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Alkynes

• Contains c to c triple bonds.


• Alkynes can be described by the formula
CnH2n  - 2where n is 2,3, ……
• The simplest member of this homologous series
has the molecular formula C2H2


• where R may be an alkyl group or H
• Alkynes are very reactive compounds and hence
they never occur in the free state in nature.
They are present to a sizeable extent in the
gases obtained by the cracking of petroleum
Preparation of ethyne in the laboratory

• Ethyne is prepared by the action of


water on calcium carbide.





The gas thus produced is collected by the downward disp
properties
• Physical properties
• It is a colourless gas with garlic-like odour
when pure. It is soluble in organic
solvents. It is poisonous and highly
explosive.
• Chemical properties
1. Combustion
• It burns in air with a sooty flame to
produce carbon dioxide and water
vapour. The flame is white, sooty and
produces an extremely high
temperature of 40000C.
Chemical properties
2. Addition reactions
Due to higher degree of unsaturation,

addition reaction in ethyne takes


place in 2 stages:
1.The 1st stage yields a product with c
=c
2.The 2nd stage converts this into a
fully saturated compound. i.e. c - c
Chemical properties

2 (a) Addition of hydrogen


• An ethyne reacts with hydrogen in


the presence of catalyst (Pt or Ni)
at 250°C, first forming ethene and
finally ethane.

b. With Halogens (e.g chlorine/bromine)

S ta g e I S ta g e II

I a n d II
co m b in e d

Try fo r b ro m in e
(Br2)

c. With the hydrogen halides ( HCl , HI , HBr )


Chemical ppties (addition
rxn)
d. With chlorine and bromine water
(HOCl & HOBr)

e . A d d itio n o f w a te r d ich lo ro e th a n a
l
In th e p re se n ce o f su lp h u ric a cid ( 4 2 % ) a n d 1 %
m e rcu ric su lp h a te a t 6 0 ° C , e th yn e a d d o n o n e
w a te r m o le cu le to g ive e th a n a l.

e th a n a
l
Xcal
ppties
3. Oxidation

• acidified KMnO4 oxidises ethyne to


oxalic acid(ethan edioic acid).
• 4[
O]

P o ly m e riza tio n
W h e n e th yn e ( a ce tyle n e ) is p a sse d th ro u g h a h o t
co p p e r tu b e , it p o lym e rize s to b e n ze n e .
Laboratory Detection of
Ethyne
• Both ethene and ethyne are
unsaturated hydrocarbons and as a
result of this, both can decolourise
bromine water (HOBr) and acidified
potassium tetraoxomanganate (VII)
(KMnO4).

• So how can we distinguish
between these?
Test to Differentiate btw ethene
and ethyne
• Ethyne has the power to undergo
certain reactions with the insoluble
salts of the noble metals, especially
those eof copper
th yn e re a cts wand
ith a m silver.
m o n ia ca l
co p p e r( I) ch lo rid e r( C u C l)
To p ro d u ce re d d ish b ro w n p re cip ita te
a n d w ith
silve r e q u iva le n ce w h ich is silve r( I) ch lo rid e ( A g C l).
To p ro d u ce y e llo w p p t w h ich ra p id ly tu rn s
g re y .
W h ile
e th e n e h a s n o e ffe ct o n a llth e se sa lts.  
Uses

• Illuminant in acetylene lamps.


• Oxy-acetylene torches for welding
metals.
• Starting material for the synthesis of
organic compounds like
acetaldehyde, acetic acid, ethyl
alcohol and tetrachloroethane.
Tetrachloroethane is a solvent and
is also called Westron.
AROMATIC HYDROCARBONS-BENZENE
•  A benzene ring is a six-membered ring
containing carbon atoms linked to each
other with alternate single and double
bonds.
• Aromatic hydrocarbons that contain one or
more benzene rings are called
( where Arenes
n = 6 or
(CnH2n-6  ) m o re ).


• Some benzene compounds

Structures of benzene
K e k u le 's  ( 1 8 6 5 )
fo rm u la
D e fe cts in K e k u le 's fo rm u la
W h ile K e ku le 's fo rm u la exp la in e d m o st o f
th e o ry se rve d fa cts fo r b e n ze n e , it co u ld still
n o t exp la in th e sa tu ra te d n a tu re o f
b e n ze n e .
R e so n a n ce h y b rid stru ctu re o f b e n ze n e
T h e cu rre n tly a cce p te d stru ctu re w a s d e ve lo p e d b y
th e a p p lica tio n o f th e th e o ry o f re so n a n ce p ro p o se d in
1 9 3 3 . T h is th e o ry sta te s th a t b e n ze n e is a re so n a n ce
h yb rid o f th e fo llo w in g ca n o n ica lfo rm s.
Properties of Benzene
• Physical
• Benzene is a colourless liquid
(melting point 5.5°C, boiling point
80.4°C) with a characteristic smell
of aroma.
• It is immiscible with water, but
dissolves organic solutes.
• It is lighter than water: density 0.87 g
cm-3
• Its vapors are toxic.

Properties of Benzene
Chemical Properties of Benzene
1 . Combustion
Benzene and its homologues are highly inflammable
liquids and burn with a sooty flame.
2C6H6 + 15O2 12CO2 + 6H2O

2 . Substitution reactions
Benzene gives substitution reactions with chlorine as
described below.
Properties of Benzene
• Addition Reactions
• Benzene gives some addition reactions. Some
typical reactions are:
 Addition of hydrogen
• Benzene on reduction with hydrogen under
pressure in the presence of finely divided nickel
at 200°C, gives an addition product
hexahydrobenzene (cyclohexane).

cyclohexane
A d d itio n o f ch lo rin e
C h lo rin e a d d s o n to b e n ze n e a t its b o ilin g p o in t, in
th e p re se n ce o f b rig h t su n lig h t, to g ive h exa ch lo rid e .

3Cl2
benzene hexachloride
Uses of Benzene
n t fo r fa ts a n d o ils, ru b b e r, re sin s e t
lfo r d ye s, d ru g s, p e rfu m e s a n d exp l
o o lle n clo th e s.
w ith p e tro l, u n d e r th e n a m e b e n zo l
Alkanols(Saturated
Monohydric
General formula :
Alcohols)
C H    OH
n 2n +1
Functional group :
 
OH
Suffix :
ol

They can be classified as:


Alcohols with one hydroxyl group - Monohydric alcohol
Alcohols with two hydroxyl groups - Dihydric alcohol
Alcohols with three hydroxyl groups - Trihydric
alcohols
Alcohols with four or more hydroxyl groups -
Polyhydric alcohols
No. of C Molecular Parent Common IUPAC
Atoms formula alkane name name
1 CH3OH CH4 (metha Methyl Methanol
ne) alcohol
2 CH3CH2O C2H6 (ethanEthyl Ethanol
H e) alcohol
3 C3H7OH C3H8(propa Propyl Propanol
ne) alcohol
4 C4H9OH C4H10 (prop Butyl Butanol
ane) alcohol

For
example:
They can be further
classified into:
P rim a ry A lco h o l
H e re th e ca rb o n a to m b e a rin g th e h yd roxylg ro u p is
a tta ch e d to ju st o n e o th e r ca rb o n a to m .

S e co n d a ry A lco h o l
H e re th e ca rb o n a to m b e a rin g th e h yd roxyl
g ro u p is a tta ch e d to tw o o th e r ca rb o n a to m s.
Te rtia ry A lco h o l
H e re th e ca rb o n a to m b e a rin g th e h yd roxylg ro u p is
a tta ch e d to th re e o th e r ca rb o n a to m s.
Ethanol(Kaikai,Ogogoro,sep
e)
E th yl a lco h o l is th e m o st im p o rta n t m e m b e r o f th e
a lco h o l se rie s a n d is o th e rw ise kn o w n a s a lco h o l, sp irit
o f w in e a n d g ra in a lco h o l. It ca n b e p re p a re d b y a n y
o n e o f th e g e n e ra lm e th o d s o f p re p a ra tio n o f p rim a ry
a lco h o l.
Pre p a ra tio n
F ro m E th y le n e
E th yle n e , o b ta in e d fro m cra cke d p e tro le u m , is
co m p re sse d to 1 1 4 0 0 - 2 2 8 0 0 m m o f H g p re ssu re
a n d a b so rb e d in co n ce n tra te d su lp h u ric a cid ( 9 8 % ) a t
340 - 350K.
T h e re su ltin g p ro d u ct is e th ylh yd ro g e n su lp h a te o r
e th yl su lp h a te .

T h e re a ctio n m ixtu re is d ilu te d w ith w a te r a n d


w a rm e d . H yd ro lysis o ccu rs a n d e th a n o lis g o t a lo n g
w ith so m e e th e r a s b y - p ro d u ct.

T h e e th a n o l fo rm e d is d istille d o ff, le a vin g th e a cid


w h ich ca n b e co n ce n tra te d a n d u se d a g a in .
Manufacture of Ethanol by Fermentation

Ethanol can be manufactured by the fermentation of:


qMolasses
qStarch. (maize (US: corn), wheat, barley or potatoes.)

rmentation is slow decomposition by micro-organisms of large


ganic molecules into smaller molecules
This is the principle behind souring of milk, batter,
putrefaction of meat, and preparation of wine and
vinegar.
Fermentation was the earliest method used for preparing
alcohol in industries. This is still used for the
manufacture of alcohol and alcoholic drinks like beer,
wine, brandy, etc,.

Assignment: find out the process of manufacturing of ethanol


from molasses
From Starch
Starchy raw materials
Wheat, barley, rice, maize and
potatoes.

Conversion of starch into maltose


( saccharification )  
It is carried out as follows:
Step I
Malting
Moist barley is allowed to germinate in dark at 290K.
Germinated barley is called Malt  and this is heated to
330K (to stop further germination). It is then crushed
and extracted with water. This Malt extract contains
the enzyme diastase.
Step II
Mashing
To break the cell walls, starch is reacted with
superheated steam. This exposes the starch inside that
forms a paste like mass called Mash.
Conversion of starch
into maltose
( saccharification )  
Step III
Hydrolysis
Mash and malt extract (supplies enzyme DIASTASE) are
treated together at 320-330K. In about half an hour,
hydrolysis is complete and maltose is formed.
Step IV
Alcoholic Fermentation
Maltose obtained from starch is fermented in the
presence of yeast. Maltase present in yeast converts
maltose into glucose. Another enzyme zymase present in
yeast, then converts glucose into ethanol and carbon
dioxide.
Concentration of ethanol

e ethanol produced by fermentation is 18% pure because yeast


ll is killed at concentrations higher than this.

tional distillation of the product, concentration of ethanol


es to 95%. This is called rectified spirit.
purification of rectified spirit by distilling over quicklim
LUTE SPIRIT which contain 99.5% ethanol.
Physical Properties
1.Ethanol is a colourless, inflammable liquid has a
spirituous odour and burning taste.
2.Ethanol boils at 780C, freezes at -18oC.
3.Mixes with water in all proportions (soluble in
water).
4.Neutral to litmus

:
boiling point and solubility of alkanols are affected by the
ence of hydrogen bonding in alkanols.

HOW?
Hydrogen bonding
Hydrogen bonding occurs between molecules where you
have a hydrogen atom attached to one of the very
electronegative elements - fluorine, oxygen or nitrogen.
In the case of alcohols, there are hydrogen bonds set
up between the slightly positive hydrogen atoms and
lone pairs on oxygens in other molecules.

The hydrogen atoms are slightly positive because the


bonding electrons are pulled away from them towards
the very electronegative oxygen atoms.
Hydrogen bonding in alcohols

ØAn alcohol is an organic molecule containing an -O-


H group.
Any molecule which has a hydrogen atom attached
directly to an oxygen or a nitrogen is capable of
hydrogen bonding.

ØSuch molecules will always have higher boiling


points than similarly sized molecules which don't
have an -O-H or an -N-H group. The hydrogen bonding
makes the molecules "stickier", and more heat is
necessary to separate them.

ØEthanol, CH3CH2-O-H, and methoxymethane, CH3-O-CH3,


both have the same molecular formula, C2H6O.
The boiling points of ethanol and methoxymethane
show the dramatic effect that the hydrogen bonding
has on the stickiness of the ethanol molecules:

ethanol (with 78.5°C


hydrogen bonding)

methoxymethane -24.8°C
(without hydrogen
bonding)

The hydrogen bonding in the ethanol has lifted its


boiling point about 100°C.
Note

The higher boiling point of the butan-1-ol is due to


the additional hydrogen bonding.
Comparing the two alcohols (containing -OH groups),
both boiling points are high because of the
additional hydrogen bonding due to the hydrogen
attached directly to the oxygen - but they aren't the
same.
The boiling point of the 2-methylpropan-1-ol isn't as
high as the butan-1-ol because the branching in the
molecule makes the van der Waals attractions less
effective than in the longer butan-1-ol.
Solubility of alcohols in water

erally, hydrocarbons are not soluble in water, but alkanols ar


uble because the hydroxyl groups in their molecules can form
rogen bondings with the water molecules.

lubility decreases as the number of carbon atoms in increases


kanols. Primary alkanol with more than five carbon atoms are
soluble in water.
Chemical Properties

1 Combustion reaction
Supply the equation of reaction

2 With sodium and potassium


When sodium, potassium or lithium is reacted with
dry ethanol, the hydrogen atom of the hydroxy group
is replaced by the metal atom to form alkoxides.
Hydrogen is liberated in the process.

This reaction also serves as an


identification test for alcohols .
3 Reaction with the chloride of phospho

Reaction with phosphorus ( III ) chloride , PCl 3


Alcohols react with liquid phosphorus(III) chloride
(also called phosphorus trichloride) to make
chloroalkanes.

Reaction with phosphorus ( V ) chloride , PCl 5


Solid phosphorus(V) chloride (phosphorus
pentachloride) reacts violently with alcohols at
room temperature, producing clouds of hydrogen
chloride gas
4 . Oxidation
Ethanol is oxidised to acetaldehyde first, which is
then oxidised to acetic acid (ethanoic acid).
Note :-
Note that both the aldehyde and the acid formed
contain the same number of carbon atoms as the
alcohol

OR

This is what is happening in the second stage:


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

Tertiary alcohols aren't oxidised by acidified


sodium or potassium dichromate(VI) solution. There
is no reaction whatsoever .
5 . Dehydration
With sulphuric acid ( another dehydrating
agent ), ethanol gives various products under
different conditions .
With excess concentrated sulphuric acid at temperature
above 170oC , ethanol reacts to form ethyl hydrogen
tetraoxosulphate(VI) which then decomposes to yield
ethene.

170
(1
)

(2
)
e other hand, if the alkanol is in excess, and the temperature
, it will react with the acid to yield ethoxyethane (diethyl

170
6 . ESTERIFICATION

Ethanol reacts reversibly with acids to form ethyl


esters. This process is known as esterification .

if you were making ethyl ethanoate from ethanoic


acid and ethanol, the equation would be:
Uses of Ethanol
Ethanol is used in the manufacture of:
1.paints and varnishes
2.alcoholic beverages
3.ether, choloform, iodoform and other
organic compounds dyes
4.power alcohol, a substitute for petrol
5.it is also used as a fuel in spirit lamps
and stoves
6.in scientific apparatus like thermometers
and spirit levels
7.Because of is low freezing point (-117oC),
ethanol is sometimes used as an anti-
freeze in automobile radiator.
Analytical Tests for Ethanol

Ethanol can be identified by the fruity odour it emits


when heated gently with sodium acetate and
concentrated sulphuric acid. This is due to the
formation of ethyl ethanoate.
Iodoform test: When a few drops of alcohol is warmed
with iodine and potassium hydroxide
yellow , of
iodoform with characteristicprecipitate
smell is got.
Reaction with Carboxylic Acids ( Esterification )
Alcohols react with carboxylic acids in the presence
of concentrated sulphuric acid as catalyst to form
esters which have generally sweet fruits smells. For
example,

This reaction is used as a test for alcohols as well


as carboxylic acids.
Analytical Tests for Ethanol
Sodium Metal Test
When a small piece of sodium metal is dropped into
alcohol, hydrogen is liberated. This is accompanied by
effervescence.

In this test, the alcohol used must be free from


moisture. This is because water reacts with sodium in
the same way as alcohol, liberating hydrogen gas. The
test could be misleading otherwise.
Alkanoic Acids or Saturated Monocarboxylic
Acid
General formula :
C n H 2n+1 COOH
carboxylic (- COOH) group
Functional group :
Suffix : oic acid

In IUPAC system, the name of an alkanoic acid is


obtained by replacing the last 'e' from the name of
the parent alkane with -oic acid.
Name of monocarboxylic acid = Name of the parent
alkane - e + oic acid= Alkanoic acid
A dicarboxylic acid contains two carboxylic groups
linked to the same or different carbon atoms. In the
IUPAC system, the name of alkanedioic acid is obtained
by adding the suffix, -dioic acid to the name of the
parent alkane.
Name of the dicarboxylic acid = Name of the parent
alkane + dioic acid
For example: Ethanedioic acid (oxalic acid, parent
alkane is ethane)

Propanedioic acid (Malonic acid


Butanedioic
), acid (Succinic
parent alkane is propane) acid, parent alkane is
butane)
Ethanoic Acid
Formula: CH3COOH, IUPAC Name: Ethanoic acid

Source: vinegar

Physical properties
qAcetic acid is a colourless, corrosive liquid with
a pungent smell at ordinary temperatures.
qBelow 290K, it solidifies to an icy mass called
glacial acetic acid.
qIt boils at 391K
qIt is miscible with water, alcohol and ether in all
ratios.
THE LAB PREPARATION OF ETHANOIC ACID

can be prepared by distilling anhydrous sodium ethanoate,


3COONa with conc. Tetraoxosulphate (VI) acid.

CH3COONa + H2SO4 CH3COOH + NaHSO4

H2SO4

CH
3 CO CH3COOH
ON
a

Ice water
thanoic acid can also be prepared by the complete oxidation o
thanol by acidified sodium heptaoxodichromate(VI) solution.

CH3CH2OH + 2[O] CH3COOH +


H2O
Chemical Properties

Physical properties
qAcetic acid is a colourless, corrosive liquid with
a pungent smell at ordinary temperatures.
qBelow 290K, it solidifies to an icy mass called
glacial acetic acid.
qIt boils at 391K
qIt is miscible with water, alcohol and ether in all
ratios.
Chemical Properties

Acidic properties
Acetic acid ionizes in polar media
to give hydrogen ion that is responsible for its
acidic behavior.

So, acetic (ethanoic) acid can react with alkalis


and alkali metal carbonates and also with metals.
(properties of an acid)
With Alkalis , Carbonates and Bicarbonates

ethanoate

Bicarbonate(hydrogen trioxocarbonate(IV)) test is used as an


identification test for the presence of carboxylic group in a
compound.
With Metals
Acetic acid reacts with strongly electropositive
metals like sodium and zinc to give the respective
acetate and liberate hydrogen.

Ester formation ( esterification )


Ethanoic acid reacts with alcohols (ethanol) in the
presence of dehydrating agents like concentrated
tetraoxosulphate(VI) acid to form esters.

ethanoate
Reduction
In the presence of lithium aluminium hydride
(LiAlH4 ), ethanoic acid can be reduced to ethanol.

Tests for Ethanoic Acid


If the compound is soluble in water and if it gives
brisk effervescence (due to the liberation of carbon
dioxide) when treated with sodium trioxocarbonate(IV)
or sodium hydrogen trioxocarbonate(IV), it is a
carboxylic acid.
Uses of Ethanoic Acid
1.Ethanoic acid is used in the: manufacture of dyes,
perfumes and rayons
2.manufacture of rubber from latex and casein from milk.
It is used for coagulation
3.form of salts in medicine and paints
4.form of acetates of aluminium and chromium is used as
mordants
5.dilute form is used as vinegar and in the concentrated
form as a solvent
6.form of organic esters as perfumes

Mordants are compounds that are used often in the production of various


textile products. The main purpose of a mordant is to interact with the
fibers of a given material and the dye solution. This interaction helps
to ensure that the dye sets properly, without splotching or
running. Mordants are employed at several different points in the
production process, depending on the type of material used and the
desired effect that the manufacturer wishes to achieve.
Ethylenediamminetetraacetat
e EDTA