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Reaksi

Reaksi Kimia
Kimia
Faktor-faktor yang mempengaruhi
1. Kolisi
2. Luas permukaan
3. Konsentrasi
4. Tekanan
5. Temperatur
6. Katalis
a. Heterokatalis
b. Homokatalis
c. Autokatalis
Order Reaksi
Jenis-jenis rekasi
Reaksi radikal bebas
Reaksi addisi dan substitusi elektrofilik
Reaksi addisi dan substitusi nukleofilik
Reaksi eliminasi

1.
Kolisi

2. Luas Permukaan

3. Konsentrasi

4. Tekanan

5. Temperature

Summary
Increasing the temperature increases reaction rates
because of the disproportionately large increase in the
number of high energy collisions

6. Katalis

a. Heterogenus katalis

b. Homogenus katalis
The reaction between persulphate ions and iodide
ions
Persulphate ions (peroxodisulphate ions), S2O82-, are very
powerful oxidising agents. Iodide ions are very easily
oxidised to iodine. And yet the reaction between them in
solution in water is very slow.
If you look at the equation, it is easy to see why that is:
S2O82-+ 2I2SO42-+ I2
The reaction needs a collision between two negative ions.
The catalysed reaction avoids that problem completely.
The catalyst can be either iron(II) or iron(III) ions which
are added to the same solution.
S2O82-+ 2Fe2+
2Fe3+ + 2I-

2SO42-+ 2Fe3+
2Fe2+ + I2

The destruction of atmospheric ozone


UV
O2
.O. + .O.
The oxygen radicals can then combine with ordinary
oxygen molecules to make ozone.

O2 + .O.
O3
Ozone can also be split up again into ordinary oxygen and
an oxygen radical by absorbing ultraviolet light.
O3

UV

O2 + .O.

Chlorofluorocarbons (CFCs) like CF2Cl2 slow breakdown


in the atmosphere produces chlorine atoms - chlorine
free radicals
Cl. + O3
ClO. + .O.

O2 + ClO.
ClO. + O2

c. Auto katalis
In autocatalysis, the reaction is catalysed by one of its products. One of the
simplest examples of this is in the oxidation of a solution of ethanedioic acid
(oxalic acid) by an acidified solution of potassium manganate(VII) (potassium
permanganate).

The reaction is very slow at room temperature. It is used as a titration to find the
concentration of potassium manganate(VII) solution and is usually carried out at a
temperature of about 60C. Even so, it is quite slow to start with.
The reaction is catalysed by manganese(II) ions. There obviously aren't any of
those present before the reaction starts, and so it starts off extremely slowly at
room temperature. However, if you look at the equation, you will find manganese(II)
ions amongst the products. More and more catalyst is produced as the reaction
proceeds and so the reaction speeds up.
You can measure this effect by plotting the concentration of one of the reactants
as time goes on. You get a graph quite unlike the normal rate curve for a reaction.

CATALYSTS IN INORGANIC INDUSTRIAL PROCESSES


The Contact Process for the manufacture of sulphuric acid
At the heart of the Contact Process is a reaction which converts
sulphur dioxide into sulphur trioxide. Sulphur dioxide gas is
passed together with air (as a source of oxygen) over a solid
vanadium(V) oxide catalyst. This is therefore an example of
heterogeneous catalysis.

The Haber Process for the manufacture of ammonia


The Haber Process combines hydrogen and nitrogen to make
ammonia using an iron catalyst. This is another reversible
reaction, and another example of heterogeneous catalysis.

CATALYSTS IN THE PETROCHEMICAL INDUSTRY


Catalytic cracking
Cracking is the name given to breaking up large hydrocarbon
molecules into smaller and more useful bits. This is achieved by
using high pressures and temperatures without a catalyst, or
lower temperatures and pressures in the presence of a catalyst.

CATALYSTS IN THE PETROCHEMICAL INDUSTRY


Isomerisation
Hydrocarbons used in petrol (gasoline) are given an octane rating
which relates to how effectively they perform in the engine. A
hydrocarbon with a high octane rating burns more smoothly than
one with a low octane rating. Molecules with "straight chains"
have a tendency to pre-ignition.

CATALYSTS IN THE PETROCHEMICAL INDUSTRY

Reforming
Reforming is another process used to improve the octane rating of
hydrocarbons to be used in petrol, but is also a useful source of
aromatic compounds for the chemical industry. Aromatic
compounds are ones based on a benzene ring. Reforming uses a
platinum catalyst suspended on aluminium oxide together with
various promoters to make the catalyst more efficient. The
original molecules are passed as vapours over the solid catalyst
at a temperature of about 500C.

ACID CATALYSIS IN ORGANIC CHEMISTRY


The nitration of benzene
Benzene is treated with a mixture of concentrated nitric acid and
concentrated sulphuric acid at a temperature not exceeding 50C.
As the temperature increases there is a greater chance of getting
more than one nitro group, -NO2, substituted onto the ring.
Nitrobenzene is formed.

ACID CATALYSIS IN ORGANIC CHEMISTRY


The hydration of ethene to make ethanol
Ethene is mixed with steam and passed over a catalyst consisting of
solid silicon dioxide coated with phosphoric(V) acid. The
temperature used is 300C and the pressure is about 60 to 70
atmospheres.

ACID CATALYSIS IN ORGANIC CHEMISTRY


Making esters - the esterification reaction
Esters are what is formed when an organic acid
reacts with an alcohol in the presence of
concentrated sulphuric acid as the catalyst.
Everything is present in a single liquid phase,
and so this is an example of homogeneous
catalysis. For example, ethanoic acid reacts with
ethanol to produce ethyl ethanoate.

ACID CATALYSIS IN ORGANIC CHEMISTRY


The acid catalysed hydrolysis of esters
In principle, this is the reverse of the esterification reaction but, in
practice, it has to be done slightly differently. The ester is heated
under reflux with a dilute acid such as dilute hydrochloric acid or
dilute sulphuric acid.

You would normally hydrolyse esters quite differently by heating


them with sodium hydroxide solution (alkaline hydrolysis). This
isn't an example of a catalytic reaction because the hydroxide
ions are used up during the reaction.

MORE EXAMPLES OF CATALYSIS IN ORGANIC CHEMISTRY


Epoxyethane is manufactured by reacting ethene with a limited
amount of oxygen in the presence of a silver catalyst at a
temperature of about 250 - 300C and a pressure of less than 15
atmospheres. Because the solid silver is catalysing a gas
reaction, this is an example of heterogeneous catalysis.

The halogenation of benzene


Benzene reacts with chlorine or bromine in the presence of a
catalyst. The catalyst is either aluminium chloride (or aluminium
bromide if you are reacting benzene with bromine).

MORE EXAMPLES OF CATALYSIS IN ORGANIC CHEMISTRY


The Friedel-Crafts alkylation of benzene
Benzene is treated with a chloroalkane (for example, chloromethane
or chloroethane) in the presence of aluminium chloride as a
catalyst. The equation shows the reaction using a methyl group,
but any other alkyl group could be used in the same way

The Friedel-Crafts acylation of benzene


An acyl group is an alkyl group attached to a carbon-oxygen double
bond. Acylation means substituting an acyl group into something
- in this case, into a benzene ring. The most commonly used acyl
group is CH3CO-. This is called the ethanoyl group .

A+B

Order
reaksi

products

1. The rate of reaction is proportional to the concentration of A


Rate = k [A]
2. The rate of reaction is proportional to the square of the
concentration of A
Rate = k [A]2
By doing experiments involving a reaction between A and B, you would
find that the rate of the reaction was related to the concentrations of A
and B in this way
Rate = k [A]a [B]b
a=
order reaksi A
b
= order reaksi B
Total order reaksi = a + b

ORDERS OF REACTION AND MECHANISMS


Monomolecular reaction
Here is the mechanism we have already looked at. How do we
know that it works like this?

By doing rate of reaction experiments, you find this rate


equation:

ORDERS OF REACTION AND MECHANISMS


Bimolecular reaction
Here is the mechanism we have already looked at. How do we
know that it works like this?

By doing rate of reaction experiments, you find this rate


equation:

Reaksi Organik Dasar


NERS-M (Name
Mechanism)

Methoda untuk mempelajari reaksi organic


- Example - Regiochemistry - Stereochemistry

Reaksi Asam-Basa
Reaksi asam/basa adalah meliputi transfer proton.

Asam/basa Lewis

Note : Seluruh reaksi asam/basa yang tidak melibatkan serah terima


proton adalah reaksi asam/basa Lewis. Reagen berlaku sebagai
electrophiles dan nucleophiles.

Reaksi Organik Dasar


Reaksi Substitusi dan Eliminasi
Nama: SN2 Reaction
Example:
H
HO +H3C Br

CH3Br + NaOH

HO
H

->

Br
H

H3C

OH + Br

CH3OH + NaBr

Regiochemistry: NA
Stereochemistry: Inversion of configuration
Comments: Reaksi ini adalah reaksi bimolecular: kecepatan reaksi akan
meningkat ketika
konsentrasi electrophile and nucleophile ditingkatkan.
Reaktifitas dari electrophile: MeX > allylic, benzylic > 1 > 2 (No 3 )
MsO-, TsO-, I- > Br- > ClLeaving groups that form stable, basa yang tidak reaktif adalah bagus sebagai
leaving groups.

Reaksi Organik Dasar


Reaktifitas dari nucleophile:
Kuat > Sedang >> lemah (unreactive)

Reaksi ini bersaingan degan reaksi E2 .


examples:
Enolate alkylation:

Tosylation/SN2

Name: E2 Reaction
Example:

Regiochemistry:
Saytzeff's rule applies to reactions using small bases.
Hofmann elimination occurs when large sterically bulky
bases are used (tBuO-).
Stereochemistry: stereospecific

Name: E2 Reaction
Mechanism:

Comments:
Reactivity of acid: 3 > 2 > 1
Competes with SN2 reaction. E2 favored at
higher T.

Name: E2 Reaction
Stereospecific examples:

Reaksi SN1
Example:

Regiochemistry: NA
Stereochemistry: Racemization
Mechanism:
Comments:
Reaksi Unimolecular. Kecepatan reaksi tergantung pada
konsentrasi dari nucleophile.
Reaktifitas dari electrophile: 3 > benzylic, allylic > 2 >
1 >> Me
Intermediate Carbocation terbentuk
Racemization b) Rearrangements

Acid-Catalyzed SN1

Example:

Regiochemistry: NA
Stereochemistry: Racemization

Acid-Catalyzed SN1
Mechanism:

Comment: E1 reaction is major competitor.

E1 Reaction
Example:

Regiochemistry:
Saytzeff's rule: the more highly substituted alkene will be
the dominant product.
Stereochemistry: nonspecific (cis and trans alkenes will
form)

E1 Reaction
Mechanism:

Comments:
Reactivity of electrophile: 3 > 2
Carbocation intermediates are formed.
Reaction competes with SN1. E1 is preferred at higher
temperature

Acid Catalyzed Elimination


Example:

Regiochemistry: Saytzeff rule applies.


Stereochemistry: nonspecific

Acid Catalyzed Elimination


Mechanism:

Competes with acid catalyzed SN1.

Markovnikov Addition
Example:

Regiochemistry:
Markovnikov's rule: the hydrogen adds to the
carbon with the greatest number of
hydrogens.
Stereochemistry: nonspecific

Markovnikov Addition
Mechanism:

Comments:
Carbocation intermediates are formed.

Anti-Markovnikov addition
Example:

Regiochemistry: Anti-Markovnikov
Stereochemistry: nonspecific

Anti-Markovnikov addition
Mechanism:

Comments:
Radical intermediates are formed.
Relative reactivity: 3 > 2 > 1 .
Related reaction: Hydroboration

REDOX
DEFINITIONS OF OXIDATION AND REDUCTION (REDOX)
This page looks at the various definitions of oxidation and
reduction (redox) in terms of the transfer of oxygen, hydrogen
and electrons. It also explains the terms oxidising agent and
reducing agent.
Oxidation and reduction in terms of oxygen transfer
Definitions
Oxidation is gain of oxygen.
Reduction is loss of oxygen.
For example, in the extraction of iron from its ore:

REDOX
Oxidising and reducing agents

An oxidising agent is substance which oxidises something else.


In the above example, the iron(III) oxide is the oxidising agent.
A reducing agent reduces something else. In the equation, the
carbon monoxide is the reducing agent.
Oxidising agents give oxygen to another substance.
Reducing agents remove oxygen from another substance.
Oxidation and reduction in terms of hydrogen transfer
These are old definitions which aren't used very much nowadays.
The most likely place you will come across them is in organic
chemistry.
Definitions
Oxidation is loss of hydrogen.
Reduction is gain of hydrogen.

REDOX
An update on oxidising and reducing agents

Oxidising agents give oxygen to another substance or remove


hydrogen from it.
Reducing agents remove oxygen from another substance or
give hydrogen to it.

Oxidation and reduction in terms of electron


transfer

This is easily the most important use of the terms oxidation and
reduction at A' level.

Definitions

Oxidation is loss of electrons.


Reduction is gain of electrons.

REDOX
OXIDATION OF ALCOHOLS

Oxidising the different types of alcohols


The oxidising agent used in these reactions is normally a solution
of sodium or potassium dichromate(VI) acidified with dilute
sulphuric acid. If oxidation occurs, the orange solution
containing the dichromate(VI) ions is reduced to a green
solution containing chromium(III) ions.
The electron-half-equation for this reaction is

OXIDATION
Primary alcohols

Primary alcohols can be oxidised to either aldehydes or carboxylic


acids depending on the reaction conditions.
Partial oxidation to aldehydes
You get an aldehyde if you use an excess of the alcohol, and distil
off the aldehyde as soon as it forms.
The excess of the alcohol means that there isn't enough oxidising
agent present to carry out the second stage. Removing the
aldehyde as soon as it is formed means that it doesn't hang
around waiting to be oxidised anyway!

OXIDATION
Primary alcohols

Full oxidation to carboxylic acids


You need to use an excess of the oxidising agent and make sure
that the aldehyde formed as the half-way product stays in the
mixture.
The alcohol is heated under reflux with an excess of the oxidising
agent. When the reaction is complete, the carboxylic acid is
distilled off.

OXIDATION
Secondary alcohols
Secondary alcohols are oxidised to ketones - and that's it.
For example, if you heat the secondary alcohol propan-2ol with sodium or potassium dichromate(VI) solution
acidified with dilute sulphuric acid, you get propanone
formed.

OXIDATION
Using these reactions as a test for the different types of
alcohol

You would need to show that it was a neutral liquid, free of water
and that it reacted with solid phosphorus(V) chloride to
produce a burst of acidic steamy hydrogen chloride fumes. You
would then add a few drops of the alcohol to a test tube
containing potassium dichromate(VI) solution acidified with
dilute sulphuric acid. The tube would be warmed in a hot water
bath. Results for the various kinds of alcohol. Picking out the
tertiary alcohol
In the case of a primary or secondary alcohol, the orange solution
turns green. With a tertiary alcohol there is no colour change.
After heating:

OXIDATION
Distinguishing
alcohols

between

the

primary

and

secondary

You need to produce enough of the aldehyde (from


oxidation of a primary alcohol) or ketone (from a
secondary alcohol) to be able to test them. There are
various things which aldehydes do which ketones don't.
These include the reactions with Tollens' reagent,
Fehling's solution and Benedict's solution. A much
simpler but fairly reliable test is to use Schiff's reagent.
Schiff's reagent is a fuchsin dye decolourised by
passing sulphur dioxide through it. In the presence of
even small amounts of an aldehyde, it turns bright
magenta.It must, however, be used absolutely cold,
because ketones react with it very slowly to give the
same colour.

OXIDATION ALDEHYDE AND KETONE


What is formed when aldehydes are oxidised?

OXIDATION ALDEHYDE AND KETONE


Using Tollens' reagent (the silver mirror test)
Tollens' reagent contains the diamminesilver(I) ion,
[Ag(NH3)2]+.
This is made from silver(I) nitrate solution. You add a drop
of sodium hydroxide solution to give a precipitate of
silver(I) oxide, and then add just enough dilute ammonia
solution to redissolve the precipitate.

OXIDATION ALDEHYDE AND KETONE


Using Fehling's solution or Benedict's solution
Fehling's solution contains copper(II) ions complexed with tartrate
ions in sodium hydroxide solution. Complexing the copper(II)
ions with tartrate ions prevents precipitation of copper(II)
hydroxide.
Benedict's solution contains copper(II) ions complexed with citrate
ions in sodium carbonate solution. Again, complexing the
copper(II) ions prevents the formation of a precipitate - this time
of copper(II) carbonate.
Both solutions are used in the same way. A few drops of the
aldehyde or ketone are added to the reagent, and the mixture is
warmed gently in a hot water bath for a few minutes