Chem 3rd Year

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What is Crystal Field Theory?

Crystal field theory describes

the net change in crystal energy resulting from the orientation of d orbitals of a transition
metal cation inside a coordinating group of anions also called ligands.
A major feature of transition metals is their tendency to form complexes. A complex may be
considered as consisting of a central metal atom or ion surrounded by a number of ligands.
The interaction between these ligands with the central metal atom or ion is subject to
crystal field theory.

Crystal field theory was established in 1929 and treats the interaction of metal ion and
ligand as a purely electrostatic phenomenon where the ligands are considered as point
charges in the vicinity of the atomic orbitals of the central atom. Development and
extension of crystal field theory taken into account the partly covalent nature of bonds
between the ligand and metal atom mainly through the application of molecular orbital
theory. Crystal field theory is often termed ligand field theory.

Overview of Crystal Field Theory


In order to understand clearly the crystal field interactions in transition metal complexes, it
is necessary to have knowledge of the geometrical or spatial disposition of d orbitals. The d-
orbitals are fivefold degenerate in a free gaseous metal ion. If a spherically symmetric field
of negative ligand filed charge is imposed on a central metal ion, the d-orbitals will remain
degenerate but followed by some changes in the energy of the free ion.

A summary of the interactions is given below.

Crystal Field Splitting


Crystal field theory was proposed which described the metal-ligand bond as an ionic bond
arising purely from the electrostatic interactions between the metal ions and ligands.
Crystal field theory considers anions as point charges and neutral molecules as dipoles.

When transition metals are not bonded to any ligand, their d orbitals degenerate that is
they have the same energy. When they start bonding with other ligands, due to different
symmetries of the d orbitals and the inductive effect of the ligands on the electrons, the d
orbitals split apart and become non-degenerate.

High Spin and Low Spin


The complexion with the greater number of unpaired electrons is known as the high spin
complex, the low spin complex contains the lesser number of unpaired electrons. High spin
complexes are expected with weak field ligands whereas the crystal field splitting energy is
small Δ. The opposite applies to the low spin complexes in which strong field ligands cause
maximum pairing of electrons in the set of three t2 atomic orbitals due to large Δo.

 High spin – Maximum number of unpaired electrons.


 Low spin – Minimum number of unpaired electrons.
Example: [Co(CN)6]3- & [CoF6]3-

High Spin and Low Spin Complex

 [Co(CN)6]3- – Low spin complex


 [CoF6]3- – High spin complex
The pattern of the splitting of d orbitals depends on the nature of the crystal field. The
splitting in various crystal fields is discussed below:

Crystal Field Splitting in Octahedral Complex


 In the case of an octahedral coordination compound having six ligands surrounding
the metal atom/ion, we observe repulsion between the electrons in d orbitals and
ligand electrons.
 This repulsion is experienced more in the case of dx2-y2 and dz2 orbitals as they point
towards the axes along the direction of the ligand.
 Hence, they have higher energy than average energy in the spherical crystal field.
 On the other hand, dxy, dyz, and dxz orbitals experience lower repulsions as they are
directed between the axes.
 Hence, these three orbitals have less energy than the average energy in the spherical
crystal field.
Thus, the repulsions in octahedral coordination compound yield two energy levels:

 t2g– set of three orbitals (dxy, dyz and dxz) with lower energy
 eg – set of two orbitals (dx2-y2 and dz2) with higher energy

Crystal Field Splitting in Octahedral Complex


This splitting of degenerate level in the presence of ligand is known as crystal field splitting.
The difference between the energy of t2g and eg level is denoted by “Δo” (subscript o stands
for octahedral). Some ligands tend to produce strong fields thereby causing large crystal
field splitting whereas some ligands tend to produce weak fields thereby causing small
crystal field splitting.

Crystal Field Splitting in Tetrahedral Complex


The splitting of fivefold degenerate d orbitals of the metal ion into two levels in a
tetrahedral crystal field is the representation of two sets of orbitals as Td. The electrons in
dx2-y2 and dz2 orbitals are less repelled by the ligands than the electrons present in dxy, dyz,
and dxz orbitals. As a result, the energy of dxy, dyz, and dxz orbital sets are raised while that of
the dx2-y2 and dz2 orbitals are lowered.
 There are only four ligands in Td complexes and therefore the total negative charge of
four ligands and hence the ligand field is less than that of six ligands.
 The direction of the orbitals does not coincide with the directions of the ligands
approach to the metal ion.

Crystal Field Splitting in Tetrahedral Complex


Thus, the repulsions in tetrahedral coordination compound yield two energy levels:

 t2– set of three orbitals (dxy, dyz and dxz) with higher energy
 e – set of two orbitals (dx2-y2 and dz2) with lower energy
The crystal field splitting in a tetrahedral complex is intrinsically smaller in an octahedral
filed because there are only two thirds as many ligands and they have a less direct effect of
the d orbitals. The relative stabilizing effect of e set will be -6Dq and the destabilizing effect
of t2 set will be +4Dq

Crystal Field Stabilization Energy


In a chemical environment, the energy levels generally split as directed by the symmetry of
the local field surrounding the metal ion. The energy difference between the eg and
t2g levels is given as or 10Dq. It states that each electron that goes into the lower t2g level
stabilizes the system by an amount of -4Dq and the electron that goes into eg level
destabilizes the system by +6Dq. That is the t2g is lowered by 4Dq and the eg level is raised by
+6Dq.

For example, the net change in energy for d5 and d10 systems will be zero as shown below.

d5 :- 3(-4Dq) + 2(+6Dq) = -12Dq + 12Dq = 0


d10 :- 6(-4Dq) + 4(+6Dq) = -24Dq + 24Dq = 0
The decrease in energy caused by the splitting of the energy levels is called the “Ligand
Field Stabilization Energy (LFSE)”.

Crystal Field Stabilization Energy Table


The crystal field stabilization energies for some octahedral and tetrahedral complexes of 3d
metal ions are tabulated below.

Octahedral Complex Tetrahedral Complex


Electronic
Configuration Weak Field (- Strong Field (- Weak Field (- Strong Field (-
Dq) Dq) Dq) Dq)

d0 0 0 0 0

d1 4 4 6 6

d2 8 8 12 12

d3 12 12 8 (18)*

d4 6 16 4 (24)*

d5 0 20 0 (20)*

d6 4 24 6 (16)*

d7 8 18 12 12

d8 12 12 8 8

d9 6 6 4 4

d10 0 0 0 0

Thus, the crystal field splitting depends on the field produced by the ligand and the charge
on the metal ion. An experimentally determined series based on the absorption of light
by coordination compound with different ligands known as spectrochemical series has been
proposed. Spectrochemical series arranges ligands in order of their field strength as:

I– < Br– < Cl– < SCN– < F– < OH– < C2O42- < H2O < NCS– < EDTA4- < NH3 < en < CN–< CO
Filling of d-orbitals takes place in the following manner; the first three electrons are
arranged in t2g level as per the Hund’s rule. The fourth electron can either enter into
the t2g level giving a configuration of t2g4eg0 or can enter the eg orbital giving a configuration
of t2g3eg1. This depends on two parameters magnitude of crystal field splitting, Δ o and
pairing energy, P. The possibilities of the two cases can better be explained as

 Δo > P – Electron enters in the t2g level giving a configuration of t2g4eg0. Ligands
producing this configuration are known as strong field ligands and form low spin
complexes.
 Δo < P – Electron enters in the eg level giving a configuration of t2g3eg1. Ligands
producing this configuration are known as weak field ligands and form high spin
complexes.

Magnitude of Crystal Field Splitting

The magnitude of the crystal field splitting (Δ) dictates whether a complex with four, five,
six, or seven d electrons (in an octahedral complex) is high spin or low spin, which affects its
magnetic properties, structure, and reactivity. Large values of Δ (i.e., Δ > P) yield a low-spin
complex, whereas small values of Δ (i.e., Δ < P) produce a high-spin complex. The
magnitude of Δ depends on four factors: the valence of the metal, the principal quantum
number of the metal (and thus its location in the periodic table), the geometry, and the
nature of the ligand(s).

Valence of the metal

Increasing the valence of a metal ion has two effects: the radius of the metal decreases and
ligands are more strongly attracted to it due to Coulombic attraction. Both factors decrease
the metal–ligand distance, which in turn causes the ligands to interact more strongly with
the d-orbitals. Consequently, the magnitude of Δo increases as the valence of the metal
increases. Typically, Δo for a M(III) is about 50% greater than for the M(II) of the same
metal; for example, for [V(H2O)6]2+, Δo = 11,800 cm−1; for [V(H2O)6]3+, Δo = 17,850 cm−1.

Principal quantum number of the metal

For a series of complexes of metals from the same group in the periodic table with the
same charge and the same ligands, the magnitude of Δo increases with increasing principal
quantum number: Δ (3d) < Δ (4d) < Δ (5d). The data for hexaammine complexes of the
trivalent Group 9 metals illustrate this point:

[Co(NH3)6]3+: Δo = 22,900 cm−1

[Rh(NH3)6]3+: Δo = 34,100 cm−1

[Ir(NH3)6]3+: Δo = 40,000 cm−1


The increase in Δ with increasing principal quantum number is due to the larger radial
extension of the d orbitals as n increases. In addition, repulsive ligand–ligand interactions
are most important for smaller metal ions. Relatively speaking, this results in shorter M–L
distances and stronger d orbital–ligand interactions. The increase in Δ going from 3d to 4d
and 5d is so large that all 4d and 5d metals will form low spin complexes.

Geometry of the complex

The number of ligands in a complex as well as how well the ligand geometry overlaps with
the d orbitals is also a factor in the magnitude of the crystal field splitting. For example,
comparing octahedral and tetrahedral geometries the octahedral geometry has 6 ligands,
and those 6 ligands overlap directly with the two d orbitals that lie along the
axes, dx2−y2��2−�2 and dz2��2. The tetrahedral geometry has fewer ligands than
octahedral, and those ligands overlap less ideally with the ligands that lie between the
axes, dxy���, dxz���, and dyz���. Because of this the crystal field splitting of a
tetrahedral complex is generally less than half ( 49 49 than an octahedral complex with the
same metal and ligands. For example [FeCl4]- has a Δt = 5,200 cm-1 and [FeCl6]3- has a Δo =
11,600 cm-1.

Nature of the ligands

In crystal field theory ligands are all modeled as negative point charges, which means that
all ligands should behave identically. Experimentally, it is found that the Δ o observed for a
series of complexes of the same metal ion depends strongly on the nature of the ligands.
For a series of chemically similar ligands, the magnitude of Δo decreases as the size of the
donor atom increases. For example, Δo values for halide complexes generally decrease in
the order F > Cl > Br > I because smaller, more localized charges, such as we see for F,
interact more strongly with the d-orbitals of the metal. In addition, a small neutral ligand
with a highly localized lone pair, such as NH3, results in significantly larger Δo values than
might be expected. Because the lone pair points directly at the metal ion, the electron
density along the M–L axis is greater than for a spherical anion such as F. The
experimentally observed order of the crystal field splitting energies produced by different
ligands is called the spectrochemical series.

Ligands are classified as strong field or weak field based on the spectrochemical series:

weak field I-< Br- < Cl-< SCN- < F-< OH- < ox-2< ONO < H2O < SCN- < NH3 < en < NO2 < CN-, CO
strong field

Note that SCN and NO2 ligands are represented twice in the above spectrochemical series
since there are two different Lewis base sites (e.g., free electron pairs to share) on each
ligand (e.g., for the SCN ligand, the electron pair on the sulfur or the nitrogen can form the
bond to a metal). The specific atom that binds in such ligands is underlined. Ligands on the
weak field end of the series (halogens, OH, H2O) will tend to form high spin complexes and
ligands on the strong field end of the series (CN, CO, NO2) will tend to form low spin
complexes. Intermediate ligands in the midle of the series could form high or low spin
complexes depending on other factors.

Organometallic Compounds are chemical compounds which contain at least one bond
between a metallic element and a carbon atom belonging to an organic molecule. Even
metalloid elements such as silicon, tin, and boron are known to form organometallic
compounds which are used in some industrial chemical reactions.

The catalysis of reactions wherein the target molecules are polymers or pharmaceuticals
can be done with the help of organometallic compounds, resulting in an increase in the rate
of the reactions.

Generally, the bond between the metal atom and the carbon belonging to the organic
compound is covalent in nature. When metals with relatively high electropositivity (such as
sodium and lithium) form these compounds, a carbanionic nature is exhibited by the carbon
which is bound to the central metal atom.

An example of an organometallic compound wherein carbons belonging to a benzene


molecule bond with chromium is illustrated above. A few more examples of these types of
compounds are Grignard reagents, tetracarbonyl nickel, and dimethyl magnesium.

Properties of Organometallic Compounds


A few properties of organometallic compounds are listed below as short points.

 The bond between the metal and the carbon atom is often highly covalent in nature.
 Most of the organometallic compounds exist in solid states, especially the
compounds in which the hydrocarbon groups are aromatic or have a ring structure.
 The compounds consisting of highly electropositive metals such as sodium or lithium
are very volatile and can undergo spontaneous combustion.
 In many cases, organometallic compounds are found to be toxic to humans
(especially the compounds that are volatile in nature).
 These compounds can act as reducing agents, especially the compounds formed by
highly electropositive metals.
From the points given above, it can be observed that the properties of organometallic
compounds differ from the other based on the properties of the metals that constitute
them.

Applications
Organometallic Compounds have a broad range of applications in the field of chemistry.
Some of them are given below-

 In some commercial chemical reactions, organometallic compounds are used as


homogeneous catalysts.
 These compounds are used as stoichiometric reagents in both industrial and
research-oriented chemical reactions.
 These compounds are also used in the manufacture of some semiconductors, which
require the use of compounds such as trimethylgallium, trimethylaluminum,
trimethylindium, and trimethyl antimony.
 They are also used in the production of light – emitting diodes (or LEDs).
 These compounds are employed in bulk hydrogenation processes such as the
production of margarine.
 These compounds are used as catalysts and reagents during the synthesis of some
organic compounds.
 The complexes formed from organometallic compounds are useful in the facilitation
of the synthesis of many organic compounds.
The points given above emphasize the importance of organometallic compounds. However,
they are also the cause of many environmental concerns due to the highly toxic nature of
some of these types of compounds.

Reduction

All organometallic compounds are potential reducing agents, and those of the
electropositive elements are very strong reducing agents because the metal gives
up electrons to the carbon, resulting in a polar M―C bond with a partial positive charge on
the metal and a negative charge on the carbon. Organometallic compounds of highly
electropositive elements such as lithium, sodium, and aluminum ignite spontaneously and
sometimes explode on contact with air or other oxidizing agents. The useful organometallic
reagents Li(CH3), Zn(CH3)2, B(CH3)3, and Al2(CH3)6 are spontaneously flammable in air
(pyrophoric). Accordingly, techniques have been developed to handle these and other
pyrophoric compounds. Glass reaction vessels sealed from the atmosphere and purged
with nitrogen gas are commonly used for handling air-sensitive organometallic compounds
in the laboratory. Large quantities of pyrophoric compounds such as Al2(C2H5)6 are routinely
handled with ease in the chemical industry by using closed metal reactors for the
production of these and other much less reactive compounds. Organometallic compounds
have reduced reactivity when the metallic component is not highly electropositive and
when the metal is completely surrounded by attached groups. For example, elevated
temperatures are required to initiate combustion with Si(CH3)4 and Sn(CH3)4, and at room
temperature they can be handled in air.
Carbanion character
alkyllithium and Grignard reagents
Highly reactive organometallic reagents, such as alkyllithium and Grignard reagents (LiR and
RMgX, respectively), have multiple synthetic applications.(more)
The partial negative charge of an organic group bonded to a highly active metal results in a
distinctive pattern of reactivity that is frequently referred to as nucleophilic
or carbanion character. Thus, organometallic compounds containing highly active
(electropositive) metals, such as lithium, magnesium, aluminum, and zinc, react rapidly and
completely with water, liberating a hydrocarbon in the process. For example, dimethylzinc
liberates methane gas along with solid zinc hydroxide.Zn(CH3)2 + 2H2O → Zn(OH)2 + 2CH4

The above hydrolysis of dimethylzinc can be viewed as a transfer of a slightly acidic H + from
water to the strongly basic carbanion CH3− in dimethylzinc.

Alkyllithium, alkylaluminum, and alkylmagnesium compounds are the most common


carbanion reagents in laboratory-scale synthetic chemistry; carbanion character is greatly
diminished for the less metallic elements boron and silicon. The nucleophilic character of
organometallic compounds of active metals has many synthetic applications. For example,
the organic group in organometallic compounds of active metals attacks the
carbonyl carbon of a ketone, and upon hydrolysis a tertiary alcohol results.
Similarly, aldehydes can be converted to secondary alcohols by reaction with an
organometallic reagent followed by hydrolysis. Double displacement reactions can be used
to prepare sulfones (R2SO2) and sulfoxides (R2SO) by treating thionyl chloride (SOCl2) or
sulfuryl dichloride (SO2Cl2) with an alkyllithium or a Grignard reagent.

One consequence of the carbanion character of organometallic compounds containing


active metals is the protolysis (proton-transfer) reaction that takes place with very weak
protonic acids, including water. Alcohols react in a manner similar to the reaction of water,
and this provides a convenient way of introducing an alkoxide (OR) substituent into an
organometallic compound.(C2H5)3Ga + HOCH3 → [(C2H5)3GaOHCH3] → (C2H5)2Ga(OCH3) +
C2H6The rate of reaction decreases with bulky organic groups on the alcohol. For

example, tert-butyl alcohol,

Nomenclature of organometallic compounds

Most of the organometallic compounds are coordination compounds that consist of one or
more ligands attached to the metal M through M-C bonds. The rules governing their
nomenclature are therefore similar to those naming of coordination compounds. In the case
of organometallic compounds few additional rules are observed.

1. The ligands (without the prefixes mono, di, tri etc.) are named in alphabetical order
irrespective of the charge present on them.
2. The presence of hydrocarbon ligands in the coordination sphere is indicated by the
names of their radicals (methyl, ethyl etc.).
3. In case of unsaturated molecules or groups, the ligand is named with the prefix η n.

Classification of Organometallic compounds.

Organometallic compounds can be classified as follows:

1. Ionic organometallic compounds

 Most of the organometallic compounds of alkali metals (with exception of lithium


compounds which are largely covalent) fall in this category.
 Such compounds are colourless salt like solids and are soluble in polar solvents.
 They are quite reactive and are kinetically unstable.
 Mostly ionic organometallic compounds have a short life.

2. Sigma (σ) bonded organometallic compounds

Metallic elements of group 2,13,14,15 as well as the transition metals with fully filled d-
orbitals such as Zn, Cd and Hg produces organometallic compounds where the bonding of
metal atoms to carbon atoms occurs via sigma (σ) bond.

3. Multicentered organometallic compounds

Organometallic compounds which are loosely bound are called electron deficient and occur
in polymeric forms that fall under this category. These compounds can be regarded as a
halfway between the σ bonded organometallic compounds of Sn, Pb etc. and ionic
organometallic compounds of alkali metals. Elements which have a high tendency to form
multicentre organometallic compounds are Li, Br, Mg, B and Al.

4. Pi (π) bonded organometallic compounds

These include organometallic compounds of alkene, alkyne and other carbon-containing


compounds which have electrons in their π - molecular orbital. Combination of these π-
molecular orbitals with the vacant orbitals of metal atoms results in a pattern where the
metal atom gets bound to all the carbon atoms which is spread by organo ligands on the π -
molecular orbitals.

Eg. Ferrocene

Preparation of Organometallic compounds

1. Direct method

Aromatic compounds directly reacts with alkali metal.


Eg. C10H8 + Na → Na (C10H8)

2. Reaction with alkyl halide metal

Magnesium reacts with alkyl or aryl halide in ether to give Grignard reagent which is an
organometallic compound.

Eg. CH3Cl + Mg ether CH3MgCl

3. Transmetallation method

It involves the replacement of one metal by another. It is achieved by the action of more
electropositive metal such as zinc with a compound having metal with low electropositivity.

Eg. (CH3)2 Hg + Zn → (CH3)2 Zn + Hg

Due to the lanthanide contraction property of mercury (Hg), it becomes more electropositive
than zinc (Zn).

4. Double decomposition method

In such a reaction, the alkyl group migrates to the more electronegative metal.

Eg. Li4 (CH3)4 + SnCl4 → 4 LiCl + Sn (CH3)4

Tin (Sn) is more electronegative than lithium (Li).

5. Oxidation addition reactions

These are the additional reactions which are accompanied by oxidation.

Eg. RhCl [P(Ph3)]3 + CH3I → RhCl I (CH3)(PPh3)2 + PPh3

Also, students can refer,

 NCERT solutions for Class 12 Chemistry Chapter 9 Coordination compounds


 NCERT Exemplar Class 12 Chemistry Solutions Chapter 9 Coordination compounds
 NCERT notes Class 12 Chemistry Chapter 9 Coordination compounds

Properties of Organometallic Compounds

The properties of organometallic compounds are given below:

 The carbon atom and the metal are usually bonded through covalent bonds.
 Mostly when the compounds have aromatic hydrocarbon groups or a ring structure,
the organometallic compound exists in solid states.
 Volatile organometallic compounds are found toxic to humans.
 They act as reducing agents.

Uses of Organometallic Compounds

Organometallic compounds have many applications in the field of chemistry. Some of them
are listed below:

 Organometallic compounds are used as homogeneous catalysts in certain commercial


chemical reactions.
 They can be used as stoichiometric reagents for both research-oriented and industrial
chemical reactions.
 These compounds are used for the production of some semiconductors, which is in
necessary of compounds like trimethylgallium, trimethylaluminum, trimethylindium,
and trimethyl antimony.
 They are used for production of light emitting diodes (or LEDs).
 These compounds are used as catalysts and reagents for the synthesis of some organic
compounds.
 Many organic compounds are synthesised from the complexes formed from
organometallic compounds.

Organolithium Compounds

Organolithium compounds are organometallic compounds that consist of carbon-lithium


bonds. These compounds are of great importance. The use of Organolithium compounds are
widely for chemical research and industrial application. The reactivity of these compounds
resembles Grignard reagents, but are more reactive.

Synthesis of Organolithium compounds

1. Reaction of aryl or alkyl chloride with lithium metal in presence of benzene or an


aliphatic hydrocarbon.

RCl + 2Li → RLi + LiCl

2. Reaction via metal-hydrogen exchange, metal-halogen exchange, and metal-metal


exchange

RH + R′Li → R′H + RLi

Structure of Organolithium compounds


The structure of organolithium compounds have high oligomeric nature due to the presence
of 3-center 2-electron bridging bonds. The extent of oligomerization depends on the alkyl or
aryl group present.

Properties of Organolithium compounds

 They are low melting solids or liquids.


 They have high volatility due to the covalent bonding.
 They are soluble in ethers, aliphatic and aromatic compounds.
 They rapidly react with air and water.
 The reaction with water is the foundation of Gillman double titration method which
determines the concentration of organolithium reagents in solution.

What is Chromatography?
Chromatography is the technique for the separation, purification, and testing of
compounds.
The term “chromatography” is derived from Greek, chroma meaning, “colour,” and
graphein meaning “to write.”

In this process, we apply the mixture to be separated on a stationary phase (solid or liquid)
and a pure solvent such as water or any gas is allowed to move slowly over the stationary
phase, carrying the components separately as per their solubility in the pure solvent.

Table of Contents

 Principles of Chromatography
 Types of Chromatography
 Related Topics on Chromatography
 What is Differential Extraction?
 Applications of Chromatography
 Frequently Asked Questions

Principles of Chromatography
Chromatography is a separation method where the analyte is combined within a liquid or
gaseous mobile phase., which is pumped through a stationary phase. Usually one phase is
hydrophilic and the other is lipophilic. The components of the analyte interact differently
with these two phases. Depending on their polarity they spend more or less time
interacting with the stationary phase and are thus retarded to a greater or lesser extent.
This leads to the separation of the different components present in the sample. Each
sample component elutes from the stationary phase at a specific time called as retention
time. As the components pass through the detector their signal is recorded and plotted in
the form of a chromatogram.

Types of Chromatography
The four main types of chromatography are

1. Adsorption Chromatography
In the process of adsorption chromatography, different compounds are adsorbed on the
adsorbent to different degrees based on the absorptivity of the component. Here also, a
mobile phase is made to move over a stationary phase, thus carrying the components with
higher absorptivity to a lower distance than that with lower absorptivity. The main types of
chromatographic techniques that are used in industries are given as under.

2. Thin Layer Chromatography


In the process of thin-layer chromatography (TLC), the mixture of substances is separated
into its components with the help of a glass plate coated with a very thin layer of
adsorbent, such as silica gel and alumina, as shown in the figure below.

The plate used for this process is known as chrome plate. The solution of the mixture to be
separated is applied as a small spot at a distance of 2 cm above one end of the plate. The
plate is then placed in a closed jar containing a fluid termed as an eluant, which then rises
up the plate carrying different components of the mixture to different heights.
3. Column Chromatography
Column chromatography is the technique used to separate the components of a mixture
using a column of suitable adsorbent packed in a glass tube, as shown in the figure below.
The mixture is placed on the top of the column, and an appropriate eluant is made to flow
down the column slowly.

Depending upon the degree of adsorption of the components on the wall adsorbent
column, the separation of the components takes place. The component with the highest
absorptivity is retained at the top, while the other flow down to different heights
accordingly.
Column Chromatography

4. Partition chromatography

In this process, a continuous differential partitioning of components of a mixture into a


stationary pWhat is a Heterocyclic Compound?
A heterocyclic compound has at least two different elements as a member of its ring.

 The most common hetero atoms found on a cyclic ring are Oxygen (O), Nitrogen (N) and Sulphur (S).

Example:

 Nucleic Acid that is present in the body responsible for storing and expressing genetic information, is an
example of a Heterocyclic compound.
 Essential micronutrient, Vitamins is also an example of a heterocyclic compound.
 The majority of drugs, pesticides, dyes, and plastics are examples of heterocyclic compounds.

Classification of Heterocyclic Compounds


Based on the electronic arrangement, we can classify Heterocyclic compounds into two types:

 Aliphatic Heterocyclic Compounds


 Aromatic Heterocyclic Compounds

Aliphatic Heterocyclic Compounds


 Aliphatic heterocyclic compounds are those cyclic heterocycles that do not contain any double bond.
 The properties of aliphatic heterocyclic compounds are mainly affected due to ring strain.
 Examples of aliphatic heterocyclic compounds are Aziridine, Ethylene Oxide, Thiirane, Oxetane,
Azetidine, Thietane, Tetrahydrofuran (THF), Dioxane, Pyrrolidine, Piperidine, etc.

Aromatic Heterocyclic Compound


 Aromatic heterocyclic compounds, as the name suggests, are cyclic aromatic compounds.
 Aromatic Heterocyclic compounds obey Huckels Rule, i.e.
 It should be cyclic.
 It should be planar.
 It should not contain any sp3 hybridised atoms.
 It must have (4n+2) 𝛑 electrons.
 Aromatic Heterocyclic compounds are analogous to Benzene.
 Examples: Furan, Pyrrole, Thiophene, Indole, Benzofuran, Carbazole, Quinoline, Isoquinoline,
Imidazole, Oxazole, Pyrazole, Pyridazine, Pyrimidine, Purine, etc.
Based on structure, we can classify Heterocyclic compounds into five types:

1. Three-Membered Heterocyclic Compounds


2. Four-Membered Heterocyclic Compounds
3. Five-Membered Heterocyclic Compounds
4. Six-Membered Heterocyclic Compounds
5. Condensed or Fused Heterocyclic Compounds

Three-Membered Heterocyclic Compounds


These heterocyclic compounds contain three atoms which may be saturated or unsaturated.

Based on the number of heteroatoms present, we can further classify them into two categories:

Heterocyclic compounds with one heteroatom.


 As the name suggests, it has one heteroatom present in its ring.
 Examples: Aziridine, Oxirane, Thiirane, Azirine, Oxirene and Thiirene.
Heterocyclic compounds with more than one heteroatom.
 As the name suggests, it has more than one heteroatom present in its ring.
 The heteroatom atom in the ring can be the same or different.
 Examples: Diaziridine and Oxiaziridine.

Four-Membered Heterocyclic Compounds


These heterocyclic compounds contain four atoms which may be saturated or unsaturated.

Based on the number of heteroatoms present, we can further classify them into two categories:

Heterocyclic compounds with one heteroatom.


 As the name suggests, it has one heteroatom present in its ring.
 Examples: Azetidine, Oxetane, Thietane, Azete, Oxete, Thiete, etc
Heterocyclic compounds with more than one heteroatom.
 As the name suggests, it has more than one heteroatom present in its ring.
 The heteroatom atom in the ring can be the same or different.
 Examples: Diazetidine and Dioxetane.

Five-Membered Heterocyclic Compounds


These heterocyclic compounds are derived from Benzene by replacing a C=C bond with a hetero
atom having a lone pair of electrons.

Based on the number of heteroatoms present, we can further classify them into two categories:

Heterocyclic compounds with one heteroatom.


 As the name suggests, it has one heteroatom present in its ring.
 Examples: furan, pyrrole and thiophene.
Heterocyclic compounds with more than one heteroatom.
 As the name suggests, it has more than one heteroatom present in its ring.
 The heteroatom atom in the ring can be the same or different.
 Examples: Pyrazole, Imidazole, Oxazole, Thiazole, Triazole and Tetrazole, etc.

Six-Membered Heterocyclic Compounds


These heterocyclic compounds are derived from Benzene by replacing one of the Carbon with a
hetero atom having a lone pair of electrons.

Based on the number of heteroatoms present, we can further classify them into two categories:

Heterocyclic compounds with one heteroatom.


 As the name suggests, it has one heteroatom present in its ring.
 Examples: Pyridine, Pyran, Thiopyran, etc.
Heterocyclic compounds with more than one heteroatom.
 As the name suggests, it has more than one heteroatom present in its ring.
 The heteroatom atom in the ring can be the same or different.
 Examples: Pyridazine, Pyrimidine, Pyrazine, etc.

Condensed or Fused Heterocyclic Compound


 Condensed or Fused Heterocyclic Compound contains two or more fused rings.
 Condensed or Fused Heterocyclic Compounds can be partly carbocyclic or partly heterocyclic.
 Examples: Indole, Quinoine, Isoquionoline, Cabazole, etc.
 Condensed or Fused Heterocyclic Compounds can also be completely heterocyclic.
 Examples: Purine, Pteridine, etc.
Applications of Heterocyclic Compound
 Heterocyclic compounds are used in agrochemicals and pharmaceuticals industries.
 Heterocyclic compounds are used as starting materials in the synthesis of organic compounds.
 Heterocyclic compounds are used in corrosion inhibitors, sanitisers, anti-ordinates, and developers.
 Heterocyclic compounds are used in pesticides, dyes and plastics.
hase and mobile phase takes place. The example of partition chromatography can be seen
in paper chromatography. In this process, chromatography paper is used as a stationary
phase which is suspended in a mixture of solvents that act as a mobile phase.

Here, we put a spot at the base of the chromatographic paper with the mixture to be
separated and as the solvent rises up this paper, the components are carried to different
degrees depending upon their retention on the paper. The components are thus separated
at different heights.
Related Topics on Chromatography

 Adsorption Chromatography
 Thin Layer Chromatography
 Column Chromatography
 Partition Chromatography
 Applications of Chromatography

What is Differential Extraction?


Differential extraction is the method of separation of any organic component present in an
aqueous solution. In this process, we use an organic solvent for which the solubility of the
desired compound is more than compared to that in water. Also, the organic solvent is
chosen such that it is immiscible with the aqueous solution so that it can form layers and
can be separated easily using a separating funnel.

The organic compound is later recovered by the process of distillation or evaporation. The
process of continuous extraction is used in cases when the solubility of the compound is
less in the organic solvent.
Applications of Chromatography
In bio analytical chemistry, chromatography is mainly used for the separation, isolation and
purification of proteins from complex sample matrices. In cells for example, proteins occur
alongside numerous other compounds such as lipids and nucleic acids. In order to be
analysed, these proteins must be separated from all the other cell components. Then the
proteins of interest might have to be isolated from other proteins and purified further.

Chromatography is an essential part of almost any protein purification strategy. A number


of different chromatographic techniques are used for the purification and analysis of
proteins. They can be classified according to the physical principle involved in the
separation process. Typical examples include reversed phase chromatography, ion
exchange chromatography, affinity chromatography and size exclusion chromatography.

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