Solutions of Nonelectrolytes

Introduction

A true solution is defined as a mixture of two or more

components that form a homogenous molecular dispersion,
in other words, a one-phase system, the composition of
which can vary over a wide range.
 Types of solutions
Example Solvent Solute
Air Gas Gas
Water in oxygen Gas Liquid
Iodine vapor in air Gas Solid
Carbonated water Liquid Gas
Alcohol in water Liquid Liquid
Aqueous sodium chloride solution Liquid Solid
Hydrogen in palladium Solid Gas
Mineral oil in paraffin Solid Liquid
Gold-silver mixture, mixture of alums Solid Solid
 Types of Solutions
 The solutes (whether gases, liquids, or solids) are
divided into two main classes: nonelectrolytes and
electroytes.

 Nonelectrolytes are substances that do not yield ions

when dissolved in water and therefore do not conduct an
electric current through the solution.

 Examples of noneletrolytes are sucrose, glycerin,

naphthalene, and urea.
 Types of Solutions

 Electrolytes are substances that form ions in solutions,

conduct the electric current.

 Examples of electrolytes are hydrochloric acid, sodium

sulfate, ephedrine, and phenobarbital.

 Electrolytes may be subdivided further into strong

electroytes (hydrochloric acid, sodium sulphate) and
weak electrolytes (ephedrine, phenobarbital).
 Concentration Expressions
Definition Symbol Expression
Moles (gram molecular weights) of solute in 1 liter M Molarity
of solution
Gram equivalent weights of solute in 1 liter of N Normality
solution
Moles of solute in 1000g of solvent m Molality
Ratio of the moles of one constituent (e.g. the X, N Mole fraction
solute) of a solution to the total moles of all
constituents (solute and solvent)
Moles of one constituent in 100 moles of the Mole percent
solution. Mole percent is obtained by multiplying
the mole fraction by 100
Grams of solute in 100g of solution % w/w Percent by weight
Milliliters of solute in 100mL of solution % v/v Percent by volume
Grams of solute in 100mL of solution % w/v Percent weight-in-
volume
Milligrams of solute in 100mL of solution - Milligram percent
Equivalent Weights
Equivalent Weights
Eq Wt (ACID)
Inorganic Acid 

HCl, HNO3, H2SO4 

+EqWt = MW/no. of replaceable H 

Eg HCl MW= 36g/mole 

EqWt=36/1 

36g= 

Eg H2SO4 

98/2= 

49g= 
 mEqwt (ACID)
EqWt = MW/no. of replaceable H+ x 1000 
Eg HCl 
mEqwt = 36/1x1000 
0.036g = 
 Eq Wt (BASE)
-Eq Wt = MW/# of replaceable OH 
Eg. NaOH, KOH, Ca(OH)2, Mg(OH)2 
Na(OH) (MW) = 40g 
EqWt = 40/1 
40g= 
 mEqWt (BASE)
Eq Wt = MW/# of replaceable OH- x 1000 
NaOH 
mEqWt = 40/1x1000 
0.040g= 
 EqWt (SALT)
Acid + Base = Salt + Water 
H Cl + Na OH = NaCl + HOH 
Eg – NaCl, AgCl, CuSO4, Na2SO4, ZnCl2 
EqWt = MW/#valence 
NaCl (MW) = 58g/mole 
EqWt = 58/1 
58g= 
mEqWt (SALT)
EqWt = MW/#valence x 1000 
Eg NaCl 
mEqWt = 58/1 x 1000 
0.058g= 
Get the Eqwt and mEqWt of the
:following
acetic acid .1 
phosphoric acid .2 
sodium borate .3 
Magnesium hydroxide .4 
zinc sulfate .5 
arsenic trioxide .6 
 Example:
An aqueous solution of ferrous sulfate was prepared by adding 41.5 g of
FeSO4 to enough water to make 1000 ml of solution at 18°C. The
density of the solution is 1.0375. Calculate:
a) The molarity.

b) The normality.

c) The molality.

d) The mole fraction and mole percent for both solute and solvent.

e) The percentage by weight of FeSO 4.

Answer:
a) Molarity = moles of FeSO4/Liters of solution
= (41.5/151.9)/ 1 L = 0.2732 M.
b) Normality = (41.5/ 75.95)/ 1L= 0.5464 N
Equivalent weight= 151.9/2= 75.95 g/Eq
c) Molality = moles of FeSO4/ kg of solvent
= 0.2732/ 0.996= 0.2743 m Grams of solution = volume * density
g 1037.5 =1.0375 * 1000 =
=Grams of solvent = 1037.5- 41.5
g 996
 :Given 
Wt Solute = 41.5g 
Dsol’n = 1.0375g/mL 
Vsol’n = 1L 
FeSO4 = 152 g/mole 
HOH = 18 g/mole 
 Molarity
MW=g/mole 
n Solute = 0.27 mole
Mole,n=g/MW 
n (solvent) = g/MW n solute=41.5g/152g/mole 
g/18 g/mole 996= mole 0.27= 
mole 55.33= M=#n/L sol’n 
0.27mole/1L= 
mole/L 27 .0 = 
M 0.27= 
 Molality
;Given m=#n/kg of solvent 
Dsol’n = 1.0375 g/mL
D=M/V mole/0.996kg 0.27= 

Msol’n=DV 0.27mole/kg= 
1.0375g/mL x 1000ml=
m 0.27= 
Gsol’n=1,037.50g
G sol’n=G solute+ G solvent
Gsol’n – Gsolute = G solvent
1,037.5g – 41.5 g = Gsolvent
996g/1000g=
Kg 0.996=
 Normality
Equivalent weight= 152/2= N=# EqWt/L sol’n 
76 g/Eq 1/)41.5g/76g(= 
Eq/L 0.55= 
N 0.55= 
 Mole Fraction (X) SOLUTE
X (FeSO4) = n (FeSO4)/{n (FeSO4) + n (HOH)} 
}55.33 + 0.27{ / 0.27= 
0.0049= 
MOLE FRACTION % 
X 100 0.0049 
0.49% = 
 Mole Fraction (X) SOLVENT
X (HOH) = n (HOH)/{n (solute) + n (solvent)} 
)0.27 + 55.33( / 55.33= 
0.9951= 
MOLE FRACTION% 
x 100 0.9951= 
99.51% = 
 FeSO4%
e) Percentage by weight of FeSO4= (g of
FeSO4/ g of solution) *100
= (41.5/ 1037.5) *100 = 4.00 %
 Compute
Problem #13: An car antifreeze mixture is made by mixing equal 
volumes of ethylene glycol (d = 1.114 g/mL, molar mass 62.07 g/mol)
and water (d = 1.000 g/mL) at 20.0 °C. The density of the solution is
.1.070 g/mL
:Express the concentration of ethylene glycol as 

volume percent )a( 

mass percent )b( 

molarity )c( 

molality )d( 

mole fraction )e( 

mole fraction% )f( 

Normality )g( 
 Example…….cont.:

d) Mole fraction and mole percent:

Moles of water = n1= 996/18.02= 55.27 moles.
Moles of FeSO4 = n2 = 0.2732 moles.

Mole fraction of water = X1 = 55.27/ (55.27 + 0.2732) = 0.9951

Mole percent of water = 0.9951 * 100%= 99.51%.

Mole fraction of FeSO4= X2= 0.2732/ (55.27 + 0.2732) = 0.0049

Mole percent of FeSO4= 0.49%

e) Percentage by weight of FeSO4= (g of FeSO4/ g of solution) *100

= (41.5/ 1037.5) *100 = 4 %
 Solution properties
 Solution properties may be classified as extensive properties ,
depending on the quantity of the matter in the system (e.g. mass and
volume) and intensive properties, which are independent of the
amount of substances in the system (e.g. temperature, pressure,
density, surface tension, and viscosity of pure liquids).

 Solution properties can also be classified as additive, constitutive

and colligative.

 Additive properties are derived from the sum of the properties of the
individual atoms or functional groups within the molecule e.g. mass

 Constitutive properties are dependent on the structural arrangement

of the atoms within the molecule e.g. optical rotation.

 Colligative properties will be discussed soon later.

 Ideal solutions
 Ideal solutions are formed by mixing substances with similar
properties.

 Ideality in solution means complete uniformity of attractive

forces (i.e. cohesive forces between A molecules are similar to
cohesive forces between B molecules; both of which are
similar to the adhesive forces between A and B molecules).

 Ideal solution is the solution in which there is no change in the

properties of the components, other than dilution, when they
are mixed to form the solution.

 In ideal solution, no heat is evolved or absorbed during the

mixing process, and the final volume of the solution represents
an additive property of the individual constituents. No
shrinkage or expansion occurs when substances are mixed
together (e.g. a solution of methanol and ethanol).
 Escaping Tendency
 When two bodies are in contact with each other and one
is heated to a higher temperature than the other, heat
will flow from the hotter to the colder body until the
bodies are in thermal equilibrium. This process is termed
the escaping tendency.

 The hotter body has a greater escaping tendency until

the temperature of both bodies is the same.

 Temperature is a quantitative measure of escaping

tendency of heat.
 Escaping Tendency

 Free energy is a quantitative measure of escaping tendencies

of substances undergoing physical and chemical
transformations – for a pure substance, it is the molar free
energy, for a solution, it is the partial molar free energy.
 Free energy of a mole of ice is greater than that of a liquid water
at 1 atm above 0ºC.
G  Gliq  Gice  0
 Above 0ºC, The escaping tendency of ice is greater than that of
liquid water, so ice is converted to water.
 At 0ºC, the escaping tendencies of ice and water are the same,
G = 0.
 Raoult’s Law

 Raoult’s Law applies for solvents while Henry’s law

applies for solutes.

 Activity, “effective concentration”, is a term used to

describe departure of the behavior of a solution from
ideality. In an ideal solution or in a real solution at infinite
dilution there is no interactions between components and
the activity equals the concentration (activity =
concentration).
 Raoult’s Law
 The activity, in general, is less than the actual or
stoichiometric concentration of the solute as
interactions occur between the components which
reduce the effective concentration of the solute.

 Non-ideality in real solutions at high concentrations

causes a divergence between the values of activity and
concentration. The ratio of the activity to the
concentration is called the activity coefficient, .

activity

concentration
 Raoult’s Law
 Depending on the units used to express the
concentration we can have either a molal activity
coefficient, m, a molar activity coefficient, c, or if
mole fractions are used, a rational activity
coefficient, x.

a   mm a   cc a  X X
where m is the molality, c is the molar
concentration, x is the mole fraction.
 Raoult’s Law
 The activity coefficient is a proportionality constant relating
activity to concentration.

 The activity coefficient usually decreases and assumes

different values as the concentration increases.

 Differences among the three activity coefficients may be

disregarded in dilute solutions in which c  m 0.01.

 The concept of activity and activity coefficient may be

applied to nonelectrolytes, weak as well as strong
electrolytes.
 Raoult’s Law- Ideal solutions
 The vapor pressure of a solution is a quantitative expression of
escaping tendency.

 Raoult’s law: In an ideal solution, the partial vapor pressure of

each volatile constituent is equal to the vapor pressure of the
pure constituent multiplied by its mole fraction in the solution.

Pt = P1ºX1 + P2ºX2

where P1ºX1 and P2ºX2 are the partial vapor pressures of the pure
components when the mole fractions are X1 and X2. P1º and
P2º are the vapor pressure of the pure components.
 Raoult’s Law- Ideal solutions
 So in ideal solutions, when liquid A is mixed with
liquid B, the vapor pressure of A is reduced by
dilution with B in a manner depending on the
mole fractions of A and B present in the final
solution. This will diminish the escaping
tendency of each constituent , leading to a
reduction in the rate of escape of the molecules
of A and B from the surface of the liquid.
 The activities and activity coefficients of solvents on the
assumption of ideal-gas behavior of the vapor

Solvent toluene Solvent benzene

(solute benzene, 20C) (solute toluene, 20C)

Act.coeff Activity Mole Act.coeff Activity Mole

 a fraction  a fraction
X X
1.00 1.00 1.00 1.00 1.00 1.00
1.01 0.78 0.77 0.97 0.65 0.67
1.07 0.55 0.57 0.98 0.54 0.55
1.04 0.47 0.45 1.07 0.46 0.43
The vapor pressures of the components and the total vapor pressures
for the nearly ideal solution benzene-toluene at 20ºC
Raoult’s Law- Ideal solutions

Total vapor pressure

PB°= 268

PA°= 236
Vapor pressure (mm Hg)

PB°XB
PA°XA

Ethylen
Benzene Mole fraction of Ethylen
XB= 1 Chloride
Chloride XA= 1
 Real (nonideal) solutions
 Many examples of solution pairs are known in which
the “cohesive” attraction of A for A exceeds the
“adhesive” attraction existing between A and B.
Similarly, the attractive forces between A and B may
be greater than those between A and A or B and B.
This may occur even though the liquids are miscible
in all proportions. Such mixtures are real or
nonideal.
 Real (nonideal) solutions
Negative deviation:

When “adhesive” attractions between molecules of

different species exceed the “cohesive” attractions
between like molecules, the vapor pressure of the
solution is less than expected from Raoult’s ideal
solution law, and negative deviation occurs.

Pt  P1ºX1 + P2 ºX2 
a1X1 , a2  X2  Pt = P1ºa1 +P2ºa2

Example: chlorofrom and acetone – due to formation of

hydrogen bonds thus reducing the escaping tendency
of each other.

Cl3C-H……O=C(CH3)2
The activities and activity coefficients of solvents showing negative
deviation from Raoult’s law

Solvent chloroform (CHCl3) Solvent acetone

(solute acetone, 35C) (solute CHCl3, 35C)

 a X  a X
1.00 1.00 1.00 1.00 1.00 1.00
0.99 0.91 0.92 1.00 0.94 0.94
0.94 0.76 0.81 0.99 0.87 0.88
0.83 0.55 0.66 0.96 0.70 0.73
0.83 0.48 0.58 0.90 0.57 0.63
0.78 0.38 0.49 0.82 0.42 0.51

Note: with dilution, a→c,  →1

Vapor pressure diagram for the system chloroform-acetone at
35C
 Real (nonideal) solutions

Positive deviation:

When interaction between A and B molecules is less than

that of the pure constituents, the presence of B molecules
reduce the interaction of A molecules, and A molecules
reduce B-B interaction  greater escaping tendency of A
and B molecules  partial vapor pressure of the
constituents is greater than that expected from Raoult’s law.

Pt  P1ºX1 + P2ºX2  a1  X1 , a2  X2 
Pt = P1ºa1 +P2ºa2

Examples: benzene and ethyl alcohol, carbon disulfide and

acetone, chloroform and ethyl alcohol, carbon tetrachloride
and methyl alcohol
 The activities and activity coefficients of solvents showing
positive deviation from Raoult’s law

Solvent carbon tetrachloride (CCl4) Solvent methyl alcohol (CH3OH)

(solute CH3OH, 35C) (solute CCl4, 35C)

 a X  a X
1.00 1.00 1.00 1.00 1.00 1.00
1.01 0.99 0.98 1.04 0.95 0.91
1.11 0.97 0.87 1.11 0.88 0.79
1.47 0.94 0.64 1.27 0.84 0.66
1.80 0.92 0.51 1.63 0.80 0.49
2.56 0.87 0.34 2.16 0.78 0.36

Note: dilution of the dimer structure in alcohol → increases the vapor

pressure of the alcohol
Vapor pressure diagram for the system carbon tetrachloride (CCl4) – methyl
alcohol (CH3OH) at 35C
 Real (nonideal) solutions

 In real solutions, Raoult’s law does NOT apply over the

entire concentration range. It can only be applicable for
a substance with high concentration (i.e. solvents in
real solutions). For the previous figures (slides 18 and
20), you can observe that the actual vapor pressure
curve of subtances approach the ideal curve defined by
Raoult’s law at high concentrations (being solvent).
 Raoult’s Law

 If you have the fourth edition of the book, solve

problems 5-9 and 5-10 page 122, and problems
6-27 and 6-28 page 142.

 If you have the fifth edition of the book, solve

problems 5-9 and 510 page 693, and problems
6-27 page 697 and 6-28 page 698.
 Colligative properties
 Colligative properties depend mainly on the number of
particles in a solution.

 The value of the colligative properties are approximately

the same for equal concentrations of different
nonelectrolytes in solution regardless of the species or
chemical nature of the constituents.

 The colligative properties of solutions are: osmotic

pressure, vapor pressure lowering, freezing point
depression, and boiling point elevation.

 In considering the colligative properties of solid-in-liquid

solutions, it is assumed that the solute is nonvolatile and
that the pressure of the vapor above the solution is
provided entirely by the solvent.
 Colligative properties

 The colligative properties of solutions of nonelectrolytes

are fairly regular. A 0.1 M solution of a nonelectroyte
produces approximately the same colligative properties
as any other nonelectrolyte solution of equal
concentrations.

 Solutions of electrolytes show apparent “anomalous”

colligative properties, that is, they produce a
considerably greater freezing point depression and
boiling point elevation than do nonelectrolytes of the
same concentration.
 Lowering of Vapor Pressure, P
 When a nonvolatile solute is combined with a
volatile solvent, the vapor above the solution is
provided solely by the solvent. The solute reduces
the escaping tendency of the solvent, and, on the
basis of Raoult’s law, the vapor pressure is lowered
proportional to the relative number (rather than the
weight concentration) of the solute molecules.

 Since the solute is nonvolatile, the vapor pressure of

the solvent P1 is identical to the total pressure of the
solution P.

 It is more convenient to express the vapor pressure

of the solution in terms of the solvent.
 Lowering of Vapor Pressure, P
 X1 is the solvent mole fraction and X2 is the solute mole
fraction
X1 + X2 = 1 i.e. X1 = 1- X2
so P = P1º (1 – X2)  P1º – P = P1ºX2

P1  P P n2
thus 
   X2 
P1 P1 n2  n1
Where ΔP is the lowering of the vapor pressure and
ΔP/P1° is the relative vapor pressure lowering.

 As ΔP/P1° depends only on the number of solute

molecules, it is considered as a colligative property.
 Lowering of Vapor Pressure, P
 For dilute solutions (n2n1) so

P n2 w2 / M 2

 X 2  
P1 n1 w1 / M 1
 When water is the solvent, 1000g = 1L

P w2 / M 2 n2

 X2  
P1 1000 / 18.02 55.5

Thus P

 X 2  0.018m
where m isPthe
1 solute molatity
(Why in molality, not in molarity or normality?)
 Lowering of Vapor Pressure, P
Q) Calculate the relative vapor pressure lowering at 20°C for a
solution containing 171.2 g of sucrose in 1000g of water. The
molecular weight of sucrose is 342.3 and the molecular weight of
water is 18.02.

Moles of sucrose (n2) = 171.2/342.3= 0.5 mol

Moles of water (n1)= 1000/18.02= 55.5 mol
ΔP/P1°= X2= 0.5/ (0.5+55.5)= 0.0089.

Q) For the above question, providing that the vapor pressure of

water at 20°C is 17.54 mm Hg. Calculate the vapor pressure when
added 171.2 g of sucrose (0.5 mol).

ΔP/P1°= (P1°- P)/ P1°= (17.54-P)/17.54=0.0089

P= 17.38 mmHg
 Elevation of the Boiling Point
 The boiling point of a solution of a nonvolatile solute is higher
than that of the pure solvent, owing to the fact that the solute
lowers the vapor pressure of the solvent.

Figure – Boiling point elevation of the solvent due to addition

of a solute (not to scale)
The elevation of the boiling point can be written as T – Tº = Tb
 Van Hoff Factor / Dissociation
factor/ i
Na Cl dissociates at 80% 

ZnCl2 dissociates at 80% Na = 80 

Zn = 80 Cl = 80 
Cl = 80 NaCl = 20 
Cl = 80
ZnCl2 = 20 100 / 180 

260/100 = 1.8 
2.6= i= 1 + a 

0.8 + 1 = 
i=1 + α
)2( 0.8 + 1 = 1.8 

1.6 + 1 =
2.6 =
 𝚫Tb = Kb m i 
Kb = Ebullioscopic constant 
C/m 0.55 
m=molal 
𝚫Tf = Kf m i 
Kf = Cryoscopic constant 
C/m 1.86 
 Elevation of the Boiling Point
 An exact equation to calculate Tb (boiling point elevation)
2
RTb
Tb  X 2  kX 2
H v

where Hv is the latent heat of vaporization of the solvent, Tb is

the boiling point of the solvent, R is the gas constant, X2 is the
mole fraction of the solute
 A less exact equation (more2 commonly used) is
RTb M 1
Tb  m  Kbm
1000H v

where M1 is the molecular weight of the solvent, m is the molal

concentration of the solute (mol.kg-1), Kb is the molal elevation
constant or the ebullioscopic constant (deg.kg.mol-1)
 What is the molecular  Given: wt cmpd – 16g 

mass of an organic Wt CCl4 = 225g = 0.225kg 

Tb = 85.36 C 
compound if 16.00 g
Kb = 5.03 C/m 
of the compound is
Tb = 76.72 C 
dissolved in 225.0 g of
carbon tetrachloride
raises the boiling point
?to 85.36 °C
 𝚫Tb = Kb m i 
C= (5.03 kg 76.72 – 85.36 
C/mole)(x/0.225kg)(1)
C = (5.03 C/mole) (x/0.225) 8.64 
8.64C x 0.225 = (5.03 C/mole) x 
)5.03 C/mole( )C/mole 5.03( 
X = 0.39 mole 
 MW = g/mole 
g/0.39 mole 16 = 
g/mole 41.03 
 When 0.258 g of a  :Given 

Wt benzoic = 0.258g 
molecular compound, Wt Benzene = 40g = 0.040kg 
benzoic acid, was Tf solution = 5.23 C 

dissolved in 40.0 g of Kf benzene = 5.12 C/m 

benzene, the freezing Tf = 5.5 C 

point of the solution

was lowered to 5.23 °C.
What is the molecular
weight of the benzoic
?acid
 𝚫Tf = Kf m i 
C – 5.23 C = (5.12 kgC/mole)(x/0.040kg) 5.5 
(1)
C x 0.040 = (5.12 C/mole) x 0.27 
X = 0.0021 mole 
MW = g/mole 
0.258g/0.0021 mole = 
g/mole 122.86 = 
 A compound contains 42.9% C, 2.4% H, 
16.6% N, and 38.1% O by mass. The addition
of 3.16 g of this compound to 75.0 mL of
cyclohexane (d= 0.779 g/mL) gives a solution
with a freezing point of 0.0 °C. The normal
freezing point of cyclohexane is 6.5 °C and its
freezing point depression constant is 20.2
°C/m. What is the molecular formula of the
?solute
Determine the mass of cyclohexane .1 
D= m/v 
M = DV 
)75ml()0.779g/ml( 
58.425g = 
Determine the mole of the .2
cmpd
𝚫Tf = Kf m i 
C= (20.2 kg C/mole)(x/0.058425 kg) 1 6.5 
C x 0.058425 = (20.2 C/mole) x 6.5 
X = 0.0188 mole 
Determine the MW
MW = g/mole 
3.16g/ 0.0188mole = 
g/mole 168.09 = 

168.09/84 
2
C = 42.9 g/12 g/mole = 3.575 mole/1.19 mole= 3 

H = 2.4 g/1 g/mole = 2.4 mole/1.19 mole = 2 

N = 16.6 g / 14 g/mole = 1.19 mole/1.19 mole = 1 

O = 38.1g/16 g/mole = 2.38 mole/1.19mole = 2 

C3 H2 N1 O2 

C 3 x 12 = 36 

H=2x1=2 

N 1x 14 = 14 

O = 2 x 16 = 32 

84 
C3x2 H2x2 N1 x2 O2x2 
C6 H4 N2 O4 
C6 H4 O4 N2 
 g of an organic solid is dissolved in 100.0 g of benzene. 5.00 
The boiling temperature of this solution is 82.42 °C. The
organic compound is 15.72% nitrogen, 7.92% hydrogen,
35.92% oxygen and the remainder is carbon. The boiling
.temperature of pure benzene is 80.1 °C; Kb = 2.53 °C-kg/mol
.a. Determine the molecular weight of the organic solid 

b. Determine the molecular formula of the solid 

c. Determine the mole fraction of the organic solid in the 

solution
d. If the density of this solution is 0.8989 g/mL , calculate the 
molarity of the solution
A solution that contain 55.0 g of ascorbic acid 
(vitamin C) in 250. g of water freezes at -2.34
°C. Calculate the molar mass (in g/mol) of the
.solute
 Elevation of the Boiling Point

 Kb (ebullioscopic constant) has a characteristic value

for each solvent; Kb for water is 0.51 deg.kg/mole.

 Kb may be considered as the boiling point elevation

for an ideal 1m solution.

 Stated another way, Kb is the ratio of the boiling point

elevation to the molal concentration in an extremely
dilute solution in which the system is approximately
ideal.
 Elevation of the Boiling Point

Figure - the influence of concentration on the

ebulioscopic constant.
 Depression of Freezing Point
 The normal freezing point or melting point of a pure
compound is the temperature at which the solid and the
liquid phases are in equilibrium under a pressure of
1atm. Equilibrium here means that the tendency for the
solid to pass into the liquid is the same as the tendency
for the reverse process to occur, since both the liquid
and the solid have the same escaping tendency.

 The T value for water saturated with air at this pressure

is arbitrary assigned a temperature of 0ºC – see figure.

 The triple point of air-free water, at which solid, liquid,

and vapor are in equilibrium, lies at a pressure of 4.58
mmHg and a temperature of 0.0098ºC.
 Depression of Freezing Point

Figure – Depression of the freezing point of the solvent,

water, by a solute ( not to scale).
 Depression of Freezing Point
 The more concentrated is the solution, the farther apart are
the solvent and the solution curves and the greater is the
freezing point depression (Tf).

 Tf is proportional to the molal concentration of the solute and

can be determined as follows:
Tf = Kfmi or
1000w2 or
RT f 2 M 1
T f  K f T f  m
w1M 2 1000 H f

where Tf is the freezing point depression, Hf is molal heat

of fusion, Tf is the freezing point of the solvent and Kf is the
molal depression constant or the cryoscopic constant, which
depends on the physical and chemical properties of the
solvent, Kf for water is 1.86 deg.kg/mole.
 Depression of Freezing Point

 The freezing point depression of a solvent is a function only of

the number of particles in the solution, and for this reason it is
referred to as a colligative property.

 The depression of the freezing point, like the boiling point

elevation, is a direct result of the lowering of the vapor pressure
of the solvent.

 Kf may be determined experimentally by measuring Tf/m at

several molal concentrations and extrapolating to zero
concentration – i.e. Kf is the intercept. Electrolytes don’t follow
this relationship. The equation is
T f
 cons tan t  K f
m
 Depression of Freezing Point

Figure – The influence of concentration on the cryoscopic constant

for water
 Depression of Freezing Point
 Citric acid shows abnormal behavior as seen in the
previous figure – This abnormal behavior is to be
expected when dealing with electrolytes.

 Freezing point depression can also be calculated from

the following equation:

RT f T
T f  X2
H f

where Tf is the freezing point of the solvent, T is the

freezing point of the solution, X2 is the mole fraction of
the solute, R is the gas constant and Hf is the heat of
fusion of the solvent.
 Osmotic Pressure 
 Escaping tendency can be measured in terms of
vapor pressure or the closely related colligative
property, osmotic pressure.

 If a solution is confined in a membrane only

permeable to the solvent molecules
(semipermeable), osmosis occurs.

 Osmosis is defined as the passage of the solvent

into a solution through a semi-permeable
membrane.
 Osmotic Pressure 

Apparatus for demonstrating osmosis.

 Osmotic Pressure 
 Van’t Hoff suggested that there is an apparent analogy
between solutions and gases and that the osmotic
pressure in a dilute solution is equal to the pressure that
the solute would exert if it were a gas occupying the
same volume. The equation is

V  nRT
in which  is the osmotic pressure in atm, V is the
volume of the solution in liters, n is the number of moles
of the solute, R is the gas constant equal to 0.082L atm
mole-1 deg -1, and T is the absolute temperature.
 Osmotic Pressure 
 The van’t Hoff equation can be rewritten as
n
  RT  cRT
V
in which c is the concentration of the solute in
moles per liter (molarity).

 Morse has shown that when the concentration is

expressed in molality rather than molarity, the
results compare more with the experimental
findings. The Morse equation is
  RTm
 Osmotic Pressure 
 Thermodynamic osmotic pressure equation is a more
exact expression for osmotic pressure. It applies to
concentrated as well as dilute solutions, provided that
the vapor follows the ideal gas law
RT P
 ln
V1 P
in which  is the osmotic pressure in atm, V1 is the
volume of 1 mole of solvent (partial molar volume) in
liters, Pº is the vapor pressure of pure solvent in atm,
and p is the vapor pressure of the solution in atm, R is
the gas constant equal to 0.082L atm mole-1 deg -1, and
T is the absolute temperature.