Binary Organic Mixture Separation and Qualitative Analysis

Organic mixtures which contain two different organic compounds are called Binary mixtures
(solid + solid or solid + liquid or liquid + liquid).
The general procedure followed for the qualitative analysis of organic mixtures is to separate
them first into their individual components. These separated compounds may then be
considered as a single organic compound. Hence in dealing with mixtures of organic
compounds special emphasis must be given to their separation.
In general, separation methods can be grouped into two categories:
i) Methods based on the differences in the physical properties. Difference in the
physical properties like boiling point, Volatilities or solubilities of components can
be used in separation by distillation, sublimation or extraction with solvents
respectively.

ii) Methods based on the differences in the chemical properties. If one of the
components of the mixtures reacts with some reagent to form a salt or compound
which can be easily reconverted back to that component and has different
solubility from the other component then advantage can be taken of this fact in
separation of mixture.

The separation of binary mixtures and classification of separated compounds is carried out in
six different steps in the following sequence.

1) Preliminary test of the mixture

2) Type of the mixture
3) Chemical nature of the mixture
4) Separation of the mixture
5) Purification and drying of the separated compounds
6) Identification of the separated compounds

Separation of Mixtures containing Two Organic Solids

Depending on the solubilities in water of the organic compounds present in the mixture one of
the two method described below may be used.

i) If both the components are insoluble in water the chemical method may be used. ii) In
case one of the components is soluble in water then separation may be achieved by
shaking the mixture with excess water. On filtration the insoluble component is recovered
as residue while soluble component passes into the filtrate. The filtrate when evaporated
solid component is obtain as residue.

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CHC 110 Organic Chemistry Practical T.Y. BSc. – Carmel College Nuvem Goa.
Preliminary tests of the mixture
State Solid Mixture is solid + solid

Semi solid or viscous Solid + solid (both low melting) or solid + solid (one is
high and other is low melting)

Solid in liquid Insoluble solid + volatile or non-volatile liquid

liquid Soluble solid + volatile liquid

Volatile liquid + non-volatile liquid

Colour Yellow Nitro compounds

Reddish-brown Aromatic amines or phenol

Dark blue/black α-naphthol, α-naphthyl amine

Buff β-naphthol

colourless Simple acids, alcohols, esters, ketones, aldehydes,

ethers and hydrocarbons.

Odour Carbolic Phenols, naphthol

Fishy Amines

Sweet or pleasant Esters, alcohols and halogen derivatives

Bitter almond Nitrobenzene, benzaldehyde, naphthalene

Moth ball naphthalene

Type of the mixture

A. For solid + solid

The physical state of the mixture is its appearance at room temperature. The actual type of
mixture can be confirmed by performing the following tests.
Test 1
Mix + ½ test tube water. Solid separates in bulk Water soluble compound is present.
Shake well and filter in a Refer Scheme 1 for large scale
porcelain dish. separation. Confirm by Ether test
Evaporate the filtrate to below and then find the Chemical
dryness. type of the water-soluble
compound.

(In some cases, this test gives a small quantity of solids due to their partial solubility in water.
However, in such cases, a water-soluble compound is considered to be absent.)
If water soluble compound is present perform Test no. 3 with the residue which remains on
the filter paper. If water soluble compound is absent directly proceed with Test no. 3 by
taking fresh mixture.

Test 2: Ether test ( to confirm presence of water soluble compound)

While performing this test the following precautions are to be taken:

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CHC 110 Organic Chemistry Practical T.Y. BSc. – Carmel College Nuvem Goa.
• Preferably use dry ether in dry test tube
• Use a small quantity of the mixture and about 1mL of ether
• Do this test in the absence of working burners.
Mix + dry ether in a dry Mixture does not dissolve Water soluble or partially
test tube and shake well. completely water-soluble compound
may be present.

Chemical Type of water-soluble solid compounds:

Shake 0.1 g compd. With 1 Blue Litmus turns red Acidic compound (i.e
mL of water and test a drop acid or phenolic)
of the solution with blue
litmus paper. Blue litmus does not turn red Non-acidic compound
(i.e basic or neutral)

For Acidic compounds

Shake 0.1 g compd. With Congo red turns blue Acid compound
1 mL of water and test a immediately
drop of the solution with
Congo red paper. No change in congo Phenolic compound
red paper

To 0.2g of compound, Effervescence observed Acid compound

add saturated NaHCO3
solution along the side No Effervescence Phenolic compound
of test tube.

For Non-acidic compounds

Shake 0.1 g compd. With Congo red turns blue Neutral compound
1 mL of water and add 1 immediately
drop of dilute HCl, and
 then test a No change in congo Basic compound
drop of the solution red paper
with Congo red paper.

Test 3 (Test for Acid)

Residue from Test no. 1. + Effervescence is observed Carboxylic acid is present.
½ test tube saturated
NaHCO3, shake well and Refer Scheme 2 for large
filter. Cool the filtrate and Regeneration of a solid scale separation
add con. HCl till acidic.
(Use residue if any for
Test no. 4)

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CHC 110 Organic Chemistry Practical T.Y. BSc. – Carmel College Nuvem Goa.
Test 4 (Test for Phenol)
Residue from Test no. 3. + Regeneration of a solid Phenol is present.
½ test tube 2N NaOH,
shake well and filter. Cool Refer Scheme 3 for large
the filtrate and add con. scale separation
HCl till acidic. (Use
residue if any for Test no.
5)

Test 5 (Test for Base)

Wash the residue obtained Regeneration of a solid Base is present.
in Test no. 4 with water
and treat it with ½ test Refer Scheme 4 for large
tube 1:1 HCl, shake well scale separation
and filter. Cool the filtrate
in ice and add NaOH till
alkaline. (Red litmus turns
blue)

If residue remains it should be considered as a water insoluble neutral compound.

Large Scale Separation:

Scheme 1
If first compound of the mixture is water soluble then the nature of the mixture is a water
soluble (Compound A) + Compound B which could be water insoluble acid or phenol or
base or neutral. Carry out large scale separation as follows.
Take the remaining mixture in a beaker + 2 t.t water, stir well and filter.
Residue
Filtrate
Wash it with water to remove traces of
Take the filtrate in an evaporating dish and water-soluble compound and dry it.
boil* till it becomes viscous and then cool. Recrystallize a small quantity for taking the
Remove the crystalline solid, dry it by melting point and performing C.T. use the
proper method and identify it. remaining for identification tests.
*Do not evaporate the filtrate to dryness
as the compound may decompose or
evaporate due to sublimation. Compound B
Compound A
Water insoluble acid/phenol/base/neutral
Water soluble

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CHC 110 Organic Chemistry Practical T.Y. BSc. – Carmel College Nuvem Goa.
Scheme 2
If first compound of the mixture is water insoluble acid then the nature of the mixture is a
water insoluble acid (Compound A) + Compound B which could be water insoluble
phenol or base or neutral. Carry out large scale separation as follows.
Take the remaining mixture in a beaker + 2 t.t saturated NaHCO3 solution, stir well and filter.
Residue
Filtrate
Wash it with saturated NaHCO3 to make it
Cool and acidify with con. HCl with stirring free from acid followed by water to remove
till acidic. Filter the solid and wash it with saturated NaHCO3 and dry. Recrystallize a
water to remove HCl. Dry it, recrystallize a small quantity for taking the melting point
small quantity for taking m.p. and use the and use the remaining for identification
remaining for identification test. tests.
Compound B
Compound A
Water insoluble phenol/base/neutral
Water insoluble Acid

Scheme 3
If first compound of the mixture is water insoluble phenol then the nature of the mixture is a
water insoluble phenol (Compound A) + Compound B which could be water insoluble
base or neutral. Carry out large scale separation as follows.
Take the remaining mixture in a beaker + 2 t.t 2N NaOH, stir well and filter.
Residue
Filtrate
Wash it with NaOH to make it free from
Cool and acidify with con. HCl with stirring phenol followed by water to remove NaOH
till acidic. Filter the solid and wash it with and dry. Recrystallize a small quantity for
water to remove HCl. Dry it, recrystallize a taking the melting point and use the
small quantity for taking m.p. and use the remaining for identification tests.
remaining for identification test. Compound B
Compound A
Water insoluble base/neutral
Water insoluble Phenol

Scheme 4
If first compound of the mixture is water insoluble base then the nature of the mixture is a
water insoluble base (Compound A) + water insoluble neutral. Carry out large scale
separation as follows.

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CHC 110 Organic Chemistry Practical T.Y. BSc. – Carmel College Nuvem Goa.
Take the remaining mixture in a beaker + 2 t.t 1:1 HCl, stir well and filter.
Residue
Filtrate
Wash it with 1:1 HCl to make it free from
Cool in ice and add 6N NaOH with stirring base followed by water to remove 1:1 HCl
till basic. Filter the solid and wash it with and dry. Recrystallize a small quantity for
water to remove NaOH. Dry it, recrystallize taking the melting point and use the
a small quantity for taking m.p. and use the remaining for identification tests.
remaining for identification test. Compound B
Compound A
Water insoluble Neutral
Water insoluble Base

B. For Liquid Mixtures.

The physical state of the mixture is its appearance at room temperature. The actual type of
mixture can be confirmed by performing the following test.

Test 1.
 Take a small Mixture solidifies Both the compounds or mixture
quantity of the completely of compounds is low melting,
mixture in a dry test hence mixture is
tube and keep it in Solid + Solid
an ice bath
Solid separates from liquid Mixture is
Low melting solid + Liquid.

Test 2: Volatility test

Pour a small Solid separates Mixture contains solid dissolved
quantity of the in volatile liquid. Therefore
mixture in a mixture is Solid + Volatile
watch glass an blow liquid
it gently
No separation of solid Mixture is:
Volatile liquid + Non-volatile
liquid.

Separation of liquid (volatile) + Liquid (Non-Volatile) Mixture.

• If liquids are immiscible they will form separate layers and therefore can be easily
separated with the help of separating funnel.
• If liquids are miscible with each other, then, they can be separated by distillation. (the
liquid with lower boiling point will distill over first leaving behind the liquid with
higher boiling point. The distillate is collected which is one component and the
residual liquid in distillation flask is the other component which can also be distilled
at its boiling point and collected in pure form.)

The mixture is taken in a dry round bottom flask of the Hickman head distillation apparatus.
A porcelain piece is added to the apparatus setup and placed in water bath. On heating, as the
boiling point of the volatile component reaches it distills in the Hickman head, remove the
fraction in a dry test tube. Continue heating and collect this fraction in another test tube. Now
replace the water condenser with an air condenser and heat directly to distill a portion of the
non volatile component which is discarded. The non volatile component is then distilled at

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CHC 110 Organic Chemistry Practical T.Y. BSc. – Carmel College Nuvem Goa.
high temperature, collect this in another dry test tube. Proceed and analyze each component
independently.

Separation of Liquid (volatile) + solid (soluble or Insoluble) Mixture.

• If one of the component is a solid and other a liquid then, advantage is taken of the
difference in the volatility of the two components and separation can easily be
achieved by distillation. On heating the liquid distil over leaving behind the solid
residue.

The separation of this type of mixture is the same as the liquid + liquid mixture except that
once the volatile component is separated the portion remaining in the round bottom flask is
poured on the watch glass to obtain the solid component.

Chemical Nature of the mixture

Test whether the solid or liquid compounds are water soluble/miscible by adding a little
compound to 1 mL water and shaking well. If the solid dissolves completely or if there is no
separation of two distinct layers than the solid or liquid is water soluble/miscible. If the solid
does not dissolve completely or if there is separation of two distinct liquid layer than the solid
or liquid is water insoluble/immiscible.

Chemical Nature of water soluble/miscible solid/liquid.

compd. + 1 mL of water and Blue Litmus turns red Acidic compound (i.e
test a drop of the solution acid or phenolic)
with blue litmus paper.
Blue litmus does not turn red Non-acidic compound
(i.e basic or neutral)

For Acidic compounds

compd. + 1 mL of water Congo red turns blue Acid compound
and test a drop of the immediately
solution with Congo red
paper. No change in congo Phenolic compound
red paper

compound, add saturated Effervescence observed Acid compound

NaHCO3 solution along
the side of test tube. No Effervescence Phenolic compound

For Non-acidic compounds

compd. + 1 mL of water Congo red turns blue Neutral compound
and add 1 drop of dilute immediately
HCl, and then test a drop
of the No change in congo Basic compound
solution with Congo red paper
red paper.

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CHC 110 Organic Chemistry Practical T.Y. BSc. – Carmel College Nuvem Goa.
Chemical Nature of water insoluble/immiscible solid/liquid.
i)Test for Acid Compound dissolves with Acid is present.
Comp + saturated effervescence (if not filter
NaHCO3, shake well and to get clear solution)
filter. Cool the clear
filtrate and add con. HCl
 till acidic. Regeneration of a solid

ii)Test for Phenol Compound dissolves Phenol is present.

Comp + 2N NaOH, shake w(if not filter to get
well and filter. Cool the clear
filtrate and add con. HCl solution)
till acidic.
Regeneration of a solid

iii)Test for Base Compound dissolves (if Base is present.

Comp. + 1:1 HCl, shake not filter to get clear
well and filter. Cool the solution)
filtrate in ice and add
NaOH till alkaline. (Red Regeneration of a solid
litmus turns blue)

If all the above test are negative the compound is water insoluble neutral compound.

After the separation of the binary mixture the identification of separated compound is
carried out separately for each compound in six different steps in the following
sequence.
1) Preliminary test
2) Detection of chemical nature
3) Detection of elements
4) Functional group test
5) Determination of physical constant (melting/ boiling point)
6) Identification & Confirmation

Note:- The chemical nature of the respective compound is already ascertained at the time of
separating the binary mixture. Therefore, tests for it need not be repeated while analyzing the
individual compounds. Only mention the chemical nature as found previously in a sentence.

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CHC 110 Organic Chemistry Practical T.Y. BSc. – Carmel College Nuvem Goa.