Dr.P.K.

Srivastava

Ecosystem

The term ecosystem was first proposed by A.G. Tansley in 1935. It

may be defined as a system formed by the community and the

environment.”
The central theme of ecosystem concept is that the living

organisms of a community not only interact among themselves but also

have functional relationship with their non-living environment. “The

structural and functional system of communities and their environment

is called an ecosystem.” Thus ecosystem is the basic structural and

functional unit of ecology.

Functioning of Ecosystem
There are mechanisms for continuous absorption of materials by

organisms for producing organic compounds and their release and

conversion into inorganic form. The whole process is called the cycling of

materials and the energy utilized to perform this act comes from the sun.
However all living organisms are not capable of utilizing the solar energy

and convert the same into chemical energy. The functional aspect of
ecosystem including the trapping of energy by green plants and its

passage into herbivorous and carnivorous animals and other organisms

which are either parasitic or saprophytic. This process is called the flow

of energy.

Types of Ecosystems
Some terrestrial ecosystems are named after the types of

organisms and habitat conditions such as (i) grassland ecosystem, (ii)

crop ecosystem (iii) forest ecosystem (iv) desert ecosystem & so on.
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Similarly fresh water ecosystems are (i) pond ecosystem (ii) Lake

ecosystem (iii) river ecosystem & so on. The largest and most uniform
aquatic ecosystem is marine ecosystem. An v may be as small as drop of

pond water. Such a small ecosystem is called micro- ecosystem. it may

be as large as an ocean.

Human activities may modify or convert natural ecosystems into man-

made or anthropogenic ecosystems.

Ecosystem Components
According to Odum, from the trophic (food) point of view, an ecosystem

has two components

(i) Autotrophic component – In which the fixation of light energy, the

use of simple inorganic substances and the manufacture of

complex materials predominates.

(ii) Heterotrophic Components – The component which utilizes,

rearranges and decomposes the complex materials synthesized

by the autotrophs.

An ecosystem can be divided into the following four structural

components –

1. Producers – Producers or autotrophic organisms are those living

organisms of the ecosystem that utilize sunlight ad their energy

source and simple inorganic materials like water, carbon dioxide

and salts etc. to produce their own food. Producers are largely
photosynthetic plants and their kind varies with the kind of

ecosystem eq. in a dense forest the trees are the most important
producers , in lakes and ponds, the producers are rooted or large
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floating plants and microscopic plants (phytoplankton) usually the

algae, in ocean the rooted and floating algae are the producers.
2. Consumers – Consumers are those living members that ingest

other organisms and are therefore called heterotrophs. They derive

their food directly or indirectly from the metabolized in the

consumers body. The vast majority of consumers are the animals.

3. The Primary Consumers in an ecosystem are herbivores, which

feed directly on the producers. However primary consumers also

vary with the kind of the ecosystem. For example, a deer or giraffe

is a primary consumer in a forest ecosystem, while a cow and goat

are the primary consumer is a grassland or crop ecosystem.

4. The secondary consumers (carnivores) such as predaceous insets

and game fish is a pond feed on the primary consumers. There are
in most ecosystems, some organisms that eat other carnivores like

a snake eat a frog on a bird eats all type of fishes including

carnivores. These are called the tertiary carnivores like the lion and

vulture, which are not killed or rarely killed and eaten by other
animals.

5. Decomposers – Decomposers or the micro consumers are also

called the saprobes or saprophytes. They are also the living

components, chiefly the bacteria and fungi that break down the

complex compounds of dead protoplasm of producers and

consumers, absorb, some of the decomposition products and

release simple decomposition usable by the producers molds and

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mushrooms (Agaricus) of the forest floor are the largest of the

decomposers that are visible to a naked eye.

6. Abiotic substances or components – The abiotic component

consists of two things. The materials and the energy. The materials
are like water, minerals, atmospheric gases and salts. They also

include some organic matter, such as the amino acids and other
products of decay of living things.

The minerals and atmosphere gases keep on cycling. They enter

into biotic system and after the death and decay of living things.

The minerals and atmosphere gases keep on cycling. They enter

into biotic system and after the death and decay of organisms
return to soil and atmosphere. This is known as biogeochemical

cycle. The circulation of materials involves trapping of the solar

energy by the green plants, which is ultimately lost by the

organisms is several ways. The amount of abiotic materials present

in an ecosystem is called standing stage.

Food Chain
The series of organisms eating one and being eaten by the other is called

the food chain. A simple food chain consists of three steps as follows –
Plant --- Herbivore --- Carnivore, but it is obvious that more than three

links may be involved in a food chain and therefore a generalized

expression plant --- herbivore --- Carnivore is changed to plant ---

Herbivore --- Carnivore ---- Carnivore ---- Carnivorer
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Eg. In a pond bond ecosystem the food chain consists of phytoplankton,

herbivorous zooplankton, small carnivorous fish, large carnivorous fish

and finally the decomposers.

In grassland ecosystem, the food chain consists of –

Grass --- Grasshoppers --- Frog --- Snakes --- Vulture

Food Web/ Trophic Web

In nature, the food chains are not isolated sequences, but are rather

interconnected with one another, “A network of food chains which are

interconnected at various trophic levels, so as to form number of feeding

connections amongst different organisms of a biotic community is called

food web.” Food web opens several alternate pathways for the flow of food
energy. It also allows an organisms to obtain it also allows an organisms

to obtain its food from more than one type of organisms of the lower
trophic level. eg. a simple food web is fresh water as producers primary

consumers secondary consumer, Tetiary consumer

Ecological Pyramids

There is some sort of relationship between the number, biomass and

energy contents of the producers and consumers of different orders in

any ecosystem. These relationship, when represented in diagrammatic

ways are referred to as ecological pyramids which are of the following

three types –

1. Pyramids of Numbers
A graphic representation of number of individuals per unit area of

various trophic level stepwise with producers forming the base and
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top carnivores at the tip is called pyramid of number is straight or

upright.
For example : in a grassland ecosystem, a large number grass or

herbs, support a lesser number of grasshoppers, the later support

fewer number of frogs and the frog to still smaller number of

snakes, the latter support to very few peacocks or falcons.

Similarly in pond ecosystem, a large number of phytoplankton

support a lesser number of zooplankton followed by carnivores –

fishes and top carnivores like stork and king fisher.

In a tree ecosystem an inverted pyramid is obtained. A large tree

provides food to several herbivores birds. The birds support still

larger population of ectoparasites.

2. Pyramid of Biomass –
The amount of living or organic matter present in a particular

environment is called biomass. “ A graphic representation of

biomass present sequences per unit are of different trophic levels,

with producers at the base and top carnivores at the tip is called
pyramid of biomass.”

In a terrestrial ecosystem, the maximum biomass occurs is

producers and there is progressive decrease in biomass from lower

to higher trophic levels. In such terrestrial ecosystem the pyramid

of upright.
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In an aquatic habitat the pyramid of biomass is inverted. The

biomass of phytoplanktons is less than that of zooplanktons. It is

still more is primary consumers and so on.

3. Pyramid of Energy
A graphic representation of the amount of energy trapped per unit

time and are in different trophic levels of a food chain with

producer forming the base and the top carnivores at the tip is

called pyramid of energy.

The maximum energy content is present in the producers. The

energy content decreases as it passes into higher trophic levels.

The pyramid of energy is always upright.

Ecological Succession

Ecological succession means ecological development. It refers to the

process of gradual change in conditions of environment and replacement

of older species. This is an ever-containing phenomenon. The occurance

of ecological succession has following characteristics.

1. It is a systematic process.
2. The changes are directional and take place as a function of time.

3. The succession occurs due to change in hysical environment and

the population of species.

4. The changes are predictable. The process of succession is self-

going, stable and biologically feasible.

According to ecological development the succession can be classified into

two
1. Primary succession –
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This is the initial stage of development of an ecosystem. It begins

with the creation of community on such a location where there was

no living organisms. such location may be a new island, newly

created body of water, a new volcanic flows etc.

2. Secondary Succession

This is a re-establishment stage of the development of an

ecosystem which existed earlier but was destroyed due to natural

calamities or man-made reasons, Such reestablishment occurs due

to the presence of seeds and organic matters of biological

communities in the soil.

Some examples of secondary succession are as follows :-

a) Forests, which were destroyed due to fire take rebirth on

abandoned land.
b) Vegitation, destroyed due to flood, grows once again.

c) Crops which were harvested grows again as some seeds of earlier

crops remain buried under soil.

d) Bushes grow on an abandoned mining site.

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UNIT – 3

STRUCTURAL AND MECHANISTIC CONCEPT OF ORGANICS

A reaction may occur or may not occur depending upon the density of
electrons at the site of reaction in the substrate. The factor which

influence the electron density in the substrate are:-

a) Inductive Effect

b) Mesomeric Effect
c) Electromeric Effect

1. Inductive Effect – In case of a co-valent bond between atoms

having similar electronegativity the electron pair of the  bond
occupies a central position between the atoms eg.

Such a covalent bond is known as non-polar bond, on the other

hand, in case of a covalent bond between two dissimilar atoms,
electrons are displaced towards the more electronegative atom.
This introduces a certain degree of polarity the bond. The more
electronegative atom acquires a small negative charge (   ). The
less electronegative atom acquires a small positive charge (   )
“The inductive effect (I effect) may be defined as the permanent
displacement of electrons forming a co-valent bond towards more
electronegative element or group.”
An inductive effect is not confined to the polarization of one bond.
But it is transmitted along the chain of carbon atoms.
Atoms or groups which lose electrons towards a carbon atom i.e.
electron releasing groups are said to have a +I effect. Those atoms
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or groups which attract electrons away from the carbon atom i.e.
electron withdrawing groups are said to have –I effect.
a) –I effect groups (Electron - attracting)
-NO2, -F, -Cl, -Br, -I, -OH, -C6H5, -CN
b) +I effect groups (Electron - releasing)
(CH3)3C-, (CH3)2CH-, CH3CH2-, CH3
2. Mesomeric Effect & It involves Ti electrons of double and triple

bonds.

“The mesomeric effect (M effect) refers to the polarity produced is a

molecule as a result of interaction between two  bonds or  bond and

lone pair of electrons. This effect is transmitted along a chain.”

It is a permanent effect. It takes place in unsaturated and especially in

conjugated system. It involves  electrons of double and triple bonds. e.g.

in carbonyl compound (>c=0) In this case the oxygen atom is more

electronegative than carbon atom. As a result, the  -electrons. of >c=0

get displaced towards the more electronegative oxygen atom.

If the >c=0 group is conjugate with carbon-carbon double bond, the

polarization will be transmitted further, via the  electrons.

The mesomeric effect may be positive or negative. Atoms which lose

electrons towards a carbon atom are said to have +M effect. While atoms

or groups which attract electrons away from the carbon atom are said to
possess a –M effect.
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3. Electromeric Effect – It is a temporary effect. “The electromeric

effect (E effect) may be defined as the polarity developed in a

multiple bonded compound as it is approached by a reagent.”.

When a multiple bond is attached by an electrophile ( E  ) the  electrons

which form the  bond are completely transferred to one atom or the

other.

Homolytic and Heterolytic Fission

In homolytic fission each of the atom acquires one of the bonding

electrons shared between them.

The products X0 and Y0 are free radicals. They are electrically neutral
and have one unpaired (odd) electron associated with them. Free radicals

are extremely reactive

Homolytic reactions are usually initiated by heat light or organic

peroxides.

In heterolytic fission one of the atoms acquires both of the bonding

electrons when the bond is broken.

The products of heterolytic fission are ions. The reactions take place at

measurable rates.
Heterolytic fission occurs most readily with polar compounds is polar

solvents.
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Reaction Intermediates – Heterolytic ahd hemolytic fissions result in

the formation of short lived fragments called reaction intermediates. The

important reaction intermediates are – carbonium ions, carbonions and

free radicals.
1. Carbonium Ions – Organic ions which contain a positively charged

carbon atom are called carbonium ions or carbocations. They are

formed by hetrolytic fission of bond.

Where Z is more electronegative than carbon.

The positively charged carbon atom is a carbonium ion is sp2 hybridized

and have planar trigonal structure. The empty p-orbital extends above &

below the plane carbocations have strong tendency to complete their

octet and thus are very reactive towards nucleophiles.

Carbocations are named as ;-

The stability of carbonium ions is influenced by both resonance and

inductive effects. Both allyl and benzyl carbonium ions can be stabilized
by resonance.
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Electron-realeasing group (+I group) also stabilize carbonium ions.

Thus, a tertiary carbonium ion is more stable than a secondary which in

turn more stable than primary because of the +I effect of alkyl groups.

Electron attracting groups (-I group) like –NO2, -Br will make carbonium

ion less stable.

2. Carbonions – Organic ions which contain a negatively charged

carbon atom are called carbonions. They are also formed by

heterolytic fission of bond.

Where z is less electronegative than carbon. The carbon atom of

carbonions is sp3 hybridized. The three out of four sp3 hybridized orbitals

form  bond with three atoms/groups while the fourth has non-bonding

pair of electrons. The configuration appears to be pyramidal.

The stability of carbanions is also influenced by resonance and inductive

effects.

Stabilization of carbanions by inductive effects is in opposite direction

from the carbonium ions. Electron releasing group (+I group) make

carbanions less stable. Thus primary carbanion is more stable than

secondary. Which in turn more stable than a tertiary because of +I effect.

Electron attracting groups (-I groups) like –NO2, -Br, will stabilize by
partial removal of negative charge on the carbon.
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3. Carbon Free Radicals – Unlike to carbonium ions and carbonions,

these free radicals have no charge. They are formed by homolytic

fission.

Here z and carbon atom have similar electronegativity

The carbon atom is a carbon free radicals is sp2 hybridized and form

three  bond at trigonal plane. A half filled p-orbital extends above &

below the plane. They are highly reactive species.

Free radicals are stabilized by hyperconjugation following is the relative

order of stability.

benzyl > allyl > Tertiary > Secondary > Primary > Methyl

Hyper Conjugation – The relative stability of various carbonium ions

may be explained by the number of no-bond resonance structures. Such

structures are formed by shifting of bonding electrons from an adjacent

C-H bond (  -carbon) to electron deficient carbon. In this way positive

charge of carbon is dispersed to the hydrogen. This dispersal of positive

charge on  -hydrogen is called Hyperconjugation or no-bond resonance.

The more hyperconjugative structure the more is he stability.

1. Ethyl carbonium ion is stabilized by three hyperconjugation

structures.

2. Isopropyl carbonium ion is stabilized by six hyperconjucation

structures.

3. t-butyl carbonium ion is stabilized by nine hyperconjugation

structures.

Thus the stability of carbonium ion will be

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(CH3)3C  > (CH3)2CH  > CH3C  H2 > C  H3

Classification of Reagents – Organic reagents are of following types –

1) Electrophiles or Electrophilic reagents

2) Nucleophiles or Nucleophilic reagents

1. Electrophilies – A reagent which can accept an electron pair in a

reaction is called an electrophile. means electron –loving. They may

be positive or neutral eg.

2. Nucleophiles – A reagent which can donate an electron pair in a

reaction is called a nucleophile. The name nucleohile means

“nucleus loving”. Nucleophiles are electron rich. They may be

negative or neutral molecules with free electron pairs e.g.

An electrophile can be represented by general symbol E+ and nucleophile

by Nu.

Types of Organic Reaction

The reactions of organic compounds can be classified as :-

1. Substitution Reaction
2. Addition Reaction

3. Elimination Reaction
1) Substitution Reaction – Substitution reactions are those

reactions in which an atom or group of atoms directly attached to a

carbon atom in the substrate molecule is replaced by another atom

or group of atoms.

2) Addition Reaction – Addition reactions are those in which atoms

or group of atoms are simply added to a double or triple bond
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without the elimination of any atom or other molecules. in these

reactions, at least one  bond is lost while two new  bonds are

formed e.g.

3) Elimination Reaction – Elimination reactions are those which

involves the removal of atoms or groups of atoms from two

adjacent atoms in the substrate molecule to form a multiple bond.

e.g.

Nucleophilic Substitution Reaction –

When a substitution reaction involves the attack of a nucleophile the

reaction is referred to as SN. e.g the hydrolysis of alkyl bromide by

aqueous NaOh.

The nucleophilic substitution reactions are divided into two classes

1) SN2 reaction - SN2 stand for bimolecular nucleophilic

substitution. When the rate of a nucleophilic substitution reaction

depends on the concentration of both the substrate and the

nucleophile, the reaction is of second order and is represented as

SN2.

Rate  [Substrate]. [Nucleophiles]

It is one step reaction e.g. the hydrolysis of methyl bromide by an aqueos

NaOH. The reaction and the transition state are as follows-

The hydroxide ion approaches the substrate carbon from the side

opposite the bromine atom. This is because both O H and the bromine

atom are electron rich which repell each other. An intermediate unstable
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compound is formed in the transition state in which both OH and Br are

partially bonded to the substrate carbon. In the transition state three C-

H bonds lie in one plane. The C-OH and C-Br bonds are perpendicular to

the plane.
In the course of the reaction, the configuration of the carbon is inverted

and is called walden inversion.

SN2 reaction is one step reaction.

SN1 reactoins –
SN1 stands for unimolecular substitution. When the rate of substitution

reaction depends only on the concentration of substrats, the reaction is

of first order and is represented as SN1.

Rate  [Substrate]

E.g. the hydrolysis of t-butyl bromide. the reaction proceed in two steps.
Step 1 – The alkyl halide ionizes to give carbonium ion. This is the rate

determining step.

The central positively charged carbon atom is sp2 hybridized and hence

planar trigonal structure.

Step 2- The nucleophile can attack planar carbonium ion from both the

sides of give t-butyl alchohol.

 SN1 reaction is two steps reaction.

 Primary alkyl halide undergo hydrolysis by SN2 mechanism

whereas t-alkyl halide undergo hydrolysis by SN1 mechanism. This

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is because the attack of OH- ion on crowded t-alkyl halide is quite

difficult.

 Secondary alkyl halide may undergo either SN1 or SN2 mechanism.

Reaction Mechanism
1. Aldol Condensation – Aldehydes containing - hydrogens

undergo self-addition is the presence of a base to form product called

Aldols. The reaction is called Aldol Condensation. The term aldol is

derived from Aldehyde and alcohol, the two functional group present in

the product.
e.g.

Mechanism –
Step 1-The enolate ion is formed

Step 2-

Step 3-

Aldols are easily dehydrated by heating

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Ketones containing  -hydrogen also undergo aldol condensation to form

ketols.

2. Cannizzaro Reaction – Aldehyds which lack an  -hydrogen.

when heated with concentrated NaOh, undergo a
disproportionation reaction. One half to a carboxylic acid and the

other half are reduced to an alcohol.

3. Diels-Alder Reaction- This involves the treatment of 1,3 butadien

(or any other conjugated diene) with alkene or alkyne. The alkene

or alkyne used in Diels Alder reaction is referred as Dienophile. the

product of Diels-Alder reaction is called Adduct.

4. Beekmann Rearrangement – The acid catalysed transformer of

ketoxime to an N-substituted amide is known as Beckman

rearrangement.

Mechanism –
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The rearrangement is highly stereo specific in that the migrating group

always approaches the nitrogen atom on the side opposite t the oxygen
atom.

5. Hofmann Rearrangement – The reaction involves the conversion

of an amide to a primary amine by the action of halogens and base.

Mechanism -