intercept along that axis is  .
ACi hem stry

z
Step-1:
Prepared by
Intercepts: a,  , 
Step-2:
V. Aditya Vardhan
Fractional coordinates: a/a,  /a,  /a = 1,  , 
Note that for cubic systems a = b = c
Step-3:
Reciprocals: 1/1, /  , /  = 1, 0, 0
Step-4 and 5 are not required here.
Therefore, the Miller indices for this plane are: (100)
Note: The reason for why should we take reciprocals of intercepts is clear now. This operation is necessary
to eliminate  values.
Example-2
For the plane shown below, the intercepts on x, y and z axes are  , a & a respectively..
Step-1:
Intercepts:  , a, a
Step-2:
x
Fractional coordinates:  /a, a/a, a/a =  , 1, 1

ACi y
hem stry
Step-3:
Reciprocals: /  , 1/1, 1/1 = 0, 1, 1
Original & Accurate copy of AdiChemistry CSIR NET & GATE study material is available only from the Author at www.adichemistry.com Therefore, the Miller indices for this plane are: (011)
Example-3
For the plane shown below, the intercepts on x, y and z axes are a, a & a respectively.
ACi hem stry

z
Step-1:
Prepared by
Intercepts: a, a, a
Step-2:
Step-3: V. Aditya Vardhan

Fractional coordinates: a/a, a/a, a/a = 
Reciprocals: 
Example-4
For the plane shown below, the intercepts on x, y and z axes are a/2, a/2 & a respectively.
y
a/2 a/2
ACi
x
Step-1:
Intercepts: a/2, a/2, a
Step-2:
Fractional coordinates: a/2a, a/2a, a/a =  hem stry
Step-3:
Reciprocals: 
Example-5
For the plane shown below, the intercepts on x, y and z axes are a, -a &  respectively..
z
ACi hem stry
-a
y
a
x
Step-1:
Intercepts: a, -a, 
Step-2:
=  
Fractional coordinates: a/a, -a/a,  /aPrepared by
Step-3:
Reciprocals: 
V. Aditya Vardhan
Therefore, the Miller indices for this plane are: (1 10)
Example-6
For the plane shown below, the intercepts on x, y and z axes are  , 0 &  respectively..
y
Step-1:
Intercepts:  , 0, 
ACi
Step-2:
Fractional coordinates:  /a, 0/a,  /a =  , 0, 
Step-3:
Reciprocals:   , 0
hem stry
Therefore, the Miller indices for this plane would be:   0)
STOP! INFINITIES ARE NOT ALLOWED.

However, infinities are not allowed in miller indices. This is the problem with planes along the axes. To
avoid this, we have to translate the plane by a unit distance along the axis or axes with non zero index/
indices. Selected Topics for CSIR NET & GATE chemistry 2017
z
ACi hem stry
y
The plane is translated by unit distance ‘a’ along the y-axis. Now the Miller index can be computed as
follows:
Step-1: Prepared by
Intercepts:  , a, 
Step-2:
Fractional coordinates:  /a, a/a,  /a =  , 1, 
Step-3:
V. Aditya Vardhan
Reciprocals: , 0
Therefore, the Miller indices for this plane are: 
Some Generalisations
* The plane is parallel to that axis for which the Miller index is zero.
* The smaller a Miller index, the more nearly parallel the plane is to the axis.
* The larger a Miller index, the more nearly perpendicular a plane is to that axis.
* Multiplying or dividing Miller indices by a constant has no effect on the orientation of the plane
* Miller indices are almost always small.
symmetry-equivalent planes
A set of equivalent planes related by symmetry are indicated by using "curly" brackets. For example,
the planes: (100), (010) and (001) as shown below are symmetrically equivalent and can be represented
as: {100}.
(001)
(100)
ACi (010)
y
hem stry
x Selected Topics for CSIR NET & GATE chemistry 2017

COREY-CHAYKOVSKY REACTION
ACi
1) Choose the correcthem stry
PRACTICE PROBLEMS (MCQ)
statement about Corey-Chaykovsky reaction.

1) The sulfur ylides are stabilized when electron donating groups are attached to it.
2) Dimethylsulfoxonium methylide is less stable than dimethylsulfonium methylide.
3) With Michael acceptors, cyclopropanation is major route when unstable ylides are used.
4) With Michael acceptors, epoxidation is major route when unstable ylides are used.
2) The major product in the following reaction is:
SPh2 BF 4
Prepared by
CHO KOH, DMSO
1)
V. Aditya VardhanCHO
2)
3) 4)
www.adichemistry.com CHO
3) The major product expected in the following reaction is:

O
O Me3S+=O I- , NaH
O
DMSO
O O
1) O 2) O
ACi
O O
3) O 4) O
N
Ph Me3S+=O I- , NaH hem stry
OH DMSO
Ph
Ph
1) N 2) N
OH
OH
3)
ACi Ph
O
NHhem stry
4)
O
Ph
NH
5) (IISc 2009)
C6H6
S + ? major product
COOEt CHO
 Prepared by
a) b) c) O d) O
H CHO EtOOC CHO EtOOC EtOOC H
V. Aditya Vardhan
EtOOC H
6) The expected product in the following reaction is:

H H H H H
SCH3
1) MeI
2) t-BuOK
O
I SCH3 SCH3
S(CH3)2 SCH3
1) 2) 3) 4)
O O O O
OH Me3S+ I-
ACi
O DMSO, NaH
1) 2) 3) 4)
OH OH OH OH
O O O
hem O
stry
8) What is the major product formed in the following reaction?

O
O O -
(H3C)2S CH2
O
BnO O DMSO/THF
1)
ACi
BnO
O
hem stry
O
O
O 2)
BnO
O
O
O
O
3) O O 4) O O
O O
BnO O BnO O
Prepared by
9) What is the major product in the following Corey-Chaykovskii reaction?
MeO
O
V. Aditya Vardhan
OMe
(H3C)2S CH2
THF, 0 oC
-
MeO MeO MeO MeO
1)
OMe
2)
OMe
3)
OMe
4)
OMe
O
O O O

MeO
OH Me3SO+ I-, NaH
MeO
DMSO, RT
ACi
MeO
MeO O
OMe
hem stry

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Prepared by V. Aditya vardhan - i - mail id: adichemadi@gmail.

ACi hem stry Study material by V. Aditya vardhan

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# ACi hem stry

1 Bioinorganic chemistry: * Distribution of elements - Bulk & Trace

metals ; non metals - biological functions * Porphyrins * Oxygen

2 Analytical chemistry: * Chromatography * Basic concepts &

3 Nuclear chemistry: Terminology, Concepts, Formulae * Stability of

Selected Topics for CSIR NET & GATE chemistry 2017

Selected Topics for CSIR NET & GATE chemistry 2017

ACi hem stry

ACi hem stry

FUNCTIONING OF HEMOGLOBIN - A BIOINORGANIC PERSPECTIVE

Selected Topics for CSIR NET & GATE chemistry 2017

Selected Topics for CSIR NET & GATE chemistry 2017

Why does carbonhem stry

5) The metals present in nitrogenase are

6) The transition metal present in vitamin B12 is_______

13) The copper containing non heme respiratory protein is

14) The oxidation state of iron stored in ferritin is

19) The function of Na+ and K+ in biological systems is

20) Fluoride is present in the teeth in the form of

21) Which of the following is a channel forming ionophore?

22) The porphin system in chlorophyll is called as hem stry

23) The metal present in both superoxide dismutase and hemocyanin is

28) Hemerythrin belongs to the group of:

a) non-heme iron protein b) heme-iron protein

* Remember transmittance (T) is inversely related to absorbance (A)

Other equations to remember:

For iron transferrin, A = 4.6 x 10-2

Selected Topics for CSIR NET & GATE chemistry 2017

or T2 =antilog(- 0.5) = antilog ( 1.5)  0.316

ACi hem stry

Selected Topics for CSIR NET & GATE chemistry 2017

Miller indices for crystal planes

How to assign Miller indices?

ACi hem stry

Fractional coordinates:  /a, a/a, a/a =  , 1, 1

ACi hem stry

Step-3: V. Aditya Vardhan

Therefore, the Miller indices for this plane are: (111)

Therefore, the Miller indices for this plane are: (221)

STOP! INFINITIES ARE NOT ALLOWED.

Therefore, the Miller indices for this plane are: 

x Selected Topics for CSIR NET & GATE chemistry 2017

statement about Corey-Chaykovsky reaction.

2) The major product in the following reaction is:

3) The major product expected in the following reaction is:

4) The major product in the following reaction is:

Selected Topics for CSIR NET & GATE chemistry 2017

6) The expected product in the following reaction is:

7) The major product in the following reaction is:

8) What is the major product formed in the following reaction?

Selected Topics for CSIR NET & GATE chemistry 2017

MeO MeO MeO MeO

10) The major product in the following reaction is:

Selected Topics for CSIR NET & GATE chemistry 2017

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