The Chemistry of Solutions

Non Electrolytes
SPT 1201: PHARMACEUTICAL FORMULATION TECHNOLOGY I
S.D. NYAKUPINDA MSc (ICP)
OUTLINE
 GENERALITIES
 IDEAL SOLUTIONS
 RAOULT’S LAW
 REAL SOLUTIONS
 VAPOUR PRESSURE
 COLLIGATIVE PROPERTIES
 ADDITIVE PROPERTIES
 CONSTITUTIVE PROPERTIES
 Generalities;
 A solution is a system in which two or more components are mixed together to
form one phase.
 In this system the solute (dispersed component) is dissolved in a solvent
(dispersing component). In a true solution, the dispersed phase completely
dissolves, cannot scatter light and cannot be visualized using microscopy.
 Thus solutions have to have these characteristics;
i. Absence of chemical reaction between solvent and solute
ii. Homogenity
 In a solution the component present in larger proportion is the solvent whilst
that present in lesser proportion is the solute. However if the solution is a liquid
and solid one, the solid is designated the solute whilst the liquid is the solvent
regardless of their quantities.
 A binary solution is a solution composed of only two substances.
Solutions can be
Solute Solvent Examples
Solid Gas Iodine vapour in air,
smoke particles in air
Liquid Gas Water in gas
Gas Gas Air
Solid Solid Gold-Silver mixture
Liquid Solid Mineral oil in Paraffin
Gas Solid Hydrogen in Palladium
Solid Liquid NaCl (aq)
Liquid Liquid Ethanol in water
Gas Liquid Carbonated water,Alums
 Generalities;
 In terms of size of the dispersed component

Examples
True solutions: NaCl (aq), vinegar, copper sulfate (aq), sugar in water
Colloidal dispersions: Blood, liposomes, zinc oxide paste, milk
Course dispersions: Emulsions, suspensions
Physical properties

 These can be classified as

i. Colligative
ii. Additive
iii. Constitutive
 Colligative properties
 These depend on the number of particles in solution and not on their identity or
nature.
 They are
i. Osmotic pressure
ii. Vapour pressure lowering
iii. Freezing point depression
iv. Boiling point elevation
 The values of colligative properties are approximately the same for equal
concentrations of different non-electrolytes in solution regardless of the species or
chemical nature of the constituents.
Additive properties

 These depend on the sum of the properties of the constituents

in a solution or total contribution of the atoms in a molecule.
E.g. molecular weight or true mass of a solution.
Constitutive properties

 These depend mainly on the arrangement and partly on the number and kind of
atom within a molecule.
 They indicate the constitution of individual compounds and groups of molecules in
a system.
 The following properties are partly additive and partly constitutive;
i. Refractive index (refraction of light)
ii. Electric properties such as conductance.
iii. Surface and interfacial characteristics e.g. surface tension and viscosity.
iv. Solubility
 Generalities [cnt’d]
 Solutes are divided into electrolytes and non-electrolytes.
 Non electrolytes do not ionize when dissolved and therefore do not conduct electric current
through the solution e.g.
Sucrose
Glycerine
Naphthalene
Urea
 Electrolytes do ionize in solution and hence conduct electricity
 Electrolytes produce greater freezing point depressions and boiling point elevations than do non
electrolytes of the same concentration.
 Examples of electrolytes are
Hydrochloric acid
Ephedrine
Phenobarbital
Sodium sulfate
Ideal solutions
 An ideal solution is one in which there is no change in properties of the
components other than dilution when they are mixed to form the solution i.e.
i. No heat absorbed or evolved
ii. No shrinkage or expansion of volume
Example; Mixing 100ml of water and 100ml of ethanol produces 200ml of ethanol
solution yet if we mix 100ml of sulfuric acid with 100ml of water, the volume
produced is 180ml and heat is evolved.
 In an ideal solution it is assumed that the strengths of the intermolecular forces
are equal i.e. solvent-solvent = solvent-solute= solute-solute.
 Some solutions therefore approach ideality (e.g. those with similar bonds and
therefore miscible) whilst others only under extreme dilution.
Escaping tendency
 It is the tendency of a substance to leave its thermodynamic state by either
physical or chemical means.
Raoult’s law

The vapour pressure of a solution is the sum of the partial vapour pressures of the individual
constituents.
 Raoult’s law
 Example; In a solution consisting of ethylene chloride of mole fraction of 0.4 and
benzene of mole fraction of 0.6 If the vapour pressure of pure ethylene chloride is
236mmHg at 50°C and that of benzene is 268mmHg, The partial vapour pressure of
ethylene chloride is given by
PA = 0.4 x 236mmHg
= 94.4mmHg
 The partial vapour pressure of benzene is
PB=0.6 x 268mmHg
= 160.8mmHg
 So we have the total vapour pressure
PA+ PB = 94.4 + 160.8
= 255.2mmHg
Raoult’s law
 The vapour pressure composition curve for the binary system Ethylene
chloride,Benzene is shown
Real solutions
 According to Raoult’s law the overall vapour pressure P
P = p1 + p2
= p1°x1 + p2°x2
 Where
p1 and p2 are the partial pressures of solute and solvent respectively
x1 and x2 are molar fractions
p1° and p2° are the vapour pressures exerted by pure solute and pure solvent respectively.
 Real solutions however do not obey Raoult’s law because of differing strengths of the
solute-solute, solute-solvent and solvent-solvent intermolecular bonds.
 They either deviate positively or negatively from Raoult’s law.
 The thermodynamic activity which represents the effective concentration replaces in
calculations so that Raoult’s law applies both to ideal and non ideal systems.
Real solutions
 Thus;

 In ideal solutions
 In non-ideal solutions and the ratio is termed the activity coefficient (f) and it gives the
measure of deviation from the ideal.
 If solute-solvent attractions are weaker than solute –solute or solvent-solvent, then the
components will have little affinity for each other and the escaping tendency of the surface
molecules is increased when compared with an ideal solution.
 The vapour pressure will be greater than predicted by Raoult’s law and thus it shows positive
deviation. Consequently the thermodynamic activites are greater than mole fractions i.e. and .
 The extent of this deviation increases as miscibility of the components decreases e.g. the
mixture of alcohol + benzene shows a smaller deviation than the less miscible water + diethyl
ether whilst the imiscible mixture of water + benzene exhibits a very large positive deviation.
 If however the solvent and solute have a strong affinity then the solution shows a negative
deviation from Raoult’s law because the escape tendency of each constituent has been reduced
by possible complex formation or bond formation between the solute and solvent.
Real solutions
 In this case the overall pressure is less than that predicted by Raoult’s law
and and .Examples of solutions that do that are
Pyridine + acetic acid
Water + nitric acid
Chloroform + acetone
 Solutions that show a positive deviation from Raoult’s law show a maximal
vapour pressure at a particular composition whereas those that deviate
negatively will show a minimum vapour pressure at a particular
composition.
 Vapour pressure
 It is the pressure exerted over the surface of a substance by the vapour of the
molecules which have escaped from its surface due to them having more energy to
overcome the attractive forces exerted by the substances’ other molecules.
 Vapour pressure in solids is less than that in liquids since the intermolecular forces
are greater in solids than in liquids.
 The escaping tendency for surface molecules is higher in liquids than in solids.
 In instances where the solute is a non-volatile solid and the solvent is liquid, the
vapour pressure is due solely to the solvent because the intermolecular forces within
the solid are too strong to permit its molecules to escape and so contribute to the
total vapour pressure.
 In a liquid-liquid solution (miscible liquids) the molecules of both components are
equally likely to escape and they therefore contribute to the overall vapour pressure
exerted by the solution.
 Mixtures of chemically similar components are the ones which obey Raoult’s law.
Distillation of Binary mixtures
 A binary mixture is one containing two liquids in solution.
 The higher the vapour pressure of a liquid, the lower its boiling
point and the more volatile it is.
 Since the vapour of a binary mixture is always richer in the
more volatile constituent, distillation can be used to separate
the more volatile from the less volatile constituent.
Distillation of Binary mixtures

 The diagram shows the b.p of pure A and that of pure B.

 A mixture of these substances having composition a is distilled at the boiling
point b. The composition of the vapour v1 in equilibrium with the liquid at the
temperature is c. This is also the composition of the distillate when it is
condensed.
 The vapour is therefore richer in B than the liquid from which it was distilled.
Colligative properties
1) Vapour pressure lowering

 According to Raoult’s law the vapour pressure of a solvent over a dilute solution is equal to the
vapour pressure of the pure solvent p°A multiplied by the mole fraction of the solvent in the solution
xA.
 It is more convenient to express the vapour pressure of a solution in terms of the concentration of
the solute than the mole fraction of the solvent.
 We have
 Hence
 Where

 A co rd in g to R a o u lt’sa w

 is the lowering of the vapour pressure

 The relative vapour pressure lowering is equal to the mole fraction of the solute.
 Example 01
 Calculate the relative vapour pressure lowering at 20°C for a solution
containing 171.2 g of sucrose (wB) in 1000 g (wA) of water. The molecular weight
of sucrose (mB) is 342.3 g/mole and the molecular weight of water (mA) is 18.02
g/mole.
 Solution
 Number of moles of sucrose are
 Number of moles of water are
 Mole fraction of sucrose (the solute) is given by

 .
Example 02
 Calculate the vapor pressure when 0.5 mole of sucrose is added to 1000 g of water at 20°C. The
vapor pressure of water at 20°C is 17.54 mm Hg.
Solution
 Mole fraction of sucrose is given by
 hence

 And the vapour pressure lowering is given by

 Which is
Colligative properties
2) Boiling point elevation
 The boiling point of a solution is higher than that of a pure solvent as the presence of a solute lowers
the vapour pressure of the solvent.
 This is called boiling point elevation and the greater the amount of solute dissolved the greater the
effect.

Diagram showing the relationship of solute concentration to boiling point

From the diagram above the elevation of the boiling point ΔTb is given by .
The ratio of b.p elevation to vapour pressure lowering ΔP at constant temperature is a constant given by
and
The b.p elevation is considered to be proportional to the relative vapour pressure lowering Δp/p° which
in turn is equal to the mole fraction of the solute, hence .
 It can be shown that

Where is the molal elevation constant or Ebullioscopic constant whose value is characteristic for
each solvent.
m is the molality of the solution
 Another way of calculating is given by the equation

 Where is the boiling point of solvent

 Vv is the molar volume of gas
 Vl is the molar volume of liquid
 ΔHv is the molar heat of vaporization
Since Vl is negligible when compared to Vv the equation becomes

And replacing Vv with RT/P for one mole of gas we get

Hence

Since
Example 03
A 0.200 m aqueous solution of a drug gave a boiling point elevation of 0.103°C. Calculate the
approximate molal elevation constant for the solvent, water
Solution

So
= 0.103/0.2
=0.515 deg kg/mole
The proportionality of to molality holds only at infinite dilutions i.e. when real solutions behave as ideal
solutions.
Ebullioscopic and Cryoscopic constants for various solvents

Substance Boiling Kb Freezing Kf

point /°C point /°C

Acetic 118.0 2.93 16.7 3.9

acid
Aceton 56.0 1.71 -94.82 2.4

Ethanol 78.4 1.22 -114.49 3.0

Benzene 80.1 2.53 5.5 5.12

Camphor 208.3 5.95 178.4 37.7

Water 100.0 0.511 0.00 1.86

 Colligative properties
3) Freezing point depression
 Solutions freeze at lower temperatures than pure solvents, the more concentrated the
solution the greater the difference between the freezing points.
 The depression of freezing point ΔTf under very dilute conditions is proportional to molality
and it also depends on the mole fraction of the solute as it is a colligative property.
Δ
 Or
Δ
 Where w1 is the mass of water
 w2 is the mass of solute
 M2 is the molecular weight of solute
 Kf is the molal depression constant or Cryoscopic constant
 The cryoscopic constant for water is taken to be 1.86 or 1.9.
Example 04
What is the freezing point of a solution containing 3.42 g of sucrose and 500 g of water? The
molecular weight of sucrose is 342. In this relatively dilute solution, Kf is approximately
equal to 1.86.
Solution
Δ
= 1.86 *1000*3.42/ (500*342)
= 0.0372°C
Therefore, the freezing point of the aqueous solution is -0.037°C.
Constitutive properties
1) Refractive index

 Refraction happens when light changes its speed as it enters a dense medium
(substance) from a vaccum or air.
 The refractive index is the ratio of its relative speeds thus

 Where i is the angle of incidence

 r is the angle of refraction
 c is the velocity of light
Medium Index
vaccum 1
air 1.00029
Water at 20°C 1.33
acetone 1.36
Sugar solution 30% 1.38
Ethyl alcohol 1.36
Sugar solution 80% 1.49
 The refractive index varies with the wavelength of light e.g. blue light is bent more than
red light and also the temperature (that means even pressure for gases).
 The refractive index can be used to
• Identify a substance
• Determine the purity of a substance
• Measure the concentration of a solution
 The molar refraction Rm given by

Where M is molecular weight

is the density of the compound
 The molar refraction depends on the number and arrangement (additive and constitutive
property) of atoms within a compound but is independent of the state of the compound.
Constitutive properties
2) Optical activity
 Compounds which have an asymmetrical carbon (achiral center) refract polarized light in specific
directions. Clockwise rotation defines the substance as dextrorotatory (+ve angle) whilst anticlockwise
defines them as levorotatory (-ve angle).
 The specific rotation angle at a certain temperature is taken as a characteristic of a pure substance.
Specific angles of rotation for some drugs
Drug Angle Temperature solvent
(degrees) /°C
ampicillin +283 20 water
benzylpenicil +305 25 water
lin
camphor +42 25 ethanol
nicotine -162 20 Pure liquid
reserpine -120 25 chloroform
Tetracycline -253 24 methanol
hydrochlorid
e
Yohimbine +51 to +62 20 ethanol
……..End