Prepared by V. Aditya vardhan adichemadi(at)gmail.

com WARANGAL
V
.
A
D
I
T
Y
A

V
A
R
D
H
A
N
W
W
W
.
A
D
I
C
H
E
M
A
D
I
.
C
O
M
155
This part (Series-3 from Q.no 61 - 80) is updated on 22nd Nov, 2009 and going to be
updated frequently. For recent updates and other parts, join the following group
http://www.adichemadi.com
SOLVED
CSIR UGC JRF NET
CHEMICAL SCIENCES
PAPER 1 (PART-B)
SERIES-3
NOTE: Related and additional questions appeared in previous GATE exams are also
solved.
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 / an
1. three dimensional conductor
2. two dimensional conductor
3. insulator
4. one dimensional conductor
Explanation:
* (SN)
n
, known as polythiazyl, is a linear polymeric sulfur nitride. It is a one dimensional
conductor. 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
N
S
N
S
N
S
N
S
N
S
N
S
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 this
conversion, silver is sulfided to silver sulfide which catalyses the conversion of S
4
N
4
to
Disulfur dinitride (S
2
N
2
), which readily polymerized to (SN)
n
.
S4N4 +8Ag Ag
2
S +2N
2
S4N4
Ag
2
S (as catalyst)
77 K
2S
2
N
2

2S
2
N
2
(SN)n
1) sublimes to surface at 0
o
C
2) 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
W
W
W
.
A
D
I
C
H
E
M
A
D
I
.
C
O
M
156
Ans:-
S
S
S
N
N
N
N
S
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 followed
by extraction into dioxane.
24 SCl
2
+64 NH
3
-------------->4 S
4
N
4
+S
8
+48 NH
4
Cl
61.3) What is the difference between cyclophosphazanes and cyclophosphazenes?
Ans:- Cyclophosphazanes: saturated cyclic systems involving P(III)nitrogen linkages; mostly
four membered.
Cyclophosphazenes: unsaturated rings with P(V)nitrogen bonds; mostly six or eight
membered.
61.4) Write the equation for the synthesis of (Cl
2
NP)
2
?
Ans:- Reaction of phosphorus pentachloride with ammonium chloride in a high-boiling solvent,
like 1,1,2,2-tetrachloroethane yields (Cl
2
PN)
2
.
TO BE COMPLETED
Practice questions:
1) The structure of P
4
N
4
Cl
8
is puckered whereas that of P
4
N
4
F
8
is planar because:
a) F is more electronegative than Cl
b) F is smaller in size than that of Cl
c) F is more polarizable than Cl
d) Extent of -electron delocalization more in P
4
N
4
Cl
8
than in P
4
N
4
F
8
63) The molar absorptivity at
max
is minimum for
1. [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 complex
have intense color and otherwise it will have pale color.
* The intensity can be determined from the following quantum mechanical selection rules that
state whether the transitions are allowed (intense color) or not allowed (pale color)
a) Symmetry forbidden or Laporte forbidden (
= 1 l
): If the molecule has centre of
symmetry, the transitions from one centrosymmetric orbital (that with centre of inversion) to
another are forbidden. i.e., transitions within a given set of p or d orbitals (i.e. those which
only 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 (
S = 0
): The number of unpaired electrons cannot change uponPrepared by V. Aditya vardhan adichemadi(at)gmail.com WARANGAL
V
.
A
D
I
T
Y
A

V
A
R
D
H
A
N
W
W
W
.
A
D
I
C
H
E
M
A
D
I
.
C
O
M
157
excitation i.e., no electron spin-flip is allowed. Always transition between triplet to triplet and
singlet to singlet states are allowed.
ANSWER TO THE QUESTION:
* All the molecules are octahedral with centre of symmetry and hence the excitations are
symmetry 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
or t
2g
3
e
g
2
spin forbidden
Cr
2+
- 3d
4
or t
2g
3
e
g
1
one spin allowed transition
Co
2+
- 3d
7
or t
2g
5
e
g
2
three spin allowed transitions
Fe
2+
- 3d
6
or t
2g
4
e
g
2
one spin allowed transition
* As the transitions in Mn
2+
are both symmetry and spin forbidden, the molar absorptivity is
minimum 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
times larger than for octrahedral complexes. Why? Ans: Do not possess centre of inversion.
Additional questions
63.1) 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 color
due to ligand to metal charge transfer (LMCT) phenomenon. MnO
4
-
absorbs yellow and
transmits violet part of light.
Charge transfer spectra: Charge transfer (CT) is of two types viz.,
i) Ligand to Metal Charge Transfer (LMCT)
ii) Metal to Ligand Charge Transfer (MLCT)
* Remember! The energy required for CT is greater than the energy for d-d transitions. But it
is spin and symmetry allowed and hence intense absorptions are possible. i.e., extinction
coefficients are higher.
LMCT: In LMCT, an electron is transferred from ligand to the metal, which is therefore
reduced in the excited state. Charge transfer is analogous to an internal redox reaction, and
hence 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 the
LMCT energy. LMCT transitions in the visible region of the spectrum give intense color as in
case 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
4
3-
>CrO
4
2-
>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 asPrepared by V. Aditya vardhan adichemadi(at)gmail.com WARANGAL
V
.
A
D
I
T
Y
A

V
A
R
D
H
A
N
W
W
W
.
A
D
I
C
H
E
M
A
D
I
.
C
O
M
158
the 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
4
2-
deep yellow (absorbs violet (high energy) and transmits yellow)
iii) VO
4
3-
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 artists pigment cadmium yellow is due to transition from S
2-
(p
orbital) to Cd
2+
(empty 5s orbital).
ii) HgS: It is red due to S
2-
(p) to Hg
2+
(6s) transition.
Note: 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 charge
transfer occurs from metal to ligand with emty orbital especially low lying
*
orbital.
e.g. Tris(2,2-bipyridyl)ruthenium(II) - [Ru(bpy)
3
]
2+
[Fe(bpy)
3
]
2+
[Fe(phen)
3
]
2+
-- ferroin
Note: phen =1,10-phenanthroline
Optical spectroscopy (UV-Visible) is a powerful technique to assign and characterize
charge transfer bands in these complexes.
Additional questions:
63.1) In general, UV-Visible absorption peaks of transition metal ions are broad, whereas
those of f-block metal ions are sharp. Explain?
Ans:- In transition metals, absorption peaks appear due to d-d transitions, which are affected by
the external environment (like solvent and ligand effects). Hence absorptions are broad.
In case of f-block elements, the f orbitals are deep inside the atom and are screened from
the external environment. Hence the peaks are sharp. However, the absorptions are less
intense.
63.2) Explain why ff transitions of lanthanide complexes are weaker than dd transitions
of transition metal complexes in the electronic spectra?
Ans:- * Both dd and ff transitions are parity forbidden (symmetry forbidden).
* But in the case of dd spectra, vibronic coupling lowers the symmetry round the metal ion,
so d/p mixing can occur and the dd transitions are to some extent allowed. (It is the reason
why the peaks are observed even though they are forbidden)
* Because the 4f orbitals are so contracted (as they are deep inside) compared with d orbitals,
f/p mixing and vibronic coupling are much more limited, thus the ff transitions are less
allowed and so the peaks are less intense.
Note: The centre of symmetry of complexes is momentarily destroyed due to asymmetric
molecular vibrations. This is called vibronic coupling.
63.3) Fe(SCN)
2+
is blood red in color eventhough d-d transitions in Fe
3+
ion with d
5
configu-
ration are forbidden. Explain.Prepared by V. Aditya vardhan adichemadi(at)gmail.com WARANGAL
V
.
A
D
I
T
Y
A

V
A
R
D
H
A
N
W
W
W
.
A
D
I
C
H
E
M
A
D
I
.
C
O
M
159
Ans:- Fe(SCN)
2+
, correctly represented as [Fe(NCS)(H
2
O)
5
]
2+
, is an octahedral complex. The
configuration of Fe
3+
is t
2g
3
e
g
2
. Hence the d-d transitions in them are spin forbidden (though
Laporte allowed).
But the intense red color is due to charge transfer from SCN
-
to Fe(III) ion (LMCT).
63.4) Predict the line width and the intensities of peaks in the electronic spectra of CuCl
4
2-
and Eu(H
2
O)
8
3+
complexes.
Ans:- The peaks are broad and intense in case of CuCl
4
2-
.
* Intense due to LMCT possible from Cl
-
ligand to Cu(II).
* The d-d component is also strong as the d-d transitions are Laporte allowed as the complex
is tetrahedral (no inversion symmetry).
* Broad because d-d transitions are vibronically coupled.
In case of Eu(H
2
O)
8
3+
the peaks are very narrow and weak.
* These are narrow as there are no crystal field effects on f-f transitions as the f-orbitals are
deeply buried inside the atom. The metal-ligand overlapping is very weak and hence no
vibronic coupling possible.
* These are also weak as there is no vibronic coupling. (The laporte forbidden transitions are
atleast possible due to vibronic coupling which destroy the symmetry of complex for a short
span of time)
63.5) [Fe(bpy)
3
]
2+
is expected to exhibit an MLCT rather than an LMCT absorption. Com-
ment.
Ans:- Iron is in the Fe(II) state which is harder to be reduced and hence LMCT is not observed.
MLCT is possible because metal d-orbitals are close in energy to the ligand
*
orbitals.
Remember this occurs in visible region.
63.6) Why is a transition from a t
2g
to an e
g
orbital spin allowed in [V(OH
2
)
6
]
3+
?
Ans:- The electronic configuration if V
3+
ion is t
2g
2
e
g
0
. The transition is allowed as it involves NO
spin-flip. i.e., transition is of triplet to triplet type and hence allowed.
spin allowed
triplet triplet
t
2g
e
g
63.6) The reaction below produces both red and green crystals with following data:
NiBr
2
+ PEtPh
2
------> NiBr
2
(PEtPh
2
)
2
( both red and green forms)
The following data is available:
Form data
Red
eff
= 0
Green
eff
= 3.0 BM
The red form has zero dipole moment, whereas the green form has net dipole mo-
ment.
When the red form is dissolved in dichloromethane, the magnetic moment of the
solution observed will be 2.69 BM.
Propose the possible geometries of both the forms.
Ans:- The four-coordinate compound can exist in two geometries:
i.e., square planar and tetrahedralPrepared by V. Aditya vardhan adichemadi(at)gmail.com WARANGAL
V
.
A
D
I
T
Y
A

V
A
R
D
H
A
N
W
W
W
.
A
D
I
C
H
E
M
A
D
I
.
C
O
M
160
As a square planar complex, the d
8
Ni(II) would be diamagnetic. Therefore the red com-
plex is square planar. It must be a trans isomer as its dipole moment is zero.
As a tetrahedral complex, the d
8
Ni(II) would have the electronic configuration (e
g
)
4
(t
2g
)
4
and have 2 unpaired electrons. Therefore the green form is Tetrahedral.
d
xz
d
yz
d
z
2
d
xy
d
x
2
-y
2
e
t
2
Square planar Tetrahedral
A square planar complex will have a large crystal field splitting energy (delta) and absorb
shorter wavelengths and reflect long wavelengths such as red. A Tetrahedral complex will
have a small delta and absorb longer wavelengths and reflect shorter wavelengths such as
green.
As the tetrahedral form is more stable, the square planar complex is converted to tetrahe-
dral. The slightly low value of 2.69 BM may indicate there is an equilibrium between square
planar and tetrahedral forms.
63.7) When an ethanolic solution of NiBr
2
is treated with two equivalents of the phosphine
PEtPh
2
, two products A and B can be obtained by varying the crystallisation condi-
tions.
Compound A has no dipole moment and is diamagnetic. One peak due to Ni-Br
stretching can be observed in its IR spectrum.
Compound B has a dipole moment and is paramagnetic. The IR spectrum of B
shows two peaks due to Ni-Br stretching.
By contrast, the analogous reaction with PtBr
2
and two equivalents of the same
phosphine PEtPh
2
gives just one compound, C, that has similar spectroscopic and
magnetic characteristics to A.
Identify A, B and C and explain the observations.
Ans:- A is square planar and trans isomer. B is tetrahedral. (see the explanation given for the
previous question)
gkuryue854wycvli8794e5hggbli[097465eyv,mk[p9-7634utdglkok
][-\=--0=]90y8oedou760656w53w57328\
==-
\pob,jgd898
\=-pho8706w42yli
\=
63.8) 1,10-Phenanthroline is added during the quantitative analysis of Fe(II) by UV-visible
spectroscopy. Explain why?
Ans:- 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 byPrepared by V. Aditya vardhan adichemadi(at)gmail.com WARANGAL
V
.
A
D
I
T
Y
A

V
A
R
D
H
A
N
W
W
W
.
A
D
I
C
H
E
M
A
D
I
.
C
O
M
161
complexing the metal ion with some suitable organic chelating agent to produce a charge-
transfer complex.
Eg., 1,10-phenanthroline improves the molar absorptivity of Fe(II).
Note: 1,10-Phenanthroline complexed with iron ions is commonly called as ferroin - reduced
form is [Fe(phen)
3
]
2+
and oxidised form is [Fe(phen)
3
]
3+
. It is 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.
Reduced form
(deep red)
oxidized form
(light blue)
N
N
N
N
N N
Fe
3+ N
N
N
N
N N
Fe
2+
Note: Ferroin shows bright colors due to MLCT.
Wait!
Lanthanides & actinides having incomplete f-levels and hence 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.(Also remem-
ber, 4f-4f transitions are sharp and not of 4f-5d.)
Practice questions
1) Account for the following molar extinction coefficients for the compounds shown.
[Mn(OH
2
)
6
]
2+

max
<10
-1
dm
3
mol
-1
cm
-1
[CoCl
4
]
2-

max
=10
2
- 10
3
dm
3
mol
-1
cm
-1
[MnO
4
]
2-

max
=10
3
- 10
5
dm
3
mol
-1
cm
-1
Hint: [CoCl
4
]
2-
is tetrahedral and the configuration of Co
2+
is e
4
t
2
3
. Hence the transitions are
both Laporte and spin allowed.
64) The acid catalyzed hydrolysis of trans-[Co(en)
2
AX]
n+
can give cis-product also due to
the formation of
1. square pyramidal intermediate
2. trigonal bipyramidal intermediate
3. pentagonal bipyramidal intermediate
4. face capped octahedral intermediate
Additional questions
64.1) Coordinated water molecules of a Cd(II) complex can be successively replaced by Br
-
finally to result in [CdBr
4
]
2-
. In this process, the fourth equilibrium constant is observe
to be higher than the third one, because;
1) Equilibrium constant for the last step is always the highest.
2) Three molecules of H
2
O are release during the fourth step.
3) The aquo Cd
2+
complex is octahedral.
4) An anion (Br
-
) rplaces a neutral (H
2
O) molecule from the coordination sphere.Prepared by V. Aditya vardhan adichemadi(at)gmail.com WARANGAL
V
.
A
D
I
T
Y
A

V
A
R
D
H
A
N
W
W
W
.
A
D
I
C
H
E
M
A
D
I
.
C
O
M
162
Ans:- The mechanism and the equilibrium constant values for each step during the reaction are
given below.
2+ - +
2 6 (aq) (aq) 2 5 (aq) 2 (l) 1
[Cd(OH ) ] + Br [CdBr(OH ) ] +H O ; logK 1.56 =
+ -
2 5 (aq) (aq) 2 2 4 (aq) 2 (l) 2
[CdBr(OH ) ] + Br [CdBr (OH ) ] +H O ; logK 0.54 =
- -
2 2 4 (aq) (aq) 3 2 3 (aq) 2 (l) 3
[CdBr (OH ) ] + Br [CdBr (OH ) ] +H O ; logK 0.06 =
- - 2-
3 2 3 (aq) (aq) 4 (aq) 2 (l) 4
[CdBr (OH ) ] + Br [CdBr ] +3H O ; logK 0.37
octahedral tetrahedral
=
It is clear from above data that, in the fourth step the octahedral aquo complex is con-
verted to tetrahedral all halo complex and 3 moles of water molecules are released (entropy
favored). Hence the K
4
is greater than K
3
.
Note: Generally aquo complexes of M
2+
ions are six coordinated, whereas halo complexes
are four coordinated. (only generalization)
More explanation: Usually the stepwise formation constants lie in the order:
K
1
>K
2
>K
3
....... >K
n
.
This general trend can be explained simply by considering the decrease in the number of
the ligand H
2
O molecules available for replacement in susequent steps.
In general, K
n
>K
n+1
. But this order is reversed, when there is some structural change
during that step.
67) The number of faces and edges in IF
7
polyhedron are, respectively
1. 15 and 15
2. 10 and 15
3. 10 and 10
4. 15 and 10
Explanation:
F F
F
F
F
F
F
I
There are 10 faces and 15 edges.
69) O
2
can be converted to O
2
+
by using
1. PtF
6
2. KF
3. Na
2
S
2
O
3
4. Br
2
Explanation:
* PtF
6
is a strong oxidising agent and can remove electron from dioxygen.
O
2
+PtF
6
------>O
2
+
[PtF
6
]
-
* Bartlett made this compound, which lead to the discovery of first compound of noble gas,
Xenon. Bartlett realized that the first ionization energy of dioxygen, 1180 kJ mol
-1
is almost
equal to that of xenon, 1170 kJ mol
-1
. Furthermore, the dioxygen cation should be roughly thePrepared by V. Aditya vardhan adichemadi(at)gmail.com WARANGAL
V
.
A
D
I
T
Y
A

V
A
R
D
H
A
N
W
W
W
.
A
D
I
C
H
E
M
A
D
I
.
C
O
M
163
same size as a Xe
+
ion, and hence the lattice energies of the corresponding compounds should
be similar.
Xe +PtF
6
------>Xe[PtF
6
]
71) CFSE of transition metal complexes can be determined by
1. UV-visible spectroscopy
2. IR spectroscopy
3. Microwave spectroscopy
4. NMR spectroscopy
Explanation:
* Crystal Field Stabilization Energy (CFSE) is calculated by using UV-visible spectroscopy.
First the
max
for a d-d electronic transition is recorded using spectrometer. The energy
corresponding to
max
is given by
max
hc
E=

. This is equal to crystal field splitting energy (

A
).
From this CFSE is calculated as follows for simple cases.
For octahedral complexes, CFSE =(-0.4a +0.6b) x
o
A
Where a =no. of electrons in t
2g
orbitals
b =no. of electrons in e
g
orbitals
For tetrahedral complexes, CFSE =(-0.6a +0.4b) x
t
A
Where a =no. of electrons in e orbitals
b =no. of electrons in t
2
orbitals
Note:
max
refers to the wavelength of peak with maximum molar absorptivity ( )
Additional questions:
71.1) Calculate the CFSE (crystal field stabilization energy) of [TiCl
6
]
3-
if the
max
is 770
nm.
Ans:- The energy corresponding to
max
=770 nm can be calculated as
-34 8 -1
-9
max
-19
-22
-22 23
hc 6.625 x 10 J .sec x 3 x 10 m.sec
E= =
770 x 10 m
=2.58 x 10 J
=2.58 x 10 kJ per one molecule
=2.58 x 10 kJ x 6.023 x 10 =155 kJ per mole
This energy is equal to the magnitude of energy separation(
o
A ) between t
2g
and e
g
in the
octahedral complex [TiCl
6
]
3-
.
E.C of Ti
3+
in the complex is 3d
1
and the only electron occupies the t
2g

.
Hence the CFSE=1 x -2/5
o
A =-2/5 x 155 = 62 kJ. mole
-1
.
Practice questions
1) The UV-Vis spectrum of ReF
6
exhibits absorption at 32,500 cm
-1
. Calculate
o
in kJ mol
-1
.
2) Which of the following is not a source of visible radiation?Prepared by V. Aditya vardhan adichemadi(at)gmail.com WARANGAL
V
.
A
D
I
T
Y
A

V
A
R
D
H
A
N
W
W
W
.
A
D
I
C
H
E
M
A
D
I
.
C
O
M
164
a) Deuterium lamp b) Tungsten lamp
c) Xenon arc lamp d) All.
Note: Deuterium and hydrogen lamps are essentially identical. But D
2
lamps are a little
brighter and hence are exclusively used over H
2
lamps.
73) In aqueous medium a mixture of KI and I
2
converts thiosulfate to
1. S
4
O
6
2
2. SO
4
2
3. S
2
O
6
2
4. S
2
O
4
2
Explanation:
* Iodine oxidises thiosulfate to tetrathionate.
2S
2
O
3
2-
+ I
2
S
4
O
6
2-
+ 2I
-
S O
-
S
O
O
-
S S
O
O
O
-
S S O
-
O
O
thiosulfate tetrathionate
KI
KI reacts with I
2
by forming KI
3
and increases its solubility in water.
* This reaction is used in iodometry.
Additional information:
Iodine is used in iodimetry and iodometry to estimate various oxidising and reducing
analytes.
Molecular Iodine(I
2
) is slightly soluble in water, but its solubility is greatly enhanced by
complexation with iodide. Hence when used as titrant, I
2
is dissolved in water containing
excess of KI. This solution has brown color.
I
2
+ I
-
---------> I
3
-
To detect the end point in titrations using iodine, starch solution is added. Iodine imparts
navy blue color to starch solutions. The blue colored starch-iodine complex contains long
linear chains of I
5
-
, [I-I-I-I-I]
-
in amylose part of starch.
IODIMETRY
* In iodimetry, reducing analyte is titrated directly with Iodine. The reducing analyte reduces
iodine(I
2
) to iodide(I
-
). This method is used in estimation of Ascorbic acid, glucose, phospho-
rus acid etc.,
* Ascorbic acid is oxidised by iodine to dehydroascorbic acid.
* Glucose is oxidised to gluconic acid (the -CHO group in glucose is converted to -COOH)
RCHO +3OH
-
+I
3
-
RCOO
-
+2H
2
O +3I
-
* Phosphorus acid is converted to phosphoric acid.
H
3
PO
3
+H
2
O +I
3
-
H
3
PO
4
+2H
+
+3I
-
* In iodimetry, the starch solution can be added at the begining of the titration.Prepared by V. Aditya vardhan adichemadi(at)gmail.com WARANGAL
V
.
A
D
I
T
Y
A

V
A
R
D
H
A
N
W
W
W
.
A
D
I
C
H
E
M
A
D
I
.
C
O
M
165
IODOMETRY:
* In iodometry, first an oxidizing analyte is added to excess of I
-
solution to liberate I
2
which
is then titrated against a standard solution of thiosulfate.
first step ---- oxidation of I
-
to I
2
by an oxidising analyte.
second step ---- reduction of I
2
to I
-
by thiosulfate.
Iodometry is used in the estimation of CuSO
4
, K
2
Cr
2
O
7
, KMnO
4
, Br
2
, Cl
2
, BrO
3
-
etc.,
Estimation of copper:
CuSO
4
is made to react with excess of I
-
solution. Thus formed I
2
is titrated with standard
thiosulfate solution.
2S
2
O
3
2-
+ I
3
-
S
4
O
6
2-
+ 3I
-
2CuSO
4
+ 4I
-
2CuI + SO
4
2-
+ I
2
white ppt
The iodine liberated in the first step is equivalent to CuSO
4
. The amount of CuSO
4
is
estimated indirectly by estimating this liberated I
2
with standard thiosulfate solution.
* In iodometry, starch solution is added only just before the equivalence point (which is
detected visually by fading of brown color of I
3
-
ions). This is because, at high concentrations,
some I
2
remains bound to starch particles.
* In the estimation of copper, the precipitated CuI tends to bind some iodine. To replace this
iodine and bring it into solution, thiocyanate solution is added at the end point.
Additional questions:
73.1) Copper(I) iodide is a stable species, while coppe(II) iodide does not exist. Explain.
Ans:- Cu
2+
can oxidise I
-
to I
2
and hence Copper(II) iodide does not exist.
2Cu
2+
+2I
-
--------> 2Cu
+
+I
2
Note:
1) In general Cu(II) ion is more stable than Cu(I) ion - (contrary to above observation).
2) Remember, other dihalides of copper (CuF
2
, CuCl
2
and CuBr
2
) are possible (Why?
Simply because other halides cannot be oxidized by Cu(II))
73.2) The black precipitate formed when hypo is added with silver nitrate solution is
a) Ag
2
S b) Na
3
[Ag(S
2
O
3
)
2
] c) S d) Na
2
S
Ans:- When less amount of hypo is added to silver nitrate, initially a white precipitate of silver
thiosulfate is formed and it is immediately reduced to black silver sulfide precipitate.
Na
2
S
2
O
3
+2AgNO
3
Ag
2
S
2
O
3
+2NaNO
3
Ag
2
S
2
O
3
+H
2
O Ag
2
S +H
2
SO
4
Black ppt.
Note: But when excess of hypo is used, the silver thiosulfate formed will be soluble in hypo
by forming a water soluble complex, sodium argento thiosulfate, Na
3
[Ag(S
2
O
3
)
2
]
3Na
2
S
2
O
3
+Ag
2
S
2
O
3
2Na
3
[Ag(S
2
O
3
)
2
]
H.W: What is the IUPAC name of above complex?Prepared by V. Aditya vardhan adichemadi(at)gmail.com WARANGAL
V
.
A
D
I
T
Y
A

V
A
R
D
H
A
N
W
W
W
.
A
D
I
C
H
E
M
A
D
I
.
C
O
M
166
73.3) Silver halides are used in photographic plates because:
a) oxidized in air
b) reduced by light
c) dissociated in air
d) soluble in hypo
e) do not undergo dissociation air
Ans:- d
Explanation: AgBr is used in making photographic films. It is dissociated by forming black
silver when exposed to light.
2AgBr -------->2Ag + Br
2
The unexposed AgBr is removed from the photographic film by treating it with hypo
solution in dark. This process is called photography fixing. The AgBr dissoves in hypo by
forming water soluble complex Na
3
[Ag(S
2
O
3
)
2
].
2Na
2
S
2
O
3
+AgBr Na
3
[Ag(S
2
O
3
)
2
] +NaBr
Note: AgBr is neither oxidized or reduced by air or light. It is just dissociated (self reduction
and oxidation). It wont be dissociated by air but dissociated in light.
74) An exothermic reaction will necessarily follow the condition
1.
H< 0
2.
> H 0
3.
= H 0
4.
= S 0
Explanation:
*
H < 0
------- Exothermic
*
H > 0
------- Endothermic
75) The unit of rate constant (k) for a zero-order reaction is
1) s
-1
2) L mol
-1
s
-1
3) s 4) mol L
-1
s
-1
Explanation:
* In general, the unit of rate constant for n
th
order reaction is given by
M
1-n
.time
-1
=(mol / L)
1-n
.time
-1
=mol
1-n
.L
n-1
.time
-1
* Hence for zero order reaction: M
1-0
sec
-1
=mol.L
-1
.sec
-1
Derivation of Unit of rate constant
For a general reaction,
A products
Rate expression can be written as
| |
n dc
rate = k A
dt
=
where n =order of the reaction
| |
n
dc 1
k= x
dt
A

Units of
( )
n
M 1
k= x
sec
MPrepared by V. Aditya vardhan adichemadi(at)gmail.com WARANGAL
V
.
A
D
I
T
Y
A

V
A
R
D
H
A
N
W
W
W
.
A
D
I
C
H
E
M
A
D
I
.
C
O
M
167
( ) ( )
1-n 1-n
M mole/ litre
=
sec sec
=
1-n 1-n n-1 -1
=M .sec mole .L .sec =
For 1
st
order reaction

sec
-1
For 2
nd
order reaction

L.mole
-1
sec
-1
For 3
rd
order reaction

L
2
.mole
-2
sec
-1
For zero order reaction

mole .L
-1
sec
-1
76) Heating is observed when N
2
gas at 200 atm is expanded at T > 600 K. It is because
1. inversion temperature is smaller than 600 K
2. N
2
is a real gas
3. Joule-Thomson coefficient is negative
4. Joule-Thomson coefficient is positive
Explanation:
Joule-Thomson effect: The change in temperature of non-ideal gas when it is allowed to
expand adiabatically from high pressure to low pressure is called Joule-Thomson effect.
The temperature may increase or decrease during this process.
Joule-Thomson coefficient =
lim 0
JT
H H
T T
as P
P P

c A
| | | |
= = A
| |
c A
\ . \ .
The value of Joule-Thompson coefficient may be positive or negative. The temperature at
which its sign is changed is called Joule-Thompson inversion temperature.
The sign of the Joule-Thompson coefficient is positive below the critical temperature and
the gas is cooled upon expansion. Hence below the critical temperature, the gas can be
liquified.
But the sign of the coefficient above the critical temperature is negative and the gas is
heated upon expansion. Hence above the critical tempertature, it is NOT possible to liquify
the gas.
Usually most of the gases are cooled upon adiabatic expansion at room temperature as
their critical temperatures are above the room temperature.
But the gases like H
2
, He and Ne have their critical temperatures below room temperature
(RT) and hence their temperature increases during adiabatic expansion at RT. These are also
difficult to liquify.
Answer to the question: inversion temperature is smaller than 600 K.
Practice questions:
1) The Joule-Thomson coefficient for N
2
is assumed to be a constant value of 0.15 K.bar
-1
. If
the N
2
undergoes a drop of pressure of 200 bar, then the temperature will be:
1) raised by 30 K 2) dropped by 30 K
3) remains constant 4) no change in temperature.