B.V.V.

Sangha’s
Basaveshwar Science College, Bagalkot
Department of Chemistry
BSc VI Sem Paper-I
e-notes

Inorganic Chemistry:

UNIT-I Coordination compounds –II 09 hours

Crystal field theory(CFT) with reference to octahedral, distorted
octahedral(JahnTellar distortion), tetrahedral and square planar complexes,
calculation of crystal field stabilization energy, factors affecting 10Dq,
consequences of crystal field splitting on ionic radii of M+2 ions, enthalpy of
hydration of M+2 ions, explanation of colour and magnetic properties of
magnetic complexes, limitations of crystal field theory, calculation of
magnetic moment using Gouy’s method,

UNIT-II Metal-ligand Equilibria: 05 hours

Stability constant, stepwise and overall formation constants, trends in step
wise constants, factors affecting the stability of the metal complexes with
reference to the nature of metal ion and ligand. Chelates - definition,
characteristics, factors influencing the stability of metal chelates and
importance of chelates.
UNIT-III Organometallic Chemistry 03 hours
Introduction, classification of organotransition metal complexes, 18 electron
rule with respect to [Fe(CO)5], [Ni(CO)5], [Mn(CO)5]+, ferrocene, structure
and bonding in metal olefins (Zeise’s Salt).

Organic Chemistry:

UNIT-I Carbohydrates 05 hours

Haworth and conformational formulae of glucose and fructose, mutarotation
and its mechanism, osazone formation, Killani’s synthesis, Ruff’s degradation,
epimers and epimerisation with respect to monosaccharides,
interconversions of glucose and fructose.

UNIT-II Vitamins and Harmones 03 hours

Vitamins: Classification and importance of vitamin-A, B6, B12, C, D and E.
Synthesis of Vitamin-C from D(+)-glucose, synthesis of vitamin-A by Vandrop
etal.

UNIT-III Amino acids, Peptides and Proteins 06 hours

Classification, structure and stereochemistry(D and L) of amino acids, acid-
base behaviour, iso-electric point and electrophoresis, peptides-
nomenclature and structure of peptides, synthesis of a dipeptide(Bergmann
synthesis), Classification of proteins, levels of protein structure(primary,
secondary and tertiary structure), protein denaturation and renaturation.
UNIT-IV Terpenoids 03 hours Introduction, classification of terpenes,
Ingold’s isoprene rule, constitution of citral with synthesis, synthesis of α and
β ionones, synthesis of α-terpeniol.
Physical Chemistry:

UNIT-I Electronic Spectrum 05 hours

Concept potential energy curves for bonding and antibonding molecular
orbitals, qualitative description of selection rules, energy levels and
respective transitions, Frank–Condon principle.

UNIT-II Physical properties and molecular structure 04 hours

Introduction-dipole moment, induced dipole moment, measurement of
dipole moment by temperature variation method and its applications.

UNIT-III Polymers 03 hours

Introduction, classification, determination of molar masses of
macromolecules by viscometry and Donnan membrane equilibrium.

UNIT-IV Quantum Chemistry 04 Hours

Photoelectric effect - Einstein’s photoelectric equation, wave particle duality,
deBroglie hypothesis, de-Broglie equation(derivation), experimental
verificationDavisson-Germer experiment.
Coordination compounds

Introduction

Crystal field theory this theory involves an electrostatic approach to

the bonding in complexes it was first applied to ionic type crystalline
substances therefore it is very Afton called The crystal field theory this
theory considers the metal iron as being placed in an electrostatic field
created by the surrounding molecules are ions this electric field changes
the energies of the electrons in the case of transition metal ion many e
of the properties of the complexes are related to this energy changes
this theory consider the bonding in complexes to be entirely
electrostatic The crystal field theory was proposed a little earlier than
the valence bond theory but it took about 20 years for this theory to be
used by chemists in 1951 miniature article chemistry working
independently use the Crystal Field theory in the spectra of competition
D block elements.
Silent features of Crystal Field theory
1. This theory considered as a complex as a combination of Central ion
surrounded by other Haryana are molecules with electrical dipole card
ligand it regards this ligands as point charges as point Dipole.
2. The bonding between the metal cation and legends arises due to the
electrostatic attraction between the nucleus of the metal cation and
 the partial negative charge in variable present on the ligand. Thus
bond between the metal and the ligand is purely ionic
3. The interaction between the electrons of the cation and those of the
ligands is entirely repulsive. these repulsive force are responsible for
the splitting up the d orbitals of the metal cation.
4. In its simplest form crystal field theory consider the overlapping
between the orbitals and ligand orbitals
5. The d orbitals which are degenerate in a free metal ion have their
degeneracy destroyed by the approach of the ligands during the
formation of a complex.

Shapes of the d orbital

Octahedral Complexes:

The octahedral arrangement of six ligands surrounding the central metal ion
is as shown in the figure.
 In an octahedral complex, the metal ion is at the center and the ligands are
at the six corners. In the figure, the directions x, y and z point to the three
adjacent corners of the octahedron. The lobes of the eg orbitals (dx2-y2 and
dz2) point along the x, y and z axis while the lobes of the t2g orbitals (dxy, dzx
and dyz) point in between the axes. As a result, the approach of six ligands
along the x, y z, -x,-y and –z directions will increase the energy of dx 2-y2 and
dz2 orbitals (which point towards the ligands) much more than that it
increases the energy of dxy, dzx and dyz orbitals ( which point in between the
metal-legand bond axis).

Thus, under the influence of an octahedral field, the d orbitals split into triply
degenerate orbitals with less energy and another as doubly degenerate
orbitals with higher energy. The main energy level between these two sets of
orbitals is taken as zero, which is called bari centre. The splitting between
these two orbitals is called crystal field splitting. The magnitude of
stabilization will be 0.4 Δo and the magnitude of destabilization will be 0.6 Δ o.

The magnitude of the splitting of the t2g and eg orbitals changes from one
octahedral complex to another. It depends on the identity of the metal ion,
the charge on this ion, and the nature of the ligands coordinated to the metal
ion.

Jahn Teller distortion

In the electronically degenerate state, the orbitals are said to be
asymmetrically occupied and get more energy. Therefore the system tries to
get rid of this extra energy by lowering the overall symmetry of the molecule
i.e., undergoing distortion, which is otherwise known as Jahn Teller distortion.
E.g. In case of octahedral d9 configuration, the last electron may occupy
either dz2 or dx2-y2 orbitals of eg set. If it occupies dz2 orbital, most of the
electron density will be concentrated between the metal and the two ligands
on the z axis. Thus, there will be greater electrostatic repulsion associated
with these ligands than with the other four on xy plane. This asymmetric
distribution of the electron density may increase the overall energy of the
system. To get rid of this, the complex suffers elongation of bonds on z-axis
and thus lowers the symmetry.
Conversely, occupation of the dx2-y2 orbital would lead to elongation of
bonds along the x and y axes.
* The Jahn Teller distortion is mostly observed in octahedral environments.
Theoretically the electronic degeneracy in octahedral symmetry is possible in
all the configurations except d3, d8, d10, high spin d5 and low spin
d6 configurations.
However considerable distortions are usually observed in high spin d4 ,
low spin d7 and d9 configurations in the octahedral environment. It is because
the Jahn Teller distortion is usually significant for asymmetrically occupied
eg orbitals since they are directed towards the ligands and the energy gain is
considerably more.
 * In case of unevenly occupied t2g orbitals, the Jahn Teller distortion is very
weak since the t2g set does not point directly at the ligands and therefore the
energy gain is much less.
E.g. d1; d2; low spin d4 & d5; high spin d7 & d7 configurations.
Because of same reason, the tetrahedral complexes also do not exhibit
Jahn-Teller distortion. Again, in this case also the ligands are not pointing
towards the orbitals directly and hence there is less stabilization to be gained
upon distortion.

Note: The Jahn-Teller distortion in case of low spin d8 octahedral systems

to give square planar complexes as explained by some authors is
controversial. This will be discussed in later sections.
 Z-OUT & Z-IN JAHN TELLER DISTORTIONS

* The degeneracy of orbitals can be removed by lowering the symmetry of

molecule. This can be achieved by either elongation of bonds along the z-axis
(Z-out distortion) or by shortening the bonds along the z-axis (Z-in
distortion). Thus an octahedrally symmetrical molecule is distorted to
tetragonal geometry.
Z-out distortion: In this case, the energies of d-orbitals with z factor ( i.e.,
dz2, dxz, dyz ) are lowered since the bonds along the z-axis are elongated. This
is the most preferred distortion and occurs in most of the cases, especially
when the degeneracy occurs in eg level.
E.g. Usually the octahedral d2, d4 high spin, d7 low spin, d8 low spin &
d9 configurations show the z-out distortion.
Theoretically it is not possible to predict the type of distortion occurs when
the degeneracy occurs in eg level. However it is observed that z-out distortion
is more preferred.
Z-in distortion: In this case the energies of orbitals with z factor
are increased since the bonds along the z-axis are shortened. This type of
distortion is observed in case of octahedral d1 configuration. The only
electron will now occupy the dxy orbital with lower energy.
E.g. The octahedral d1 configurations like Ti(III) in [Ti(H2O)6]3+ can show z-
in distortion (theoretically?). In this case, the z-out distortion do not remove
the degeneracy since even after distortion there are still two degenerate
orbitals i.e., dxz and dyz available for the electron to occupy. See the following
diagram.
Also remember that the Jahn-Teller theorem does NOT predict how large
a distortion should occur.
Tetrahedral Complex:

The tetrahedral arrangement of four ligands surrounding the metal ions is as

shown in the figure.

A regular tetrahedron is a cube. One atom is at the centre of the cube and
four of the eight corners of the cube are occupied by ligands. The directions
x, y and z point to the face centres. The dx2-y2 and dz2 orbitals point along the
x, y and z directions and dxy, dzx and dyz orbitals point in between x, y and z
directions.

The direction of approach of ligands does not coincide exactly with either the
e or t2 orbitals. The t2 orbitals are pointing close to the direction in which the
e orbitals are lying in between the ligands. As a result, the energy of t2 orbitals
increases compared to the energy of e orbitals. Thus, d orbitals again split into
two sets- triply degenerate t2 of higher energy and doubly degenerate e
orbitals of lower energy. That is, t2 orbitals are raised by 0.4 Δ t in energy and
the e orbitals are stabilized by 0.6 Δt in energy.
The energy difference between the two sets of orbitals (Δ t) will be about half
the magnitude of that in an octahedral complex (Δ o).

The d-orbitals will thus split as shown below:

Crystal Field Stabilization Energy:

The crystal field stabilization energy (CFSE) is the stability that results from
placing a transition metal ion in the crystal field generated by a set of ligands.
It arises due to the fact that when the d-orbitals are split in a ligand field (as
described above), some of them become lower in energy than before with
respect to a spherical field known as the bari centre in which all five d-orbitals
are degenerate. For example, in an octahedral case, the t 2g set becomes lower
in energy than the orbitals in the bari centre. Owing to the splitting of the d
orbitals in a complex, the system gains an extra stability due to the
rearrangement of the d electrons filling in the d levels of lower energy. The
consequent gain in bonding energy is known as crystal field stabilization
energy (CFSE).
If the splitting of the d-orbitals in an octahedral field is Δ oct, the three
t2g orbitals are stabilized relative to the bari centre by 2/5 Δ oct, and the eg
orbitals are destabilized by 3/5 Δ o.

For an octahedral complex, CFSE:

CSFE = - 0.4 x n(t2g) + 0.6 x n(eg) Δ0

Where, n(t2g) and n(eg) are the no. of electrons occupying the respective
levels.

CFSE For tetrahedral complex,

The tetrahedral crystal field stabilization energy is calculated the same way as
the octahedral crystal field stabilization energy. The magnitude of the
tetrahedral splitting energy is only 4/9 of the octahedral splitting energy,
or Δ t =4/9 Δ0.
CSFE = 0.4 x n(t2g) -0.6 x n(eg) Δt
Where, n(t2g) and n(eg) are the no. of electrons occupying the respective
levels.
Example:
1) Calculate the CFSE for K4[Fe(CN)6] ii) [Ti(H2O6)]+3.
Answer: K4[Fe(CN)6]
Atomic Number of Fe=26
Ground term Electronic configuration=[Ar] 3d6 4s2
Electronic configurationin [Fe]+2=[Ar] 3d6 4s0
CFSE=(-0.4*t2g+0.6*eg)∆0
[-0.4(6)+0.6(0)] ∆0
-2.0∆0
2) Calculate the CFSE for [Ti(H2O6)]+3.
Answer: [Ti(H2O6)]+3
Atomic Number of Ti=22
Ground term Electronic configuration=[Ar] 3d2 4s2
Electronic configurationin [Ti]+3=[Ar] 3d1 4s0
CFSE=(-0.4*t2g+0.6*eg)∆0
 [-0.4(1)+0.6(0)] ∆0
-0.4∆0

CFSE for square planar complex

Factors Affecting the magnitude of ∆
There are several factors that affect the magnitude of splitting (∆ 0)of d-
orbitals by the surrounding ligands.

1. Oxidation State of the Metal Cation:

The higher the oxidation state of the metal cation, the greater will be the
magnitude of ∆. The higher the oxidation state of the metal causes the ligand
to approach more closely to it and, therefore the ligand causes more splitting
of metal d-orbitals.
2+ -1
For example ∆0 for [Co(H2O)6] = 9200 cm
and ∆0 for [Co(H2O)6]3+ = 20760 cm-1
2. Number of d-electrons:
In general, for a given series of transition elements (say 3d-series), in
complexes having the metal cation with the same oxidation state but the
different number of electrons in the d-orbitals, the magnitude of ∆ 0 decreases
with increase in the number of d-electrons. It is due to the fact that the higher
number of d-electrons prevents the ligands to come closer to the metal
cation.
For example ∆0 for [Co(H2O)6]2+ = 9200 cm-1(3d7)
and ∆0 for [Ni(H2O)6]2+ = 8500 cm-1(3d8)
3. Principal Quantum Number(n) of the d-orbital of the Metal Cation:
In case of complexes having the metal cation with the same oxidation states
and the same number of d-electrons, the magnitude of for analogous
complexes within a given group increases about 30% to 50% from 3d to 4d
and by about the same amount from 4d to 5d. It is because:
(1) On moving from 3d to 4d and 4d to 5d, the size of the d-orbital increases
and electron density decreases in them, Therefore the ligands can approach
the metal cation with larger d-orbital more closely.
(2) There is less steric hindrance around a larger metal cation.
For example ∆0 for [Co(NH3)6]2+ = 2300 cm-1
∆0 for [Rh( NH3)6]2+= 34100 cm-1
∆0 for [Ir( NH3)6]2+= 41200 cm-1
4. Nature of Ligands:
The ligands are classified as a weak and strong ligand. The ligand which
causes a small degree of splitting of d-orbitals are called weak ligands and
the ligands which cause a large splitting are called strong ligands. The
common ligands have been arranged in order of their increasing crystal field
splitting power to cause splitting of d-orbitals from a study of their effects
on the spectra of transition metal ions.
(weak end)O22−< I− < Br− < S2− < SCN− (S–bonded) < Cl− < N3− < F−< NCO− <
OH− < C2O42− < H2O < NCS− (N–bonded) < CH3CN < gly (glycine) < py (pyridine)
< NH3 < en (ethylenediamine) < bipy (2,2'-bipyridine) < phen (1,10-
phenanthroline) < NO2− < PPh3 < CN− < CO < CH2(strong end)
This order s usually called as Spectrochemical series
The order of the field strength of common ligands is independent of the
nature of the metal cation and the geometry of the complex.
5. Number of Ligands:
The magnitude of crystal field splitting(∆)increases with the increase of the
number of ligands. For example ∆0 > ∆t
Though the number of ligands in a square planar complex is smaller than that
of octahedral complexes, the magnitude of ∆sp is greater than ∆0. It is because
of the fact that square planar complexes are formed by much strong ligands
with d8 metal cation of 3d-series transition metal cation and 4d and 5d
series d8metal cation with either weak or strong ligand. The very strong
ligands and 4d or 5d series transition metal cations are responsible for higher
crystal field splitting. Also in square planar complexes of d8 metal cation, the
dZ2 orbital with two electrons is stabilized and the vacant d X2-y2 orbital is
destabilized.

Consequences of d-Orbital Splitting

The splitting of the d orbitals because of their interaction with the ligands in
a complex has important consequences for the chemistry of transition-metal
complexes. Although the two kinds of effects are interrelated, we will
consider them separately.

Ionic Radii of M+2 ion

The Effect is a plot of the ionic radii of the divalent fourth-period metal ions
versus atomic number. Only Ca2+(d0), Mn2+ (high-spin d5), and Zn2+ (d10) fall on
the smooth curve calculated based on the effective nuclear charge (Zeff),
which assumes that the distribution of d electrons is spherically
symmetrical. All the other divalent ions fall below this curve because they
have asymmetrical distributions of d electrons. (The points shown for
Cr2+ and Cu2+ are only estimated values; as you will learn shortly, these two
ions do not form any truly octahedral complexes.) To see why an
asymmetrical distribution of d electrons makes a metal ion smaller than
expected, consider the Ti2+ ion, which has a d2 configuration with both
electrons in the t2g orbitals. Because the t2g orbitals are directed between the
ligands, the two d electrons are unable to shield the ligands from the nuclear
charge. Consequently, the ligands experience a higher effective nuclear
charge than expected, the metal–ligand distance is unusually short, and the
ionic radius is smaller than expected. If instead the two electrons were
distributed uniformly over all five d orbitals, they would be much more
effective at screening the ligands from the nuclear charge, making the metal–
ligand distances longer and giving a larger ionic radius.

Because these radii are based on the structures of octahedral complexes and
Cr2+ and Cu2+ do not form truly octahedral complexes, the points for these ions
are shown as open circles. The dashed line represents the behavior predicted
based on the effects of screening and variation in effective nuclear charge
(Zeff), assuming a spherical distribution of the 3d electrons.

A similar effect is observed for the V2+ ion, which has a d3 configuration.
Because the three electrons in the t2g orbitals provide essentially no shielding
of the ligands from the metal, the ligands experience the full increase of +1 in
nuclear charge that occurs in going from Ti2+ to V2+. Consequently, the
observed ionic radius of the V2+ ion is significantly smaller than that of the
Ti2+ ion.

Skipping the Cr2+ ion for the moment, we next consider the d5 Mn2+ ion.
Because the nuclear charge increases by +2 from V2+ to Mn2+, we might expect
Mn2+ to be smaller than V2+. The two electrons that are also added from V2+ to
Mn2+ occupy the eg orbitals, however, which point directly at the six ligands.
Because these electrons are localized directly between the metal ion and the
ligands, they are effective at screening the ligands from the increased nuclear
charge. As a result, the ionic radius actually increases significantly as we go
from V2+ to Mn2+, despite the higher nuclear charge of the latter.

Exactly the same effects are seen in the second half of the first-row transition
metals. In the Fe2+, Co2+, and Ni2+ ions, the extra electrons are added
successively to the t2g orbitals, resulting in poor shielding of the ligands from
the nuclear charge and abnormally small ionic radii. Skipping over Cu2+, we
again see that adding the last two electrons causes a significant increase in
the ionic radius of Zn2+, despite its higher nuclear charge.

Enthalpy of hydration of M+2ions

The hydration energy of a metal ion is defined as the change in enthalpy for
the following reaction:

M2+(g) + H2O(l) → M2+(aq)

Although hydration energies cannot be measured directly, they can be

calculated from experimentally measured quantities using thermochemical
cycles. As shown in part in Figure "Thermochemical Effects of ", a plot of the
hydration energies of the fourth-period metal dications versus atomic
number gives a curve with two valleys. Note the relationship between the plot
in part in Figure "Thermochemical Effects of " and the plot of ionic radii
in "The Effect of ": the overall shapes are essentially identical, and only the
three cations with spherically symmetrical distributions of d electrons (Ca2+,
Mn2+, and Zn2+) lie on the dashed lines. In part in Figure "Thermochemical
Effects of ", the dashed line corresponds to hydration energies calculated
based solely on electrostatic interactions. Subtracting the CFSE values for the
[M(H2O)6]2+ ions from the experimentally determined hydration energies
gives the points shown as open circles, which lie very near the calculated
curve. Thus CFSEs are primarily responsible for the differences between the
measured and calculated values of hydration energies.

A plot of the hydration energies of the divalent fourth-period metal ions

versus atomic number (solid circles) shows large deviations from the smooth
curve calculated, assuming a spherical distribution of d electrons (dashed
line). Correcting for CFSE gives the points shown as open circles, which, except
for Ti2+ and Cr2+, are close to the calculated values. The apparent deviations
for these ions are caused by the fact that solutions of the Ti2+ ion in water
are not stable, and Cr2+ does not form truly octahedral complexes.
Colour and magnetic properties of magnetic complexes

The striking colors exhibited by transition-metal complexs are caused by

excitation of an electron from a lower-energy d orbital to a higher-
energy d orbital, which is called a d–d transition . For a photon to effect such
a transition, its energy must be equal to the difference in energy between the
two d orbitals, which depends on the magnitude of Δ o.
 d–d Transition

In a d–d transition, an electron in one of the t2g orbitals of an octahedral

complex such as the [Cr(H2O)6]3+ ion absorbs a photon of light with energy
equal to Δo, which causes the electron to move to an empty or singly
occupied eg orbital.

The color we observe when we look at an object or a compound is due to

light that is transmitted or reflected, not light that is absorbed, and that
reflected or transmitted light is complementary in color to the light that is
absorbed. Thus a green compound absorbs light in the red portion of the
visible spectrum and vice versa, Because the energy of a photon of light is
inversely proportional to its wavelength, the color of a complex depends on
the magnitude of Δo, which depends on the structure of the complex. For
example, the complex [Cr(NH3)6]3+ has strong-field ligands and a relatively
large Δo. Consequently, it absorbs relatively high-energy photons,
corresponding to blue-violet light, which gives it a yellow color. A related
complex with weak-field ligands, the [Cr(H2O)6]3+ ion, absorbs lower-energy
photons corresponding to the yellow-green portion of the visible spectrum,
giving it a deep violet color.

We can now understand why emeralds and rubies have such different colors,
even though both contain Cr3+ in an octahedral environment provided by six
oxide ions. Although the chemical identity of the six ligands is the same in
both cases, the Cr–O distances are different because the compositions of the
host lattices are different (Al2O3 in rubies and Be3Al2Si6O18 in emeralds). In
ruby, the Cr–O distances are relatively short because of the constraints of the
host lattice, which increases the d orbital–ligand interactions and makes
Δo relatively large. Consequently, rubies absorb green light and the
transmitted or reflected light is red, which gives the gem its characteristic
color. In emerald, the Cr–O distances are longer due to relatively large
[Si6O18]12− silicate rings; this results in decreased d orbital–ligand interactions
and a smaller Δo. Consequently, emeralds absorb light of a longer wavelength
(red), which gives the gem its characteristic green color. It is clear that the
environment of the transition-metal ion, which is determined by the host
lattice, dramatically affects the spectroscopic properties of a metal ion.
Figure . (a) An object is black if it absorbs all colors of light. If it reflects all
colors of light, it is white. An object has a color if it absorbs all colors except
one, such as this yellow strip. The strip also appears yellow if it absorbs the
complementary color from white light (in this case, indigo). (b)
Complementary colors are located directly across from one another on the
color wheel. (c) A solution of [Cu(NH3)4]2+ ions absorbs red and orange light,
so the transmitted light appears as the complementary color, blue.

MAGNETIC PROPERTY OF d-BLOCK ELEMENTS

1) Due to the presence of unpaired electrons in the (n-1)d-orbitals ,
most ofthe transition metals ions and their compounds are
paramagnetic i.e. they are attracted by the magnetic field.
 2) As the number of number of unpaired electrons increases from 1 to
5 the magnetic moment and hence paramagnetic character also
increases.
3) Those transition elements which have paired electrons are
diamagnetic i.e.they repelled by magnetic field.
4) Metals like Co and Ni possess high paramagnetism where they obtain
permanent magnetic moment and are refereed as ferromagnetic.
6) Magnetic Properties of Coordination Complexes μeff = 2 √S(S+1) =
√n(n+2) BM If there is a possibility for contribution from the orbital
angular momentum. Where n is the number of unpaired electron.

limitations of crystal field theory:

1. The assumption that the interaction between metal-ligand is purely

electrostatic cannot be said to be very realistic.
2. This theory takes only d-orbitals of a central atom into account. The s
and p orbits are not considered for the study.
3. The theory fails to explain the behaviour of certain metals which cause
large splitting while others show small splitting. For example, the theory
has no explanation as to why H2O is a stronger ligand as compared to
OH–.
4. The theory rules out the possibility of having p bonding. This is a serious
drawback because is found in many complexes.
5. The theory gives no significance to the orbits of the ligands. Therefore
it cannot explain any properties related to ligand orbitals and their
interaction with metal orbitals.

Magnetic susceptibility by gouys method

Magnetic susceptibility measures the force experienced by a substance in a

magnetic field. When we compare the weight of a sample to the weight
measured in a magnetic field (Figure), paramagnetic samples that are
attracted to the magnet will appear heavier because of the force exerted by
the magnetic field. We can calculate the number of unpaired electrons based
on the increase in weight.

The Gouy balance measures the apparent change in the mass of the sample
as it is repelled or attracted by the region of high magnetic field between the
poles. Some commercially available balances have a port at their base for this
application. In use, a long, cylindrical sample to be tested is suspended from
a balance, partially entering between the poles of a magnet. The sample can
be in solid or liquid form, and is often placed in a cylindrical container such as
a test tube. Solid compounds are generally ground into a fine powder to allow
for uniformity amongst the sample. The sample is suspended between the
magnetic poles through an attached thread or string. The experimental
procedure requires two separate reading to be performed. An initial balance
reading is performed on the sample of interest without a magnetic field (m a).
A subsequent balance reading is taken with an applied magnetic field (m b).
The difference between these two readings relates to the magnetic force on
the sample (mb – ma)
The apparent change in mass from the two balance readings is a result of
magnetic force on the sample. The magnetic force is applied across the
gradient of a strong and weak magnetic field. A sample with
a paramagnetic compound will be pulled down towards the magnetic, and
provide a positive difference in apparent mass mb –
ma. Diamagnetic compounds can either exhibit no apparent change in weight
or a negative change as the sample is slightly repelled by the applied magnetic
field. With a paramagnetic sample, the magnetic induction is stronger than
the applied field and magnetic susceptibility is positive. A diamagnetic sample
has a magnetic induction much weaker than the applied field, and a
respective negative magnetic susceptibility. The following mathematical
equation relates the apparent change in mass to the volume susceptibility of
the sample:
Force=(mb-ma) g=1/2(K2-K1) AH2

 mb – ma = apparent difference in mass

 g = gravitational acceleration
 K1 = volume susceptibility of medium, usually air and of negligible value
 K2 = volume susceptibility of sample
 H = applied magnetic field
 A = area of the sample tube
Organometallic Chemistry
 Physical properties & Molecular structure
Introduction: -
All the physical properties are due to the chemical structure of the
compound. The chemical structure includes the bonding angle, the type of bonds,
the size of the molecules & the interactions between molecules. Slight change in
the chemical structure can drastically affect the properties of the compound.

Dipole moment (µ):-

A dipole moment is the product of the magnitude of the charge and the
distance between the centers of the positive and negative charges. It is denoted by
the Greek letter ‘µ’.
Mathematically,
Dipole Moment (µ) = Charge (q) * distance of separation (d)
It is measured in Debye units denoted by ‘D’. 1 D = 3.33564 × 10-30 C.m, where C is
Coulomb and m denotes a meter.

In general polar diatomic molecule AB in which atom B is more

electronegative than A, If +q is the charge on one end A & -q is the charge on the
end of B of the molecule. ‘d’ is called distance between the (Two Charges) centers
of their nuclei. The dipole moment of a molecule µ=q*d

If the molecule is non polar q=0

Then µ=0
The charge present on the ends of the molecule is usually the order of 10-10 esu
(electrostatic unit) and the distance between the atoms is usually the order of 10 -8
cm

Therefore µ=10-10 esu*10-8 cm=10-18 esu cm

1Debye(D)= 10-18 esu cm

Ex: - The dipole moment of HCl molecule is 1.03*10-18 & it is written as 1.03D

Dipole moment is a vector quantity, it has both magnitude as well as

direction. Therefore it is represented by as Arrow, pointing from positive to the
negative end of the molecule

Polarization: - When a molecule is placed in an electric field but the field polarizes
in different ways

1. Induced polarization
2. Orientation polarization
3. Molar polarization

When the molecule is placed in an electric field there will be small

displacement of the electrical centers with the result of a dipole.

Definition: - The molecules are neutral particles it is composed of positively

charged nuclei & negatively charged electrons. If it is placed in an electric
field between two charged plates, the positively charged nuclei directed
towards negative plate & the electrons get directed towards positive plate
this is called Polarization.

The distorted molecule with positive & negative ends is called an

electric dipole.

Induced polarization: - An induced dipole moment is an attraction that

occurs when a polar molecule induces a dipole in an atom or in a nonpolar
molecule by changing the arrangement of electrons in the nonpolar species.
Induced molar polarization represented by Pi

Pi= (D-1)/(d+2)*M/d

Where, D= Dielectric Constant

M= Molecular Mass

d= density

Induced molar polarization is defined as the amount of polarization

produced in one mole of the substance when placed between the plates of
an electric field of unit strength.

Determination of dipole moment

When a gas or vapour is placed in an electric field, it is noticed that
molecules tends to set themselves in the direction so that their field acting
opposition to the electric field. The extent of orientation depends upon the
strength of the field & nature of the molecule this effect is called molecular
orientation polarization (P0)
 Further it is noticed that electrons of the atom will be displaced slightly from
their normal orbits & attracted towards the positive pole of the field this is called
as Electron Polarization (Pe)

In addition to these two polarizations nuclei themselves will be slightly

displaced towards the negative pole of the field this effect is called Atomic
Polarization (Pa)

Therefore, totally 3 types of polarizations are taking place when the gaseous
substance is placed in an electric field.

The electron & electric polarization make up the polarization due to distortion of
the molecule.

Therefore Pd= Pe+ Pa

The total polarization PT= Pd+Po

Determination of dipole moment by temperature

variation method
The molecular orientation polarization depends on temperature. It
follows that the orientation will decreases as the temperature is increased, the
exact relation between temperature & molecular orientation polarization (P 0) was
derived by Debye in the following equation.

P0=4π/3*Nµ2/3kT

Where N= Avogadro’s no

µ= Dipole Moment

k= Boltzmann Constant

T= Temperature on a absolute scale

The total polarization PT= Pd+Po

PT= Pd+4π/3*Nµ2/3kT

But A= Pd, B=4πNµ2/9k

Then PT= A+B/T

Where A & B are constant for particular substances

If molecular orientation polarization is plotted against reciprocal of T in all

the cases, we shall get a straight line. If the above equation is satisfied but if the
substance is non polar B=0 since µ=0. So obtained straight line will be horizontal.

The substance is polar B has a definite value. It should be noticed that distortion
polarization is independent of temperature.
 Substituting the values of

N=6.023*1023 & k=1.37*10-23 J/K

In the following equation

B=4πNµ2/9k

µ2= 9kB/4πN

The value of µ=0.0127*√B*10-18esu

Applications of dipole moment

A. Polarity of a Bond:- The value of dipole moment gives indication of polar character
of a bond. The dipole moment of HF, HCl, HBr & HI are 2.0, 1.03, 0.78 & 0.38D
respectively. This shows that the polar character of the molecule decreases as we
move from HF to HI
B. Shapes of Molecule:- Dipole moments have been useful in indicating shapes of
covalent molecules
Ex:- i. Triatomic Molecules
Water (H2O) has a bent or linear structure
Water molecules can have a linear structure dipole moments of 2-OH bonds
in structure. The magnitude of 2-OH bonds equal & opposite direction.

Linear, µ=0

ii. Water molecule has a bent structure

The bond moments will acts vectorly to hive a definite net dipole moment
(µ=1.85D).
Therefore water has a bent structure

bent, µ=1.85D
 iii. Carbon dioxide has linear & SO2 has bent structure

CO2 has no dipole moment, µ=0 this is possible only if the molecule has a linear
structure & the bond moments of the two C=O units cancel each other

Linear, µ=0

SO2 has a dipole moment µ=1.63D two S=O bonds are not cancelled, the molecule
has bent structure the vector addition of the bond moments of two S=O bonds
gives net dipole moment 1.63D

Bent µ=1.63D

C. Tetra atomic molecules:- In tetra atomic molecules of the type AB3, the two
possibilities are
i. The dipole moment of the molecule may be Zero as in BF3. In such a case all the 4
atoms must be in one plane and the angles between bonds must be equal such a
shape is called planar trigonal.

µ=0

ii. The molecule may have some definite values of dipole (Ex: NH 3, PCl3, PF3 etc). This
indicates that one atom lies out of the plane of rest of the atoms.
Ex: NH3

Pyramidal shape of structure