PHASE EQUILIBRIUM

PHYSICAL CHEMISTRY For STPM

Introduction
Mixture of Liquids
1. Miscible Liquid: Two liquids dissolve completely in each
other to form homogeneous solution. Similar in structure
Examples: Ethanol and water.
2. Immiscible Liquids: Two layers are formed. Example:
Benzene and water
3. Partially miscible liquids: Small amount dissolves in each
other to form homogeneous solution. Example: Ether and
water
4. Ideal Solution: Intermolecular force of attraction between
molecules of solvents and solution are equal. No change of
volume and no enthalpy change on mixing.
Raoult’ Law
1. The partial vapor pressure of A in a solution at a given
temperature is equal to the vapor pressure of pure A
multiplied by mole fraction of A in solution.
PA = PoA XA
2. There is actually no such thing as an ideal mixture! However,
some liquid mixtures get fairly close to being ideal. These are
mixtures of two very closely similar substances.
Commonly quoted examples include:
 hexane and heptane
 benzene and methylbenzene
 propan-1-ol and propan-2-ol
Ideal mixtures and intermolecular forces
 In a pure liquid, some of the more energetic molecules have
enough energy to overcome the intermolecular attractions and
escape from the surface to form a vapor.
 The smaller the intermolecular forces, the more molecules
will be able to escape at any particular temperature.
Ideal mixtures and intermolecular forces
If the red molecules still have the same tendency to escape as before, that
must mean that the intermolecular forces between two red molecules must
be exactly the same as the intermolecular forces between a red and a blue
molecule.
The intermolecular attractions between two red molecules, two blue
molecules or a red and a blue molecule must all be exactly the same if the
mixture is to be ideal
 The total vapour pressure of the mixture is equal to the sum of the
individual partial pressures.


 The Po values are the vapour pressures of A and B if they were on their
own as pure liquids.
 xA and xB are the mole fractions of A and B.
 You calculate mole fraction using, for
example:
Practice
 The vapor pressure of benzene and mehylbenzene at 298 K
are 8.2 x 104 and 3.6 x 104Pa respectively. A mixture consists
of 19.5 g of benzene and 36.8 g of methylbenzene is
maintained at 298 K. Calculate:
a) The partial pressure of benzene and methylbenzene in the
mixture
b) The total pressure of the mixture. [3.12, 2.23, 5.36 x 104]
2. A mixture contains 38 g of heptane and 50g of octane are 45
kPa and 26 kPa respectively. Calculate:
a) The total pressure
b) The composition of the vapor [34.8kPa, 0.60, 0.40]
Vapor Pressure Composition Diagram
Xbenzene 0.00 0.20 0.40 0.60 0.80 1.0
Pressure (x104 Pa) 0.00 1.64 3.28 4.92 6.56 8.20
Xmethylbenzene 1.00 0.80 0.60 0.40 0.20 0.00
Pressure (x104 Pa) 3.60 2.88 2.16 1.44 0.72 0.00
Total 3.60 4.52 5.44 6.36 7.58 8.20

Pressure
Pure benzene has a higher vapor
Ptotal pressure than methylbenzene.
Hence, benzene is volatile and has
Pbenzene
lower boiling point.

Pmethylbenzene

0 X benzene mole fraction

Composition of Vapor above the Ideal Solution
1. The composition of vapor above the liquid mixture is different
from the composition of the liquid mixture.
2. When an ideal solution is at equilibrium with its vapor, the
vapor always contains a higher percentage of the more volatile
component than in the liquid mixture.
3. The composition of the vapor is calculated using Dalton’s
Law Partial Pressure:
X benzene = partial pressure of benzene/total pressure.
Xbenzene 0.00 0.20 0.40 0.60 0.80 1.0
Pressure (x104 Pa) 0.00 1.64 3.28 4.92 6.56 8.20
Total 3.60 4.52 5.44 6.36 7.58 8.20
Xbenzene (g) 0.00 0.36 0.60 0.77 0.87 1.00
Practice 2
a) Which liquid is more volatile, X or Y? Explain your answer.
b) What is composition of the vapor in equilibrium with a liquid
mixture containing:
i) 50% mole fraction of X
ii) 30% mole fraction X.
c) Determine the partial pressure of Y in a mixture containing
60% mole fraction of X.

0 0.3 0.4 0.5 0.6 mole fraction for X

The Effect of Temperature on the Vapor Pressure Phase
pressure

1 atm A B

temperature
t1 t2
1. The presence of solute molecules decreases of molecules of solvent that reach surface of
the liquids. As a result, the number of solvent molecules escape as a vapor decrease.
2. The presence of a non volatile solute decreases the vapor pressure of a solvent. Hence,
the boiling point of the solvent increases.
3. In order for a liquid to solidify, the molecules must begin to form a cluster of molecules.
When a solute is added to a solvent, the solute particles deter the solvent molecules from
being able to get closer effectively.
4. In order for the solute molecules to reach the closer, they must be slowed down, by
having a lower temperature. Thus the freezing point is reduced.
Enthalpies of Vaporization and Boiling Point.
1. The molar enthalpy of vaporization is proportional to the strength of the
international forces of attraction.
2. Strong intermolecular forces of attraction that exist in the liquid will have:
a) low vapor pressure
b) high molar enthalpy of vaporization.
c) high boiling point
Liquid Enthalpy of Vaporization (kJ/mol) Boiling Point (oC)
CH4 8.2 -161
HCl 16.1 -85
NH3 23.4 -33
CCl4 30.0 77
H2O 41.0 100
Boiling Point/Composition Graph
1. From the graph, we can determine the boiling point of any composition as
well as the composition of the vapor given off at the boiling point of that
mixture.
2. For example, a mixture containing 0.2 mole fraction of benzene will boil
at 102oC and vapor given off will have a composition of 0.8 mole fraction
of benzene.
3. If this vapor is condensed and collected, it will produce a liquid mixture
with 0.8 mole fraction of benzene. This liquid will boil at 94 oC.

Temperature

110 V
102
94 L

0.2 0.8 mole fraction of benzene

  Fractional distillation in the lab The apparatus
 A typical lab fractional distillation would look like this:

1. The fractional column is a long tube filled with glass beads or short pieces of glass
tubing. The fractioning column provides a large surface area so that the condensed liquid
and ascending vapor would have maximum contact.
2. The smaller the difference boiling point of the component separated, the longer the
column needed.
 Low
temperature

High
temperature

1. In the fractionating column, the temperature decreases from the bottom of the
column to the top of the column.
2. If you boil a liquid mixture C1, you will get a vapour with composition C2, which
you can condense to give a liquid of that same composition (the pale blue lines).
3. If you reboil that liquid C2, it will give a vapour with composition C3. Again you
can condense that to give a liquid of the same new composition (the red lines).
4. Reboiling the liquid C3 will give a vapour still richer in the more volatile
component B (the green lines). You can see that if you were to do this once or
twice more, you would be able to collect a liquid which was virtually pure B.
Positive Deviation from Raoult’s Law
1. Raoult's Law only works for ideal mixtures. In these, the forces between
the particles in the mixture are exactly the same as those in the pure
liquids. The tendency for the particles to escape is the same in the
mixture and in the pure liquids. That's not true in non-ideal mixtures.
2. In mixtures showing a positive deviation from Raoult's Law, the vapour
pressure of the mixture is always higher than you would expect from an
ideal mixture.
Positive Deviation from Raoult’s Law
1. The fact that the vapour pressure is higher than ideal in these mixtures
means that molecules are breaking away more easily than they do in the pure
liquids.
2. That is because intermolecular forces between molecules of A and B are less
than they are in the pure liquids.
3. When the solution of positive deviation is prepared, heat is absorbed and the
volume increases slightly. The enthalpy change of mixing is endothermic.
4. If a mixture has a high vapour pressure it means that it will have a low
boiling point. The molecules are escaping easily and you won't have to heat
the mixture much to overcome the intermolecular attractions completely.
5. The implication of this is that the boiling point / composition curve will have
a minimum value lower than the boiling points of either A or B.
6. In the case of mixtures of ethanol and water, this minimum occurs with
95.6% by mass of ethanol in the mixture. The boiling point of this mixture is
78.2°C, compared with the boiling point of pure ethanol at 78.5°C, and
water at 100°C.
Positive Deviation from Raoult’s Law: Ethanol and water mixtures
1. Suppose you are going to distil a mixture of ethanol and water with composition C1
as shown on the next diagram. It will boil at a temperature given by the liquid curve
and produce a vapour with composition C2.
2. When that vapour condenses it will, of course, still have the composition C2. If you
reboil that, it will produce a new vapour with composition C3.
3. You can see that if you carried on with this boiling-condensing-reboiling sequence,
you would eventually end up with a vapour with a composition of 95.6% ethanol. If
you condense that you obviously get a liquid with 95.6% ethanol.
Positive Deviation from Raoult’s Law: Ethanol and water mixtures
1. What happens if you reboil that liquid?
2. The liquid curve and the vapour curve meet at that point. The
vapour produced will have that same composition of 95.6%
ethanol. If you condense it again, it will still have that same
composition.
 You have hit a barrier. It is impossible to get pure ethanol by
distiling any mixture of ethanol and water containing less
than 95.6% of ethanoll.
 This particular mixture of ethanol and water boils as if it were
a pure liquid. It has a constant boiling point, and the vapour
composition is exactly the same as the liquid.
 It is known as a constant boiling mixture or an azeotropic
mixture or an azeotrope.
Positive Deviation from Raoult’s Law: Ethanol and water mixtures
1. To summarise:
 Distilling a mixture of ethanol containing less than 95.6%
of ethanol by mass lets you collect:
 a distillate containing 95.6% of ethanol in the collecting
flask (provided you are careful with the temperature
control, and the fractionating column is long enough);
 pure water in the boiling flask.
2. What if you distil a mixture containing more than 95.6%
ethanol?
 a distillate containing 95.6% of ethanol in the collecting
flask (provided you are careful with the temperature
control, and the fractionating column is long enough);
 pure ethanol in the boiling flask.
Negative Deviation from Raout's Law:
1. In exactly the same way, you can have mixtures with vapour
pressures which are less than that expected by Raoult's Law.
It giving a minimum value for vapour pressure lower than that
of either pure component.
Negative Deviation from Raoult’s Law:
1. The molecules break away from the mixture less easily than
they do from the pure liquids. New stronger forces must exist
in the mixture than in the original liquids.
2. The intermolecular attraction between molecules in the non
ideal solution causes:
a) A slight decrease in volume
b) Heat energy to be liberated
c) A decrease tendency of the molecules to escape from the
surface of the liquid mixture.
3. Consequently, the vapor pressure of the liquid mixture decrease.
Negative Deviation from Raoult’s Law: Concentrated HNO3
1. The mixtures of nitric acid and water have boiling points higher than
either of the pure liquids because it needs extra heat to break the stronger
attractions in the mixture.
2. In the case of mixtures of nitric acid and water, there is a maximum
boiling point of 120.5°C when the mixture contains 68% by mass of nitric
acid. That compares with the boiling point of pure nitric acid at 86°C, and
water at 100°C.
Negative Deviation from Raoult’s Law:
1. Start with a dilute solution of nitric acid with a composition of C1. The vapour
produced is richer in water than the original acid. If you condense the vapour and
reboil it, the new vapour is even richer in water. Fractional distillation of dilute nitric
acid will enable you to collect pure water from the top of the fractionating column.
2. As the acid loses water, it becomes more concentrated. Its concentration
gradually increases until it gets to 68% by mass of nitric acid. At that point,
the vapour produced has exactly the same concentration as the liquid,
because the two curves meet.
Negative Deviation from Raoult’s Law:
1. This time you are starting with a concentration C2 to the right of the azeotropic
mixture. The vapour formed is richer in nitric acid. If you condense and reboil
this, you will get a still richer vapour. If you continue to do this all the way up the
fractionating column, you can get pure nitric acid out of the top.
2. As far as the liquid in the distillation flask is concerned, it is gradually losing nitric
acid. Its concentration drifts down towards the azeotropic composition.
3. Distilling a nitric acid / water mixture containing more than 68% by mass of nitric
acid gives you pure nitric acid from the top of the fractionating column and the
azeotropic mixture left in the distillation flask.
Separation of Azeotropic Mixture

1. Using a third component: Mixture of ethanol and water can

be separated by adding benzene.
2. Using chemical method: Calcium oxide will be used to
absorb water from azetropic of ethanol and water. The
mixture is then filtered to remove excess calcium oxide and
the filtrate is redistilled to obtain pure ethanol.
3. Using an adsorbent: Silica gel can be used to remove one
component from the azeotropic mixture
4. Using solvent extraction: Ether is normally used.
Fractional Distillation under Reduced Pressure
1. Distillation under educed pressure is usually used to distill out substances
that have highly boiling point.
2. Some organic liquids decompose at temperature below their boiling point
at atmospheric pressure. It is necessary to distil the liquid at reduced
pressure in order to lower the boiling point.
3. Steam is blown through the mixture and the water and phenylamine turn
to vapour. This vapour can be condensed and collected.

As the hot steam passes through the

mixture it condenses, releasing heat. This
will be enough to boil the mixture of
water and phenylamine at 98°C provided
the volume of the mixture isn't too great.
The condensed vapour will consist of both
water and phenylamine. If these were truly
immiscible, they would form two layers
which could be separated using a
separating funnel
Fractional Distillation under Reduced Pressure
1. Phenylamine decomposes at normal boiling (184oC) at
atmospheric pressure.. However, at lower pressure,
phenylamine can be distilled out without decompose at
100oC.
2.
Pressure (kNm ) 101.
-2
12.9 6.1 2.4
3
B.P. (oC) 184 120 100 80
3. Steam distillation can be used to extract some natural
products - for example, to extract eucalyptus oil from
eucalyptus, citrus oils from lemon or orange peel, and to
extract oils used in perfumes from various plant materials.
Immiscible Liquid Mixture.
1. Two liquids are immiscible if the intermolecular forces of attraction
between their molecules are very different.
2. Immiscible liquids are those which won't mix to give a single phase.
3. Oil and water are examples of immiscible liquids because water is polar
molecule with hydrogen bonding while oil is non polar molecules with van
der waals forces of attraction.
4. In a mixture if immiscible liquid, the total vapor pressure of the mixture is
the sum of the vapor pressure of the pure components:
5. At 98°C, the saturated vapour pressures of the two pure liquids are:
 phenylamine7.07 kPa
 water94.30 kPa

The total vapour pressure of an agitated

mixture would just be the sum of these - in
other words, 101.37 kPa
Composition of The Distillate of Steam Distillation
mA = pAMA
mB = pBMB
Practice:
1. The RMM of an organic compound X is 156. A liquid mixture containing
two immiscible liquid X and water is steam distilled at 95 C under a
pressure 1.01 x 105 Nm-2. The vapor pressure of water is 8.5 x 104 Nm-2.
Calculate the percentage by mass of X in the distillate.
[1.63/(1+1.63)]x100% = 62%

2. An organic liquid is steam distilled. The vapor pressures for the organic
liquid and water are 5.3 kPa and 96 kPa respectively. If the distillate
contains 32.43% by mass of organic liquid, what is the RMM of the
organic liquid? [156.5]
The Distribution of a Solute between Two Solvents.
1. If a solid or liquid, X is added to a mixture of two immiscible liquids, X
may distribute by dissolving in both liquid.
2. According to Distribution Law: At constant temperature, a solute
distributes itself between two immiscible liquids so that the ratio of its
concentration in each solvent is constant, regardless of the amount of
solute added.
Example:
100 cm3 of water contains 10 g of an organic compound, X. if the mixture is shaken
with 50 cm3 of ethoxyethane, calculate the mass of X that dissolves in
ethoxyethane. The partition coefficient for X between ethoxyethane and water is 9.
Solution
9.0 = [X] in ethoxyethane layer/[X] in water
Let m is the mass of X in ethoxyethane.
(m/50) ÷ (10-m)/100 = 9.0
m = 8.19 g
The Distribution of a Solute between Two Solvents.
1. The partition law only holds under certain conditions:
a) The two solution must be reasonably dilute.
b) The solute must not react, associate or dissociate in the solvents.
c) The temperature must be kept constant.
Example
1. 1.0 g of iodine is shaken with 50 cm3 of water and 50 cm3 of water and 50 cm3 of
CCl4. 25 cm3 of the aqueous solution requires 4.5 cm3 0f 0.01M sodium thiosulphate
(S2O32-) for titration using starch as the indicator. Calculate the partition coefficient
of iodine between water and CCl4.
Solution:
I2 + 2S2O32-  S4O62- + 2I-
(MV)I2 in water / (MV)I2 inS2O3 = ½
MI2 in water = 0.0009 M
Mass of iodine in 50 cm3 water: 0.0009 x 50/1000 x (2x127) = 0.01143 g
Mass of iodine in 50 cm3 of CCl4: 1.0 – 0.01143 = 0.989 g
K = 0.01143/0.989 = 0.01156
The Distribution of a Solute between Two Solvents.
1. The distribution of iodine between CCl4 and water is 85 at 298K. 10 g of iodine
is shaken with 100 cm3 of water and 100 cm3 of CCl4. Calculate the mass of
iodine dissolve in CCl4. [9.88g]

Solvent Extraction
1. Organic compounds can be extracted from aqueous solution by using
organic solvents. (Ether extraction)
2. The advantages using ether to extract organic compounds from aqueous
from aqueous solution are as follow:
a) Ether is a good solvent for many organic compounds.
b) Ether is chemically inert and does not react with organic compounds.
c) Ether is immiscible with water and can be separated easily as the
upper layer from the aqueous layer.
d) Ether has a low boiling and is therefore very volatile. It is easily
distilled off.
Practice
1. The partition coefficient of X between ether
and water is 40 at room temperature. 1.0 dm3
of an aqueous solution containing 5.0 g of X is
extracted with ether. Calculate the mass of X
extracted from the aqueous from the aqueous
solution by shaking the solution with:
a) 50 cm3 ether. [3.33g]
b) Two successive of 25 cm3 portion of ether.
[3.75g]
Determination of An Equilibrium Constant
1. Iodine is not very soluble in water, dissolves readily in potassium iodide
solution due to the formation of a complex ion.
I2(aq) + I- (aq)  I3- (aq)
2. [I2] cannot be obtained directly from titration because thiosulphate ion react
with both the iodine molecules in the complex ion I3- and the free I2 molecules.
3. However, only free covalent I2 molecules can dissolve in both water and organic
solvents.
Practice
1. A small amount of iodine is dissolved in aqueous potassium iodide of
concentration 0.20 M. Te mixture is then shaken with tetrahloromethane (CCl4)
until equilibrium is established. The concentration of iodine in the aqueous and
CCl4 are determined by using standardized sodium thiosulphate solution. If the
concentration of iodine in the aqueous layer is 0.10 M and the concentration of
iodine in the CCl4 layer s 0.102 M, calculate the equilibrium constant for the
reaction at room temperature.
I2(aq) + I- (aq)  I3- (aq)
The partition coefficient for the distribution of iodine between water and CCl4
is 0.012.
Determination of An Equilibrium Constant
Solution:
K = [I2]water/[I2]CCl4
0.012 = [I2]water/0.102
[I2]water = 1.22 x 10-3 moldm-3
In aqueous layer: I2, I- and I3- , in the CCl4 : I2
0.10 = 1.22 x 10-3 + [I3-]
[I3- ] = 0.09878 moldm-3
Total concentration of I- ions in water = [I-] and [I3-]
0.20 = 0.09878 + [I-]
[I-] = 0.1012 moldm-3

K = [I3-] / [I2] [I-]

= 0.09878/(1.22x10-3)(0.1012)
= 800 dm3mol-1
Determination of The Formula of a Complex Ions
Cu2+ (aq) + nNH3 (aq)  [Cu(NH3)n]2+ (aq)
1. In order to determine the formula of the complex ion, we need to know
the number of moles of ammonia that combine with one mole of Cu2+
ions using titration of dilute acid.
2. The aqueous layer contains cu2+ ions, NH3 and [Cu(NH3)n]2+ . The acid
used in the titration of the aqueous layer reacts with ammonia from NH3
and [Cu(NH3)n]2+ .
3. However, the complex ions are not soluble in organic solvent. Only free
ammonia molecule can distribute themselves between water and organic
solvent.
Practice:
1. 100 cm3 aqueous CuSO4 of 0.1M were mixed with 100 cm3 of ammonia 1.0M.
The mixture was shaken with 100 cm3 CHCl3. The concentration of ammonia
in the organic layer was determined by using titration of HCl of 0.016 M. The
partition coefficient for ammonia between water and CHCl 3 is 25.0 . Calculate
the formula of the complex ion, [Cu(NH3)n]2+ [Cu(NH3)n]2+
Determination of The Formula of a Complex Ions
Cu2+ (aq) + nNH3 (aq)  [Cu(NH3)n]2+ (aq)
1. The aqueous layer contains cu2+ ions, NH3 and [Cu(NH3)n]2+ . However,
the complex ions are not soluble in organic solvent.
Solution:
K = [NH3]water/ [NH3]organic
25.0 = [NH3]water/ 0.0116.
[NH3]water = 0.29 M
Total Volume = 200 cm3
No. of mole free ammonia: 0.29x200/1000 = 0.058 mol
No. of moles of ammonia in organic layer: 0.0116x100/1000 = 0.00116 mol
No. of moles of ammonia added initially: 1x100/1000 = 0.1 mol
Thus, no of mole of ammonia in the complex: 0.1-0.058 – 0.00116 = 0.041 mol
No of mole of Cu2+ = 0.1x100/1000
= 0.01 mol
Ratio Cu2+: NH3 = 0.01/0.041
= 1/4
The Solubility of Gases in Liquids
1. The mass of the gas solubility depends on:
a) Properties of gases
b) Properties of Liquids
c) Temperature of the liquids
d) Pressure on the gas.
2. The adsorption coefficient is the volume of gas dissolves in liquids at room
temperature
Solvent Water Ethanol Propanone Ethanone Ethoxyethane
Adsorption 0.028 0.144 0.163 0.208 0.416
coefficient
Effect of Temperature on the Solubility of Gas
1. The solubility of gas decreases when the temperature increases because
the dissolution of a gas is an exothermic reaction.
Gas (in gaseous state) Gas (in the solvent) (exothermic)
2. There are some cases in which the solubility of a gas (noble gas)
increases with increasing temperature.

Effect of Pressure on the solubility of Gas

1. Henry’s Law: the mass of an ideal gas dissolved in a given volume of solvent at
constant temperature I s directly proportionally to the pressure of gas.
C = Kh p
Gas (in solvent) Gas (in vapor phase)
2. According to Le Chateliar’s Principle: the increase n pressure will shift the
position of equilibrium in the direction that will reduce the pressure.
3. The pressure will be reduced if the gas dissolves in solvent. Thus, an increase in
pressure increases the solubility of a gas.
Application of Henry’s Law
1. Carbonated drinks are made by dissolving carbon dioxide gas at high
pressure of 8atm.
2. When a bottle of carbonated drink is opened, the pressure above the liquid
drops to 1 atm., and the carbon dioxide rapidly bubbles out of the solution.
3. If deep sea divers breathe ordinary air at high pressure, a large quantity of
nitrogen will dissolve in blood. When a diver goes rapidly from a great
depth (high pressure) to the surface, the decrease in pressure causes air,
dissolved in blood to bubble out of solution.
4. A mixture of 95% helium and 5% oxygen is breathe in. Helium is less
soluble and hence less gas will come out from the solution.
CHROMATOPRAHY
1. Chromatography is used to separate mixtures of substances into their
components. All forms of chromatography work on the same principle.
2. They all have a stationary phase (a solid, or a liquid supported on a
solid) and a mobile phase (a liquid or a gas). The mobile phase flows
through the stationary phase and carries the components of the mixture
with it. Different components travel at different rates.
3. Two forms of chromatography:
a) Adsorption: a substance adheres to the surface of a solid called the
adsorbent. The stationary phase is solid phase.
b) Partition: stationary phase is liquid while mobile phase either gas or
liquid. The component in a mixture are partitioned between the liquid
and the mobile phase.
Adsorption Chromatography
1. Adsorption may be physical process or chemical process.
2. In physical process, the substances are hold by Van der Waals @
hydrogen bonding on the adsorbent while in chemical process, the
substances are hold by covalent (hydrogenation by nickel).
3. Adsorption chromatography is widely used for separation, purification
and identification of organic and inorganic compound.
4. The stationary phase (solid) adsorb to varying extent the different
constituent of a mixing in a solution.
5. The most highly adsorbed substance will be adsorbed at then top of the
column and the weakly adsorbed substances lower down.
Partition Chromatography
1. Partition Coefficient K:
K = [X]mobile phase / [X] stationary phase
2. If component X in the mixture has a high value of K, means that X
dissolves readily in the mobile phase and therefore moves rapidly along
the stationary phase.
3. Conversely, if component X has low value of K, then X will remain
largely adsorbed on the stationary phase.
Type of Mobile Stationary Method of
Chromatography phase phase separation
Column Liquid Solid Adsorption
Thin layer Liquid Solid Adsorption
Gas-Liquid (GLC) Gas Liquid Partition
Paper Liquid Liquid Partition
Paper Chromatography
1. In paper chromatography, the stationary phase is a very uniform
absorbent paper. The mobile phase is a suitable liquid solvent such
as methanol.
2. Suppose you have three blue pens and you want to find out which one
was used to write a message. Samples of each ink are spotted on to a
pencil line drawn on a sheet of chromatography paper.
The paper is suspended
in a container with a
shallow layer of a
suitable solvent or
mixture of solvents in
it. It is important that
the solvent level is
below the line with the
spots on it.
Paper Chromatography
1. The reason for covering the container is to make sure that the
atmosphere in the beaker is saturated with solvent vapor. Saturating the
atmosphere in the beaker with vapor stops the solvent from evaporating
as it rises up the paper.
2. As the solvent slowly travels up the paper, the different components of
the ink mixtures travel at different rates and the mixtures are separated
into different colored spots.
Paper Chromatography
 Rf values
1. Some compounds in a mixture travel almost as far as the solvent does;
some stay much closer to the base line. The distance traveled relative to
the solvent is a constant for a particular compound as long as you keep
everything else constant - the type of paper and the exact composition
of the solvent, for example.
2. The distance traveled relative to the solvent is called the Rf value. For
each compound it can be worked out using the formula
Paper Chromatography
 Rf values
1. For example, if one component of a mixture traveled 9.6 cm from the
base line while the solvent had traveled 12.0 cm, then the Rf value for
that component is:

2. In some cases, it may be possible to make the spots visible by reacting

them with something which produces a coloured product. A good
example of this is in chromatograms produced from amino acid
mixtures.
 Ninhydrin reacts with amino acids to give coloured compounds, mainly
brown or purple.
 The left-hand diagram shows the paper after the solvent front has
almost reached the top. The spots are still invisible. The second diagram
shows what it might look like after spraying with ninhydrin.
                                                                                                              

There is no need to measure the Rf values

Paper Chromatography
Two way paper chromatography
 Two way paper chromatography gets around the problem of separating
out substances which have very similar Rf values.
 In the diagram, the position of the solvent front is marked in pencil
before the paper dries out. This is labelled as SF1 - the solvent front for
the first solvent. We shall be using two different solvents.
Paper Chromatography
1. If you look closely, you may be able to see that the large central spot in
the chromatogram is partly blue and partly green.
2. Wait for the paper to dry out completely, and then rotate it through 90°,
and develop the chromatogram again in a different solvent.

3. Paper chromatography is used to analyze: dyes in foods and drinks, dyes

in inks, plants pigments and mixture of amino acid.
Column Chromatography
1. In column chromatography, the stationary phase, a solid adsorbent, is
placed in a vertical glass (usually) column and the mobile phase, a
liquid, is added to the top and flows down through the column (by
either gravity or external pressure).

The mixture to be
analyzed by column
chromatrography is
applied to the top of the
column.
Column Chromatography
1. The liquid solvent (the eluent) is passed through the column by gravity.
2. An equilibrium is established between the solute adsorbed on the adsorbent
and the eluting solvent flowing down through the column.

The process of passing the solvent

through the column is called
elution.
The rate at which each component
travels down the column
depends on how strong it is
adsorbed.
In term of partition coefficient, the
component that has a higher
partition coefficient will move
through the column faster.
The polar solvent will compete for
space on the silica gel or
alumina
Thin Layer Chromatography
1. Thin layer chromatography is done exactly as it says - using a thin, uniform
layer of silica gel or alumina coated onto a piece of glass, metal or rigid
plastic.
2. The silica gel (or the alumina) is the stationary phase. The stationary phase
for thin layer chromatography also often contains a substance which
fluoresces in UV light. The mobile phase is a suitable liquid solvent or
mixture of solvents.
Thin Layer Chromatography

These measurements are then taken:

                                                                                                           
The Rf value for each dye is then worked out using the formula:
                                                                                         
Thin Layer Chromatography
 The stationary phase - silica gel
 Silica gel is a form of silicon dioxide (silica). The silicon atoms are joined
via oxygen atoms in a giant covalent structure. However, at the surface of
the silica gel, the silicon atoms are attached to -OH groups.
 So, at the surface of the silica gel you have Si-O-H bonds instead of Si-O-
Si bonds. The diagram shows a small part of the silica surface.
 The surface of the silica gel is very polar and, because of the -OH groups,
can form hydrogen bonds with suitable compounds around it as well as van
der Waals dispersion forces and dipole-dipole attractions.
Gas Liquid Chromatography
1. In gas-liquid chromatography, the mobile phase is a gas such as helium and
the stationary phase is a high boiling point liquid absorbed onto a solid.

Flow scheme for gas-liquid Very small quantities of the sample are
injected into the machine using a small
chromatography                                                            
syringe. Hot temperature is required so
that all the sample boils and is carried
into the column as a gas by the helium
(or other carrier gas). One of three
things might happen to a particular
molecule in the mixture injected into
the column:
a) It may condense on the stationary
phase.
b) It may dissolve in the liquid on the
surface of the stationary phase.
c) It may remain in the gas phase.
The time taken for a particular compound
to travel through the column to the
detector is known as its retention time.
Gas Liquid Chromatography
1. High boiling point compound has a long retention time.
2. The more soluble a compound is in the liquid phase, the less time it will
spend being carried along by the gas.
propanone
propanol
ethanol

Elution time

Gas Chromatography is used to:

a) Analyze hydrocarbon
b) Analyze trace pollutant in water and in air.
c) Identify toxic substance in food.
d) Detect small quantity of alcohol or drug in blood and urine.
Ion-Exchange Chromatography
1. The separation of a mixture of ions in solution can be carried out using ion
exchange chromatography.
2. Stationary Phase: synthetic resins (polymer of polar group: cation or anion),
Mobile Phase: solution.
3. Ion exchange chromatography can be classified: cation exchange resins and
anion exchange resins.
Cation Exchange Resin:
1. Contains a sulphonic acid group or carboxylic acid group. This resin can
exchange hydrogen ions in its molecules with other cations in the solution..
Ion Exchange Chromatography
1. An anion exchange resin: contains a quaternary ammonium group, for
example:

2. A combination of anion and cation ion exchange resin are

needed to produce deionized water.