POLARITY OF BONDS Bond polarity is a concept that explains the polarity of covalent bonds.

Covalent
bonds are formed when two atoms share their unpaired electrons. Then, the bond electrons or the
electrons that are involved in the bonding, belong to both atoms. Hence there is an electron density
between two atoms. If the two atoms are of the same chemical element, then no bond polarity can
be observed since both atoms show equal attraction to the bond electrons. But if the two atoms belong
to two different chemical elements, the more electronegative atom will attract the bond electrons
than the less electronegative atom. Then, the less electronegative atom gets a partial positive charge
since the electron density around that atom is reduced. But the more electronegative atom gets a
partial negative charge because the electron density around that atom is high. This charge separation
is known as bond polarity in covalent bonds. When there is a charge separation, that bond is known
as a polar bond. In the absence of bond polarity, it is known as a nonpolar bond. Let us consider two
examples in order to understand bond polarity. ExamplesCF Here, C is less electronegative than F atom.
Therefore the bond electrons are more attracted towards the F atom. Then, F atom obtains a partial
negative charge whereas C atom gets a partial positive charge Molecular Polarity is a concept that
explains the polarity of covalent compounds. Here, the overall charge separation in a molecule is
considered. For that, the polarity of each and every covalent bond present in the molecule is used.
According to molecular polarity, compounds can be classified as polar compounds and nonpolar
compounds. Molecular polarity creates dipole moments in molecules. A dipole moment of a molecule
is the establishment of a dipole with separation of two opposite electrical charges. Molecular polarity
mainly depends on molecular geometry. When the molecular geometry is symmetrical, there is no net
charge separation. But if the geometry is asymmetrical, there is a net charge separation. Let us
consider an example in order to explain this [Link] H2O A water molecule has a dipole
moment due to the charge separation. There, oxygen is more electronegative than hydrogen atoms.
Hence the bond electrons are more attracted towards the oxygen atom. The molecular geometry of
water molecule is asymmetrical: trigonal planar. Therefore, the water molecule shows molecular
polarity. The Brønsted-Lowry In 1923, chemists Johannes Nicolaus Brønsted and Thomas Martin Lowry
independently developed definitions of acids and bases based on the compounds' abilties to either
donate or accept protons (H+ ions). In this theory, acids are defined as proton donors; whereas bases
are defined as proton acceptors. A compound that acts as both a Brønsted-Lowry acid and base
together is called [Link] took the Arrhenius definition one step further, as a substance no
longer needed to be composed of hydrogen (H+ ) or hydroxide (OH- ) ions in order to be classified as
an acid or base. Consider the following chemical equation: HCl(aq)+NH3(aq)→NH+4(aq)+Cl−(aq)(1.9)
(1.9)HCl(aq)+NH3(aq)→NH4+(aq)+Cl−(aq) Here, hydrochloric acid (HCl) "donates" a proton (H+ ) to
ammonia (NH3) which "accepts" it , forming a positively charged ammonium ion (NH4 + ) and a
negatively charged chloride ion (Cl- ). Therefore, HCl is a Brønsted-Lowry acid (donates a proton) while
the ammonia is a BrønstedLowry base (accepts a proton). Also, Clis called the conjugate base of the
acid HCl and NH4 + is called the conjugate acid of the base NH3. The Brønsted-Lowry Theory of Acids
and Bases •A Brønsted-Lowry acid is a proton (hydrogen ion) donor.• A Brønsted-Lowry base is a
proton (hydrogen ion) acceptor. In this theory, an acid is a substance that can release a proton (like in
the Arrhenius theory) and a base is a substance that can accept a proton. A basic salt, such as Na+F - ,
generates OHions in water by taking protons from water itself (to make HF):
F−(aq)+H2O(l)⇌HF(aq)+OH−(1.10)(1.10)F(aq)−+H2O(l)⇌HF(aq)+OH−When a Brønsted acid
dissociates, it increases the concentration of hydrogen ions in the solution, [H+][H+]; conversely,
Brønsted bases dissociate by taking a proton from the solvent (water) to generate [OH−][OH−]. 12 •
Acid dissociation HA(aq)⇌A−(aq)+H+(aq)(1.11)(1.11)HA(aq)⇌A(aq)−+H(aq)+ • Acid Ionization
Constant:Ka=[A−][H+][HA](1.12)(1.12)Ka=[A−][H+][HA]•[Link]: B(aq)+H2O(l)⇌HB+(aq)
+OH−(aq)(1.13)(1.13)B(aq)+H2O(l)⇌HB(aq)++OH(aq)−•BaseIonizationConstant Kb=[HB+][OH−][B]
(1.14)(1.14)Kb=[HB+][OH−][B] Conjugate Acids and Bases One important consequence of these
equilibria is that every acid (HAHA) has a conjugate base (A−A−), and vice-versa. In the base,
dissociation equilibrium above the conjugate acid of base BB is HB+HB+. For a given acid or base, these
equilibria are linked by the water dissociation equilibrium: H2O(l)⇌H+(aq)+OH−(aq)(1.15)
(1.15)H2O(l)⇌H(aq)++OH(aq)−withKw=[H+][OH−](1.16)(1.16)Kw=[H+][OH−] for which the equilibrium
constant Kw is 1.00 x 10-14 at 25°C. It can be easily shown that the product of the acid and base
dissociation constants Ka and Kb is Kw. Strong and Weak Acids and Bases Strong acids are molecular
compounds that essentially ionize to completion in aqueous solution, disassociating into H + ions and
the additional anion; there are very few common strong acids. All other acids are "weak acids" that
incompletely ionized in aqueous solution. Acids and bases that dissociate completely are. Said
.[Link],e.g.•HClO4(aq)→H+(aq)+ClO−4(aq)HClO4(aq)→H(aq)++ClO4(aq)−•HBr(aq)→H+(a
q)+Br−(aq)HBr(aq)→H(aq)++Br(aq)•CH3O−(aq)+H2O(l)→CH3OH(aq)+OH−(aq)CH3O(aq)−+H2O(l)→C
H3OH(aq)+OH(aq)−•NH−2(aq)+H2O(l)→NH3(aq)+OH−(aq)NH2(aq)−+H2O(l)→NH3(aq)+OH(aq)−
Conjugate Acids and Bases One important consequence of these equilibria is that every acid (HAHA)
has a conjugate base (A−A−), and vice-versa. In the base, dissociation equilibrium above the conjugate
acid of base BB is HB+HB+. For a given acid or base, these equilibria are linked by the water dissociation
equilibrium:H2O(l)⇌H+(aq)+OH−(aq)(1.15)(1.15)H2O(l)⇌H(aq)++OH(aq)−with Kw=[H+][OH−](1.16)
(1.16)Kw=[H+][OH−] for which the equilibrium constant Kw is 1.00 x 10-14 at 25°C. It can be easily
shown that the product of the acid and base dissociation constants Ka and Kb is Kw. Strong and Weak
Acids and Bases Strong acids are molecular compounds that essentially ionize to completion in
aqueous solution, disassociating into H + ions and the additional anion; there are very few common
strong acids. All other acids are "weak acids" that incompletely ionized in aqueous solution. Acids and
bases that dissociate completely are said to be strong acids, e.g.: • HClO4(aq)→H+(aq)+ClO
−4(aq)HClO4(aq)→H(aq)++ClO4(aq)−•HBr(aq)→H+(aq)+Br−(aq)HBr(aq)→H(aq)++Br(aq)− • CH3O
−(aq)+H2O(l)→CH3OH(aq)+OH−(aq)CH3O(aq)−+H2O(l)→CH3OH(aq)+OH(aq)−•NH−2(aq)+H2O(l)→
NH3(aq)+OH−(aq)NH2(aq)−+H2O(l)→NH3(aq)+OH(aq)− Here the right-handed arrow (→→) implies
that the reaction goes to completion. That is, a 1.0 M solution of HClO4 in water actually contains 1.0
M H+ (aq) and 1.0 M ClO4 - (aq), and no undissociated HClO4. Conversely, weak acids such as acetic
acid (CH3COOH) and weak bases such as ammonia (NH3) dissociate only slightly in water - typically a
few percent, depending on their concentration and exist mostly as the undissociated molecules. •
STRONG ACIDS: HCl, HNO3, H2SO4, HBr, HI, HClO4 • WEAK ACIDS: All other acids, such as HCN, HF,
H2S, HCOOH Strong acids such as HClHCl dissociate to produce spectator ions such as Cl−Cl− as
conjugate bases, whereas weak acids produce weak conjugate bases. This is illustrated below for acetic
acid and its conjugate base, the acetate anion. Acetic acid is a weak acid (Ka = 1.8 x 10-5 ) and acetate
is a weak base (Kb = Kw/Ka = 5.6 x 10-10) Like acids, strong and weak bases are classified by the extent
of their ionization. Strong bases disassociate almost or entirely to completion in aqueous solution.
Similar to strong acids, there are very few common strong bases. Weak bases are molecular
compounds where the ionization is not complete Lewis Theory The Lewis theory of acids and bases
states that acids act as electron pair acceptors and bases act as electron pair doners. This definition
doesn't mention anything about the hydrogen atom at all, unlike the other definitions. It only talks
about the transfer of electron pairs. To demonstrate this theory, consider the following example.
NH3+BF3= H3NBF3 This is a reaction between ammonia (NH3) and boron trifluoride (BF3). Since there
is no transfer of hydrogen atoms here, it is clear that this is a Lewis acid-base reaction. In this reaction,
NH3 has a lone pair of electrons and BF3 has an incomplete octet, since boron doesn't have enough
electrons around it to form an octet. Because boron only has 6 electrons around it, it can hold 2 more.
BF3 can act as a Lewis acid and accept the pair of electrons from the nitrogen in NH3, which will then
form a bond between the nitrogen and the boron. This is considered an acid-base reaction where NH3
(base) is donating the pair of electrons to BF3. BF3 (acid) is accepting those electrons to form a new
compound, H3NBF3.
ALCOHOLS: Alcohols with one to four carbon atoms are frequently called by common names, in which
the name of the alkyl group is followed by the word alcohol: According to the International Union of
Pure and Applied Chemistry (IUPAC), alcohols are named by changing the ending of the parent alkane
name to -ol. Here are some basic IUPAC rules for naming alcohols: CH3OH (methyl alcohol) CH3CH2OH(
ethyl alcohol) 1. The longest continuous chain (LCC) of carbon atoms containing the OH group is taken
as the parent compound—an alkane with the same number of carbon atoms. The chain is numbered
from the end nearest the OH group. 2. The number that indicates the position of the OH group is
prefixed to the name of the parent hydrocarbon, and the -e ending of the parent alkane is replaced by
the suffix -ol. (In cyclic alcohols, the carbon atom bearing the OH group is designated C1, but the 1 is
not used in the name.) Substituents are named and numbered as in alkanes. 3. If more than one OH
group appears in the same molecule (polyhydroxy alcohols), suffixes such as -diol and -triol are used.
In these cases, the -e ending of the parent alkane is retained. ALDEHYDES The IUPAC system of
nomenclature assigns a characteristic suffix -al to aldehydes. For example, H2C=O is methanal, more
commonly called formaldehyde. Since an aldehyde carbonyl group must always lie at the end of a
carbon chain, it is always is given the #1 location position in numbering and it is not necessary to
include it in the name. There are several simple carbonyl containing compounds which have common
names which are retained by IUPAC. Also, there is a common method for naming aldehydes and
ketones. For aldehydes common parent chain names, similar to those used for carboxylic acids, are
used and the suffix –aldehyde is added to the end. In common names of aldehydes, carbon atoms near
the carbonyl group are often designated by Greek letters. The atom adjacent to the carbonyl function
is alpha, the next removed is beta and so on. CARBOXYLIC ACID The IUPAC system of nomenclature
assigns a characteristic suffix to these classes. The –e ending is removed from the name of the parent
chain and is replaced -anoic acid. Since a carboxylic acid group must always lie at the end of a carbon
chain, it is always is given the #1 location position in numbering and it is not necessary to include it in
the name. Many carboxylic acids are called by the common names. These names were chosen by
chemists to usually describe a source of where the compound is found. In common names of
aldehydes, carbon atoms near the carboxyl group are often designated by Greek letters. The atom
adjacent to the carbonyl function is alpha, the next removed is beta and so on CYCLOALKANES are
cyclic hydrocarbons, meaning that the carbons of the molecule are arranged in the form of a ring.
Cycloalkanes are also saturated, meaning that all of the carbons atoms that make up the ring are single
bonded to other atoms (no double or triple bonds). There are also polycyclic alkanes, which are
molecules that contain two or more cycloalkanes that are joined, forming multiple rings.
Nomenclature 1. Determine the cycloalkane to use as the parent chain. The parent chain is the one
with the highest number of carbon atoms. If there are two cycloalkanes, use the cycloalkane with the
higher number of carbons as the parent chain. 2. If there is an alkyl straight chain that has a greater
number of carbons than the cycloalkane, then the alkyl chain must be used as the primary parent
chain. Cycloalkane acting as a substituent to an alkyl chain has an ending "-yl" and, therefore, must be
named as a cycloalkyl. 3) Determine any functional groups or other alkyl groups. 4) Number the
carbons of the cycloalkane so that the carbons with functional groups or alkyl groups have the lowest
possible number. A carbon with multiple substituents should have a lower number than a carbon with
only one substituent or functional group. One way to make sure that the lowest number possible is
assigned is to number the carbons so that when the numbers corresponding to the substituents are
added, their sum is the lowest possible. 5) When naming the cycloalkane, the substituents and
functional groups must be placed in alphabetical order. 6) Indicate the carbon number with the
functional group with the highest priority according to alphabetical order. A dash"-" must be placed
between the numbers and the name of the substituent. After the carbon number and the dash, the
name of the substituent can follow. When there is only one substituent on the parent chain, indicating
the number of the carbon atoms with the substituent is not necessary
BAEYER STRAIN THEORY was formulated when it was thought that rings were flat. It states that larger
rings would be very highly strained, as their bond angles would be very different from the optimum
109.5°. • It turns out that cycloalkanes with more than three C atoms in the ring are not flat molecules.
They are puckered to reduce strain. Angle Strain The first thing to notice about cyclopropane and
cyclobutane is the non-ideal bond angles. The ideal bond angle in tetrahedral carbon is 109 degrees.
However, constrained to a triangle and a square, the interior angles of cyclopropane (60 deg) and
cyclobutane (90) are considerably less. This means that the electron clouds surrounding each atom
will be considerably closer together than ideal, and since like charges repel, this will be energetically
more unfavorable than for a straight-chain alkane. The additional instability caused by this constraint
is called angle strain or Von Baeyer strain. Elimination Reaction? Elimination reaction is a type of
reaction is mainly used to transform saturated compounds (organic compounds which contain single
carbon-carbon bonds) to unsaturated compounds (compounds which feature double or triple carbon-
carbon bonds). Besides, it is an important method for the preparation of alkenes. An elimination
reaction is a type of chemical reaction where several atoms either in pairs or groups are removed from
a molecule. The removal usually takes place due to the action of acids and bases or action of metals.
It can also happen through the process of heating at high temperatures. Important Methods of
Elimination Reaction Normally, elimination reactions are distinguished by the kind of atoms or groups
of atoms that leave the molecule. Due to this, there are two main methods involved in this type of
reaction; • Dehydration • Dehydrohalogenation In the dehydration method, there is the elimination of
a water molecule mostly from compounds such as alcohol. Sometimes, this method is also called Beta
elimination reaction where the leaving group and H are placed at neighbour carbon atoms. On the
other hand, in dehydrohalogenation, there is a removal of a hydrogen atom and a halogen atom
Mechanism Of Elimination Reaction The elimination reaction consists of three fundamental events,
and they are; 1. Proton removal. 2. C-C pi bond is formed. 3. There is a breakage in the bond of the
leaving group. E1 Reaction • In the E1 mechanism which is also known as unimolecular elimination,
there are usually two steps involved – ionization and deprotonation. • During ionization, there is a
formation of carbocation as an intermediate. In deprotonation, a proton is lost by the carbocation. •
This happens in the presence of a base which further leads to the formation of a pi-bond in the
molecule. • In E1, the reaction rate is also proportional to the concentration of the substance to be
transformed. • It exhibits first-order kinetics. E 1 mechanism shares the features of the SN1 reaction.
The initial step is the formation of a carbocation intermediate through the loss of the leaving group.
This slow step becomes the ratedetermining step for the whole reaction. E2 Reaction • In an E2
mechanism which refers to bimolecular elimination is basically a one-step mechanism. • Here, the
carbon-hydrogen and carbon-halogen bonds mostly break off to form a new double bond. • However,
in the E2 mechanism, a base is part of the rate-determining step and it has a huge influence on the
mechanism. • The reaction rate is mostly proportional to the concentrations of both the eliminating
agent and the substrate. • It exhibits second-order kinetics. The E2 mechanism can generally be
represented as below. In the below-mentioned representation, B stands for base and X stands for the
halogen. SN1 reactions E1 reactions The SN1 reaction is defined as the nucleophilic substitution
reaction The E1 reaction is defined as the unimolecular elimination reaction In SN1 reaction there is a
substitution of a nucleophile In E1 reaction there is an elimination of a functional group There is no
formation of double bonds There is a formation of double bonds There is an involvement of one central
carbon atom There is an involvement of two adjacent carbon atoms ELIMINATION Vs SUBSTITUTION
SN1 reactions E1 reactions The SN1 reaction is defined as the nucleophilic substitution reaction The
E1 reaction is defined as the unimolecular elimination reaction In SN1 reaction there is a substitution
of a nucleophile In E1 reaction there is an elimination of a functional group There is no formation of
double bonds There is a formation of double bonds There is an involvement of one central carbon
atom There is an involvement of two adjacent carbon atoms
SN1 reaction mechanism follows a step-by-step process wherein first, the carbocation is formed from
the removal of the leaving group. Then the carbocation is attacked by the nucleophile. Finally, the
deprotonation of the protonated nucleophile takes place to give the required product. The rate
determining step of this reaction depends purely on the electrophilicity of the leaving group and is not
impacted at all by the nucleophile. What is an SN1 Reaction? The SN1 reaction is a nucleophilic
substitution reaction where the rate determining step is unimolecular. It is a type of organic
substitution reaction. SN1 stands for substitution nucleophilic unimolecular. Thus, the rate equation
(which states that the SN1 reaction is dependent on the electrophile but not on the nucleophile) holds
in situations where the amount of the nucleophile is far greater than the amount of the carbocation
intermediate. This reaction involves the formation of a carbocation intermediate. It is generally seen
in the reactions of tertiary or secondary alkyl halides with secondary or tertiary alcohols under strongly
acidic or strongly basic conditions. The SN1 reaction is often referred to as the dissociative mechanism
in inorganic chemistry. Given below are some examples of an SN1 type of nucleophilic substitution
reaction. SN1 Reaction Mechanism Taking the hydrolysis of tertiary butyl bromide as an example, the
mechanism of the SN1 reaction can be understood via the following steps. Step 1 • The carbon-
bromine bond is a polar covalent bond. The cleavage of this bond allows the removal of the leaving
group (bromide ion). • When the bromide ion leaves the tertiary butyl bromide, a carbocation
intermediate is formed. • As mentioned earlier, this is the rate determining step of the SN1 mechanism
Step 2 • In the second step of the SN1 reaction mechanism, the carbocation is attacked by the
nucleophile. • Since water is used as a solvent, an oxonium ion intermediate is formed. • Since the
solvent is of a neutral nature, a third step where deprotonation occurs is necessary. Step 3 • The
positive charge on the carbocation was shifted to the oxygen in the previous step. • The water solvent
now acts as a base and deprotonates the oxonium ion to yield the required alcohol along with a
hydronium ion as the product. Stereochemistry of SN1 Reaction The carbocation intermediate formed
in step 1 of the SN1 reaction mechanism is an sp2 hybridized carbon. Its molecular geometry is trigonal
planar, therefore allowing for two different points of nucleophilic attack, left and right. If the reaction
takes place at a stereocenter and if neither avenue for nucleophilic attack is preferred, the carbocation
is then attacked equally from both sides, yielding an equal ratio of left and right-handed enantiomers
as shown below. Thus, the tertiary/secondary alkyl halides can react with tertiary/secondary alcohols
to undergo a nucleophilic substitution reaction. The halide is replaced with the nucleophile in the
product A carbocation is a molecule in which a carbon atom has a positive charge and three bonds.
We can basically say that they are carbon cations. Formerly, it was known as carbonium ion.
Carbocation today is defined as any even-electron cation that possesses a significant positive charge
on the carbon atom. Talking about some general characteristics, the carbon cations are very reactive
and unstable due to an incomplete octet. In simple words, carbocations do not have eight electrons,
therefore they do not satisfy the octet rule. In carbocation, the hybridization of carbon will be sp2 and
its shape is trigonal planar. There is also a vacant p orbital which indicates its electron-deficient nature.
The carbon has 6 electrons in its valence shell. Due to this, it is an electron-deficient species, also
known as an electrophile. A carbocation is generally observed in an SN1 reaction, elimination reaction,
etc. Carbocation Stability Order When we compare stabilities of carbocations it must be understood
that our standard for each cation is the substrate from which it is formed. From experimental evidence,
we have come to know that 3o carbocation is more stable and need lower activation energy for its
formation. Next to this species is the 2o carbocation is more stable than 1o carbocation and requires
less activation energy than 1o species. The 1o and methyl carbocations are so unstable that they are
rarely observed in solution. It is also evident that a more stable carbocation intermediate forms faster
than a less stable carbocation intermediate species. A system bearing a charge whether positive or
negative is considered to be more stable if the charge is delocalized. The SN2 reaction mechanism
involves the nucleophilic substitution reaction of the leaving group (which generally consists of halide
groups or other electron-withdrawing groups) with a nucleophile in a given organic compound. The
rate-determining step of this reaction depends on the interaction between the two species, namely
the nucleophile and the organic compound. SN2 reaction mechanism requires the attack of
nucleophile from the back side of the carbon atom. So the product assumes a stereochemical position
opposite to the leaving group originally occupied. This is called inversion of configuration. The SN2
reaction is a good example of stereospecific reaction, one in which different stereoisomers react to
give different stereoisomers of the product. Also, SN2 reaction is the most common example of Walden
inversion where an asymmetric carbon atom undergoes inversion of configuration. What is an SN2
Reaction? The SN2 reaction is a nucleophilic substitution reaction where a bond is broken and another
is formed synchronously. Two reacting species are involved in the rate determining step of the reaction.
The term ‘SN2’ stands for – Substitution Nucleophilic Bimolecular. This type of reaction is also referred
to as bimolecular nucleophilic substitution, associative substitution, and interchange mechanism.
“Reaction Kinetics: Since an SN2 Reaction is a second-order reaction, the rate-determining step is
dependant on the concentration of nucleophile as well as the concentration of the substrate”. SN2
Reaction Mechanism This reaction proceeds through a backside attack by the nucleophile on the
substrate. The nucleophile approaches the given substrate at an angle of 180o to the carbon-leaving
group bond. The carbon-nucleophile bond forms and carbon-leaving group bond breaks
simultaneously through a transition state. Now, the leaving group is pushed out of the transition state
on the opposite side of the carbonnucleophile bond, forming the required product. It is important to
note that the product is formed with an inversion of the tetrahedral geometry at the atom in the
centre. The SN2 reaction mechanism for the nucleophilic substitution of chloroethane with bromine
acting as the nucleophile is illustrated below Stereochemistry of SN2 Reactions There are two ways in
which the nucleophile can attack the stereocenter of the substrate: 1. A frontside attack where the
nucleophile attacks from the same side where the leaving group is present, resulting in the retention
of stereochemical configuration in the product. 2. A backside attack where the nucleophile attacks the
stereocenter from the opposite side of the carbon-leaving group bond, resulting in inversion of
stereochemical configuration in the product. Since purely SN2 reactions show 100% inversion in
stereochemical configuration, it is clear that these Reactions occur through a backside attack. Thus,
the nucleophile displaces the leaving group in the given substrates. It can be noted that primary and
secondary substrates can take part in SN2 reactions whereas tertiary substrates can not. To learn more
about this topic and other related topics, such as the mechanism of SN1 reactions, Inhibition by steric
hindrance SN2 reactions are particularly sensitive to steric factors, since they are greatly retarded by
steric hindrance (crowding) at the site of reaction. In general, the order of reactivity of alkyl halides in
SN2 reactions is: methyl > 1° > 2°. The 3° alkyl halides are so crowded that they do not generally react
by an SN2 mechanism. Difference between SN1 and SN2 The major difference involved between these
two types of reactions is to study the different properties of the departure group that helps us in
finding out the pathway of the group. Understanding the major differences between these two will
give us the key differences between one and the other. For a full list of differences between the two,
check out the tabular column below: SN1 SN2 The rate of reaction is unimolecular. The rate of reaction
is bimolecular It is a two-step mechanism It is only a one-step mechanism Carbocation is formed as an
intermediate part of the reaction. No carbocation is formed during the reaction. There is no partial
bond formed with the carbon during this reaction. Carbon forms a partial bond with the nucleophile
and the leaving group. There are many steps in this reaction which start with the removal of the group
while attacking the nucleophile. The process takes place in only one cycle, with a single intermediate
stage. The solvent in which the nucleophilic substitution reaction is carried out also has an influence
on whether an SN2 or an SN1 reaction will predominate.
MARKOVNIKOV’S RULE To simplify the rule, it can also be stated as – “Hydrogen is added to the carbon
with the most hydrogens and the halide is added to the carbon with least hydrogens”. An example of
a reaction that observes Markovnikov’s rule is the addition of hydrobromic acid (HBr) to propene,
which is shown below. It can be observed from the reaction illustrated above that the majority of the
product formed obeys Markovnikov’s rule, whereas the minority of the product does not. Let us
consider the addition reaction wherein an alkene reacts with water to give rise to an alcohol. This
reaction proceeds via the formation of a carbocation. It is observed in this reaction that the hydroxyl
group attaches itself to the carbon with more carbon-carbon bonds whereas the hydrogen atom
attaches itself to the other carbon in the double bond which has more carbon-hydrogen bonds. What
is the Mechanism Behind Markovnikov’s Rule? To understand this mechanism, let us consider the
same example illustrated earlier, i.e. the addition reaction of hydrobromic acid with propene. The
Mechanism of Markovnikov’s rule can be broken down into the following two steps. Step 1 The alkene
is protonated and it gives rise to the more stable carbocation as shown below. From the illustration
shown above, we can see that there are two types of carbocations that can be formed from the
protonation of the alkene, one is a primary carbocation and the other is a secondary carbocation.
However, the secondary carbocation is far more stable and therefore, its formation is preferred over
the formation of a primary carbocation. Step 2 The halide ion nucleophile now attacks the carbocation.
This reaction yields the alkyl halide. Since the formation of the secondary carbocation is preferred, the
major product of this reaction would be 2-bromopropane as illustrated below. It is important to note
that the Markovnikov’s rule was developed specifically for its application in the addition reaction of
hydrogen halides to alkenes. The opposite of ‘Markovnikov’ addition reactions can be described as
Anti-Markovnikov based on the regioselectivity of the reaction. Anti Markovnikov addition In an
addition reaction of a generic electrophile HX to an alkene or alkyne, the hydrogen atom of HX
becomes bonded to the carbon atom that had the least number of hydrogen atoms in the starting
alkene or [Link] belong to the group of unsaturated hydrocarbons, that is, one molecule of
alkene contains at least one double bond. Due to the presence of pi electrons, they show addition
reactions in which an electrophile attacks the carbon- carbon double bond to form the additional
products. Anti Markovnikov Addition When HBr is added to unsymmetrical alkenes in the presence of
peroxide, 1- bromopropane is formed contrary to 2- bromopropane (according to Markovnikov's rule).
This reaction is better known as anti-Markovnikov addition or Kharash effect after the name of M. S.
Kharash who first observed it. This reaction is also known as Kharash effect or peroxide effect. Anti
Markovnikov addition is also an example of addition reaction of alkenes which is an exception to the
Markovnikov's rule. It is one of the few reactions following free radical mechanism in organic chemistry
in place of electrophilic addition as suggested by Markovnikov. This reaction is observed only with HBr,
not with HCI or [Link] of Anti Markovnikov addition Anti Markovnikov addition reaction is
found to follow a free radical mechanism. The peroxide compound involved helps in the generation of
free radicals. A general mechanism of anti-Markovnikov addition reaction is discussed below:•
Generation of free radical through homolytic cleavage of peroxide compound.• Attack of generated
free radical on hydrogen halide to form halide radical through hemolysis• Attack of generated halide
radical on alkene molecule to form alkyl radical through hemolysis.• Attack of a generated alkyl radical
on hydrogen halide to form alkyl halide through homolytic cleavage of hydrogen halide
[Link] EFFECT: The change in regioselectivity of the addition of HBr to an alkene or alkyne in
the presence of a peroxide. The regioselectivity for the addition reactions of other electrophiles such
as HCl and H3O + are not altered in the presence of a peroxide. In the absence of a peroxide, HBr adds
to propene via an ionic mechanism (with a carbocation intermediate) to give 2-bromopropane.
Markovnikov's Rule is obeyed. Pharm D | Dr Pharma 78 In the presence of a peroxide such as HOOH,
HBr adds to propene in an anti-Markovnikov sense and via a radical mechanism, giving 1-
bromopropane.
HEAT OF HYDROGENATION Heat of hydrogenation (symbol: ΔHhydro, ΔHº) of an alkene is the standard
enthalpy of catalytic hydrogenation of an alkene. Catalytic hydrogenation of an alkene is always
exothermic. Therefore, heat of hydrogenation of alkenes is always negative. eg: Standard enthalpy of
this reaction is -30.3 kcalmol-1 . Thus, heat of hydrogenation of 1-butene is - 30.3 kcalmol-1 . Heat of
hydrogenation of alkenes is a measure of the stability of carbon-carbon double bonds. All else being
the same, the smaller the numerical value of heat of hydrogenation of an alkene, the more stable the
double bond therein. Based on heats of hydrogenation of alkenes, the trend in the stability of carbon-
carbon double bonds is tetrasubstituted > trisubstituted > disubstituted > monosubstituted >
unsubstituted. Heat of hydrogenation of alkenes is additive, provided that the double bonds are not
conjugated FREE RADICAL HALOGENATIONS OF ALKENES Initiation Steps Hydrogen Peroxide is an
unstable molecule, if we heat it, or shine it with sunlight, two free radicals of OH will be formed. These
OH radicals will go on and attack HBr, which will take the Hydrogen and create a Bromine radical.
Hydrogen radical do not form as they tend to be extremely unstable with only one electron, thus
bromine radical which is more stable will be readily formed HO-OH=2HO Propagation Steps The
Bromine Radical will go on and attack the LESS SUBSTITUTED carbon of the alkene. This is because
after the bromine radical attacked the alkene a carbon radical will be formed. A carbon radical is more
stable when it is at a more substituted carbon due to induction and hyperconjugation. Thus, the radical
will be formed at the more substituted carbon, while the bromine is bonded to the less substituted
carbon. After a carbon radical is formed, it will go on and attack the hydrogen of a HBr, which a bromine
radical will be formed again. Termination Steps There are also Termination Steps, but we do not
concern about the termination steps as they are just the radicals combining to create waste products.
For example two bromine radical combined to give bromine. This radical addition of bromine to alkene
by radical addition reaction will go on until all the alkene turns into bromoalkane, and this process will
take some time to finish. ELECTROPHILIC ADDITION OF CONJUGATED DIENES The mechanism below
explains the formation and distribution of addition products to conjugated dienes using 1,3-butadiene
as an example. The first step, as with isolated alkenes, is the formation of a carbocation. For 1,3-
butadiene, the proton is added to form the allylic, resonance stabilized carbocation intermediate. The
resulting cation has a substantial delocalization energy, with the charge distributed over two carbons.
The nucleophile reacts with both carbons, but favors the carbon bearing the larger partial positive
charge. The reaction yields both the 1,2- or the 1,4- addition products. The more stable the
intermediate produces the greater the percentage of the final products as shown in the mechanism
below. Formation of both 1,2- and 1,4-addition products occurs not only with hydrohalic acids, but
with halogens, catalytic hydrogenation or radical, and other polar additions associated with the
electrophilic addition reactions of isolated alkenes. In a tertiary (3°) alcohol, the carbon atom holding
the -OH group is attached directly to three alkyl groups, which may be any combination of same or
different. Examples: 1,4 ADDITION1,4-Addition is an electrophilic addition reaction of conjugate
dienes. eg: Two electrophilic addition reactions could occur between 1,3-butadiene (1) and hydrogen
chloride. In Reaction 1, the net reaction is addition of a hydrogen atom to C-1 and a chlorine atom to
C-4 in 1. Hence, Reaction 1 is called 1,4-addition and its product (2) 1,4-adduct. In Reaction 2, the net
reaction is addition of a hydrogen atom to C-1 and a chlorine atom to C-2 in 1. Hence, Reaction 2 is
called 1,2-addition and its product (3) 1,2-adduc. The regioselectivity of the overall reaction depends
on the temperature. At low temperature (eg: –78 °C), the major product is 3; at high temperature (Δ),
it is 2. The carbon-carbon double bond in 2 is more highly substituted than the one in 3, so 2 is more
stable than 3. That the less stable 3 is the major product at low temperature implies that at low
temperature the system is under kinetic control and 3 is the faster-forming product. That the more
stable 2 is the major product at high temperature means the system is under thermodynamic control.
Activating groups (ortho or para directors) When the substituents like -OH have an unshared pair of
electrons, the resonance effect is stronger than the inductive effect which make these substituents
stronger activators, since this resonance effect direct the electron toward the ring. In cases where the
subtituents is esters or amides, they are less activating because they form resonance structure that
pull the electron density away from the ring. By looking at the mechanism above, we can see how
groups donating electron direct the ortho, para electrophilic substition. Since the electrons locatinn
transfer between the ortho and para carbons, then the electrophile prefer attacking the carbon that
has the free electron. Inductive effect of alkyl groups activates the direction of the ortho or para
substitution, which is when s electrons gets pushed toward the ring. Deactivating group (meta
directors) The deactivating groups deactivate the ring by the inductive effect in the presence of an
electronegative atom that withdraws the electrons away from the ring. we can see from the
mechanism above that when there is an electron withdraw from the ring, that leaves the carbons at
the ortho, para positions with a positive charge which is unfavorable for the electrophile, so the
electrophile attacks the carbon at the meta positions. Halogens are an exception of the deactivating
group that directs the ortho or para substitution. The halogens deactivate the ring by inductive effect
not by the resonance even though they have an unpaired pair of electrons. The unpaired pair of
electrons gets donated to the ring, but the inductive effect pulls away the s electrons from the ring by
the electronegativity of the halogens O,P,M DIRECTING GROUPS A monosubstituted benzene, when
treated with an electrophile, could undergo three electrophilic aromatic substitution reactions. Each
reaction yields a disubstituted benzene as the organic product, which can be identified using the
descriptors ortho, meta, and para. If the relative yield of the ortho product and that of the para product
are higher than that of the meta product, the substituent on the benzene ring in the monosubstituted
benzene is called an ortho, para directing group. If the opposite is observed, the substituent is called
a meta directing group. IONISATION OF CARBOXYLIC ACIDS Water-soluble carboxylic acids ionize
slightly in water to form moderately acidic solutions RCOOH+H2O⇌RCOO−+H3O+RCOOH+ H2O
⇌RCOO−+H3O+ Their aqueous solutions exhibit the typical properties of acids, such as changing litmus
from blue to red. The anion formed when a carboxylic acid dissociates is called the carboxylate anion
(RCOO− ). Whether soluble in water or not, carboxylic acids react with aqueous solutions of sodium
hydroxide (NaOH), sodium carbonate (Na2CO3), and sodium bicarbonate (NaHCO3) to form salts:
RCOOH + NaOH(aq) → RCOO−Na+ (aq) + H2O 2RCOOH + Na2CO3(aq) → 2RCOO−Na+ (aq) + H2O +
CO2(g) RCOOH + NaHCO3(aq) → RCOO−Na+ (aq) + H2O + CO2(g) In these reactions, the carboxylic
acids act like inorganic acids: they neutralize basic compounds. With solutions of carbonate (CO3) and
bicarbonate (HCO3) ions, they also form carbon dioxide gas. Carboxylic acid salts are named in the
same manner as inorganic salts: the name of the cation is followed by the name of the organic anion.
The name of the anion is obtained by dropping the - ic ending of the acid name and replacing it with
the suffix -ate. This rule applies whether we are using common names or International Union of Pure
and Applied Chemistry (IUPAC) names: CONVERSION OF ACID TO ACID CHLORIDE Carboxylic acids
react with Thionyl Chloride (SOCl2SOCl2) to form acid chlorides. During the reaction the hydroxyl group
of the carboxylic acid is converted to a chlorosulfite intermediate making it a better leaving group. The
chloride anion produced during the reaction acts a nucleophile. Mechanism 1) Nucleophilic attack on
Thionyl Chloride 2) Removal of Cl leaving group 3) Nucleophilic attack on the carbonyl 4) Leaving group
removal 5) Deprotonation Aldol Condensation In some cases, the adducts obtained from the Aldol
Addition can easily be converted (in situ) to α,β-unsaturated carbonyl compounds, either thermally or
under acidic or basic catalysis. The formation of the conjugated system is the driving force for this
spontaneous dehydration. Under a variety of protocols, the condensation product can be obtained
directly without isolation of the aldol. The aldol condensation is the second step of the Robinson
Annulation. Mechanism of the Aldol Condensation
CANNIZZARO REACTION Cannizzaro reaction is a chemical reaction named after Stanislao Cannizzaro
that involves the base-induced disproportionation of two molecules of a non-enolizable aldehyde to
yield a carboxylic acid and a primary alcohol. Cannizzaro Reaction Mechanism details the method to
get one molecule of alcohol and one molecule of carboxylic acid from two molecules of a given
aldehyde. Scientist Stanislao Cannizzaro, in 1853 succeeded in obtaining benzyl alcohol and potassium
benzoate from benzaldehyde. The reaction is executed by a nucleophilic acyl substitution on an
aldehyde where the leaving group attacks another aldehyde. A tetrahedral intermediate results from
the attack of hydroxide on a carbonyl. This tetrahedral intermediate collapses, thereby reforming the
carbonyl and transferring a hydride which attacks another colony. Now, a proton is exchanged by acid
and alkoxide ions. When a base of high concentration is introduced, the aldehyde forms an anion which
has a charge of 2. From this, a hydride ion is transferred to a second molecule of the aldehyde, forming
carboxylate and alkoxide ions. The alkoxide ion also obtains a proton from the solvent for the reaction.
Mechanism Step 1 A nucleophile such as a hydroxide ion is used to attack the carbonyl group of the
given aldehyde, causing a disproportionation reaction and giving rise to an anion carrying 2 negative
charges. Mechanism Step 2 This resulting intermediate can now function as a hydride reducing agent.
Due to its unstable nature, the intermediate releases a hydride anion. This hydride anion proceeds to
attack another aldehyde molecule. Now, the doubly charged anion is converted into a carboxylate
anion and the aldehyde is converted into an alkoxide anion Mechanism Step 3 In this final step, water
offers a proton to the alkoxide anion which gives rise to the final alcohol product. The reaction can
proceed since the alkoxide is more basic than water. Now, the carboxylate ion gives rise to the final
carboxylic acid product when acid workup is used (the acid workup is required since carboxylate is less
basic than water and therefore cannot obtain a proton from water). PERKIN CONDENSATION Perkin
Reaction is an organic chemical reaction which was discovered by William Henry Perkin, an English
chemist. This reaction yields an α, β -unsaturated aromatic acid. Perkin reaction mechanism includes
the reaction between aromatic aldehydes, the aliphatic acid anhydride, and the alkali salt of the acid
to give cinnamic acid derivatives. The Perkin reaction is an organic chemical reaction named after its
discoverer – William Henry Perkin. Example The Perkin reaction gives an alpha, beta-unsaturated
aromatic acid via the aldol condensation of an aromatic aldehyde and an acid anhydride. The alkali salt
of the acid is also present. This alkali salt acts as a base catalyst. Other bases can be used instead of
the alkali salt of the acid in the Perkin reaction. WITTING REACTION Wittig reaction is an organic
chemical reaction wherein an aldehyde or a ketone is reacted with a Wittig Reagent (a triphenyl
phosphonium ylide) to yield an alkene along with triphenylphosphine oxide. This Reaction is named
after its discoverer, the German chemist Georg Wittig. He was also awarded the 1979 Nobel Prize in
Chemistry for this discovery. An example of the Wittig Reaction is provided below. This reaction is a
very common method used in the organic synthesis of alkenes. One of the prime advantages of alkene
synthesis is that the site of a double bond is precisely fixed in comparison to the mixtures of differently
located double bonds formed by alcohol dehydration. Wittig Reaction Mechanism The Wittig reaction
mechanism proceeds via three steps. These steps are: Step 1: The negatively charged carbon belonging
to the ylide is nucleophilic. This carbon proceeds to execute a nucleophilic attack on the carbonyl
carbon of the aldehyde or ketone. This leads to the formation of a charge separated (and dipolar)
intermediate called a betaine. This step can be illustrated as follows: Step 2: The betaine intermediate
which is formed in step 1 is now subject to the formation of a new oxygen phosphorus bond, yielding
another intermediate which has a four-membered ring structure. This step is illustrated below Step 3:
In the four-membered ring intermediate, the carbon-oxygen bond and the carbonphosphorus bonds
are cleaved. The oxygen takes both the bonding electrons and forms a new double bond with the
phosphorus which lost the bonding pair of electrons to the carbon atom. A new carbon-carbon double
bond is formed with this electron pair as well, yielding the required alkene product. This step is
illustrated below.
SANDMEYER’S REACTION Sandmeyer reaction is a type of substitution reaction that is widely used in
the production of aryl halides from aryl diazonium salts. Copper salts like chloride, bromide, or iodide
ions are used as catalysts in this reaction. Notably, Sandmeyer reaction can be used to perform unique
transformations on benzene. The transformations include hydroxylation, trifluoromethylation,
cyanation, and halogenation. Sandmeyer Reaction Mechanism The Sandmeyer reaction follows a free
radical mechanism. The reaction is actually a two-step process where the synthesis of aryl halides from
primary aryl amines involves the formation of diazonium salts and the transformation of diazo
intermediates into aryl halides (displacement with a nucleophile). Interestingly, the nucleophile can be
a halide anion, cyanide, water, etc. To elucidate further, the Sandmeyer reaction mechanism
commences with a transfer of a single electron from the copper to the diazonium. This results in the
formation of a non-participating diazo radical as well as copper(II) halide. A molecule of nitrogen gas
is then released by diazo radical to give aryl radical, which then reacts with the copper(II) halide to
restore the catalyst [copper(I) halide]. After all this, the final product, aryl halide is obtained
WILLIAMSON SYNTHESIS This method is suitable for the preparation of a wide variety of unsymmetric
ethers. The nucleophilic substitution of halides with alkoxides leads to the desired products. If the
halides are sterically demanding and there are accessible protons in the β-position, the alkoxide will
act as a base, and side products derived from elimination are isolated instead BASICITY OF AMINES
Unlike ammonia, amines serve as bases and are reasonably strong. The basicity of amines varies by
molecule and largely depends on: the presence of the lone pair of nitrogen electrons The electronic
properties of the substituent groups attached (e.g., alkyl groups increase the basicity, aryl groups
decrease it, etc.) the degree of solvation of the protonated amine, which mostly depends on the
solvent used in the reaction. Simple amine water solubility is largely due to the hydrogen bonding
capacity that can exist between the protons on the water molecules and these lone electron pairs. We
usually consider amines as bases, but remember that 1o and 2o-amines (not 3o-amines without N-H
protons) are also weak acids ( pKa value of ammonia is 34). In this regard, it should be noted that, as
in the previous section, amine’s acidity is measured by the pKa rather than its conjugate acid. The
relevance of all these acid-base relationships to functional organic chemistry lies in the need for
differing intensity organic bases as reagents suited to the particular reaction requirements. In many
organic solvents, the common base such as sodium hydroxide is not soluble and is therefore not
commonly used as a reagent like organic reactions. Alkoxide salts, amines or amide salts are the bulk
of the base reagents. Since alcohols are much stronger acids than amines, they have weaker conjugate
bases than amide bases and fill the gap between amines and amide salts in the base strength. Factors
affect the basicity of the amines: • Presence of electron-donating group increases the basicity of the
amines Examples: CH3 , -CH3CH2 • The electron-withdrawing group decreases the basicity. Example:
Nitro group Reimer Tiemann reaction is a type of substitution reaction, named after chemists Karl
Reimer and Ferdinand Tiemann. The reaction is used for the ortho-formylation of C6H5OH (phenols).
Reaction: When phenols i.e. C6H5OH is treated with CHCl3 (chloroform) in the presence of NaOH
(sodium hydroxide), an aldehyde group (-CHO) is introduced at the ortho position of benzene ring
leading to the formation of o-hydroxybenzaldehyde. The reaction is popularly known as Reimer
Tiemann reaction. A common example of Reimer Tiemann reaction is the conversion of phenol to
salicylaldehyde (2-hydroxy benzaldehyde) as shown below. Mechanism The mechanism of Reimer
Tiemann reaction begins with the deprotonation of chloroform by a strong base to form a chloroform
carbanion. This chloroform carbanion quickly undergoes alpha elimination and gives rise to
dichlorocarbene – the principle reactive species for this reaction. The Reimer Tiemann reaction is an
organic chemical reaction where phenol is converted into an ortho hydroxy benzaldehyde using
chloroform, a base, and acid workup. This name reaction can also be described as the chemical
reaction used for the ortho-formylation of phenols. 9 major steps: • The chloroform is deprotonated
by the strongly basic aqueous hydroxide solution, giving the chloroform carbanion.
NUCLEOPHILIC AROMATIC SUBSTITUTION is not limited to arenes, however; the reaction takes place
even more readily with heteroarenes. Pyridines are especially reactive when substituted in the
aromatic ortho position or aromatic para position because then the negative charge is effectively
delocalized at the nitrogen position. One classic reaction is the Chichibabin reaction (Aleksei
Chichibabin, 1914) in which pyridine is reacted with an alkali-metal amide such as sodium amide to
form 2-aminopyridine. In the compound methyl 3-nitropyridine-4-carboxylate, the meta nitro group is
actually displaced by fluorine with cesium fluoride in DMSO at 120 °C. Oxidation and Reduction
Reaction In order to understand redox reactions, let us first deal with oxidation and reduction reactions
individually. What is Oxidation Reaction? Oxidation may be defined as loss of electrons from a
substance, the other definition of oxidation reactions states that addition of oxygen or the more
electronegative element or removal of hydrogen or the more electropositive element from a substance
is called as an oxidation reaction. Following are some examples of oxidation reactions: 2S(s) + O2 (g)
→ SO2 (g) CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l) What is Reduction Reaction? Like oxidation reactions,
reduction reactions are defined as the gain of electrons. Any substance that gains electron during a
chemical reaction gets reduced. In other forms, the reduction reaction is stated as the addition of
hydrogen or more electropositive element or removal of a more electronegative element or oxygen
from a substance. Below are some examples of reduction reactions: • 2CH2CH2 (g) + H2 (g) → CH3CH3
(g) • 2FeCl3 (aq) + H2 (g) → 2FeCl2 (aq) + 2HCl (aq) Now if we closely examine the above reaction we
would find that all the reactions above have both, reduction and oxidation reactions. The reaction in
which FeCl3 is getting reduced as electronegative element chlorine is being removed from it. While
hydrogen is getting oxidized due to the addition of chlorine, an electronegative element, in the same
reaction. Oxidizing and Reducing Agents • The substance (atom, ion, and molecule) that gains
electrons and is thereby reduced to a low valency state is called Oxidising agent. • The substance that
loses electrons and is thereby oxidised to a higher valency state is called a reducing agent. Important
Oxidizing Agents • Molecules made up of electronegative elements. Eg: O2, O3, and X2 (halogens) •
Compounds containing an element which is in the higher oxidized state. Eg: KMnO4, K2Cv2O7, HNO3,
KClo3 • Oxides of metals and non-metals. Eg: MgO, CuO, CrO3, P4O10 • Fluorine is the strongest
oxidizing agent. Important Reducing Agents • All metals, Eg: Na, Zn, Fe, Al • A few non-metals Eg: C,
Hydrogen, S, P • Hydracids, Eg: HCl, HBr, HI, H2S • Few compounds containing an element in the lower
oxidation state, Eg: FeCl2, FeSo4, SnCl2, Hg2Cl2 • Metallic hydrides, Eg: NaH, LiH, CaH2, etc.. • Organic
compounds like HCOOH, Lithium is the strongest reducing agent in the solution and Cesium is the
strongest reducing agent in the absence of water. The substances which act as oxidizing as well as
reducing agents are H2O2, SO2, H2SO3, HNO2, NaNO2 Reduction Potential of a Half-Reaction Each of
the half-reactions that make up a redox reaction has a standard electrode potential. This potential
equals the voltage produced by an electrochemical cell in which the cathode reaction is the half-
reaction considered, whereas the anode is a standard hydrogen electrode. This voltage produced by
the half-reactions is called their reduction potentials (denoted by E0 red). The value of the reduction
potential of a half-reaction is positive for the oxidizing agents that are stronger than H+ and negative
for the ones that are weaker. Examples of the reduction potentials of some species are +2.866 V for F2
and -0.763 V for Zn2+ . Identification of Oxidizing and Reducing Agents • If an element is in its higher
possible oxidation state in a compound. It can function as an oxidising agent. Eg: KMnO4, K2Cr2O7,
HNO3, H2SO4, HClO4 • If an element is in its possible lower oxidation state in a compound, it can
function as a reducing agent. Eg: H2S, H2C2O4, FeSO4, SnCl2 • If a highly electronegative element is
in its highest oxidation state, the compound will act as an oxidising agent. • If a highly electronegative
element is in its lowest oxidation state the compound acts as a reducing agent.
 DIMERCAPROL FORMULA : C3H8OS2 : OTHER NAME : 2,3 dimercapto-1-propanol ASSAY : Dissolve
about 0.12 gm,accurately weighed in 20 ml of HCl (0.1 mol/lt) Vs and titrate rapily with ioine Vs using
starch is an indicator. Report the experiment test without the test liquid being examined, and make
any necessary corrections. Each 1ml of iodine Vs is equvivalent to 6.211mg of C3H8OS2. USE :Antidote
for arsenic,gold and mercury poisoning. VANILLIN FORMULA C8H8O3 PREPARATION : Vanillin –
C6H3(OMC)(OH).CHO It is the flavouring agent of the vanilla pods can be made synthetically from
guaicol by remier – tiemann reaction. It is also prepared by eugenol. This compound is first isomerised
by the alkali to isoeugenol and the later is then subjected to controlled oxidation. ASSAY : Weigh
accurately about 0.12gm dissolve 20ml of ethanol add 60ml of CO2 free H2O and titrate with 0.1m
NaOH determining the end point ,potentiometrically each 1ml of 0.1m NaOH is equivalent to 0.01521g
of C8H8O3.. USES : As a flavouring agent particularly in chocolate ice ceam and confectionary.
PARALDEHYDE FORMULA (C2H4O)3PREPARATION : When acetaldehyde is treated with a small
amount of con. H2SO4 of room temperature a cyclic trimer paraldehyde is formed. USES• sedative
and hypnotic • obstetric analgesic CITRIC ACID FORMULA :C6H8O7.H20 PREPARATION: From
molasses- it containing sucrose is diluted to water and subjected to fermenting with a micro organism
Aspergillus niger. C12H22O11+H2O Æ HO-C ASSAY The fermentation process is carried out for 7-10
days at 26-280 [Link] resulting solution of citric acid is neutralized with Ca(OH)2 to form insoluble
calcium [Link] is washed with H2O and decomposed with dilute [Link] calcium sulphate is
filtered of and the solution concentration under vaccum to get crystals of citric acid. USES• Used as a
mordant• As a esters that are good plasticizers for lacquers and vanishers SALICYLIC
ACID FORMULA :C6H4(OH).CO2H PREPARATION: This involves the treatment of sodium phenoxide
with CO2 at 1250 C under 6atm of pressure followed by acid hydrolyses therefore acid is formed. ASSAY
:Titration with N/2 NaOH in alcoholic solution using phenol as red indicator. The end point marks the
completion of sodium salt. The presence of hydroxyl group makes the acid stonger than benzoic. The
constant is 1×10-3 and the pH of sodium salicylate is therefore close to 7.
NaOH+C6H6(OH).CO2HÆC6H4.CO2Na+H2O 1,000ml of N/2 alkali are equivalent to ½ C6H4(OH)CO2H
USES : Used as antiseptic and disinfectant ASPIRIN FORMULA :C6H4([Link].CH3)CO2H STRUCTURE :
PREPARATION: It is prepared by heating salicylic acid with acetyl chlorine in the presence of phosphoric
acid. Notice that only OH group isinvolved in the reaction. ASSAY : Hydrolysis with a measured volume
of N/2 NaOH and titration of excess of alkali with N/2 [Link] final neutralized solution contains
sodium acetate and monosodium salicylate. 1,000ml of N/2 alkali are equivalent to ¼
C6H4(OCOCH3)CO2H USES: •Used as a painkiller •It is sold under the trade name aspirin. BENZYL
BENZOATE FORMULA :C14H12O2PREPARATION: 1. Prepared by esterification of benzyl alcohol with
benzoic acid of catalyst. 2. By heating benzyl chloride with potassium benzoate in the presence of
diethyl amine. 3. Condensation of sodium benzyl oxide in non aqueous solution. ASSAY: Add about
2.0g accurately weighted 240ml of KOH/C2H5OH Vs and boil under reflex for 1hr. Cool and titrate with
HCl Vs using phenolphthalein or ethanol as indicator. Repeat the operation without the test liquid
being examined and make any necessary correction. Each 1ml of KOH/C2H5OH Vs equivalent to
106.1mg of C14H12O2. USES : Used as a antiparasitic(scabicide-topical use). SACCHARIN SODIUM
FORMULA :C7H4NNaO3S: PREPARATION: When saccharin is treated with aqueous NaOH to form
saccharin sodium. ASSAY :Weigh accurately about 0.15g, dissolve in 50ml of anhydrous glacial acetic
acid. With slight heating if necessary and carry out method A for non aqueous titration, determining
the end potentiometrically perform a blank determination and make any necessary correction. Each
ml of 0.1M perchloric acid is equivalent to 0.02052g of C7H4NNaO3S. USES: Pharmaceutical aid,
preparation of toothpaste. MEPHENSIN FORMULA : (C11H17N) 2H2SO4:PREPARATION:It is
synthesized from [Link] is treated with [Link] to convert sodium salt which undergoes
nucleophillic substitute with 3-chloro-1,2 propane diol to give mephensin ASSAY: Test for mephensin,