Simple Mixtures

Colligative Properties

Chapter 7 : Slide 1
 Colligative Properties
Colligative properties of a solution are properties which depend only upon
the number of moles of a solute, and not upon its specific nature.
• Vapor Pressure Lowering
When an involatile (e.g. solid) solute is dissolved in a solvent,
the vapor pressure drops below that of the pure solvent.
• Boiling Point Elevation
When an involatile (e.g. solid) solute is dissolved in a solvent, the
boiling point of the solution is higher than that of the pure solvent.
• Freezing Point Depression
When a solute (usually a solid) is dissolved in a solvent, the
freezing point of the solution is lower than that of the pure solvent.
• Osmotic Pressure
Solvent tends to flow from a pure solvent chamber into a solution
chamber until a sufficient pressure (the “Osmotic Pressure”) has
developed to stop further flow.
Chapter 6: Slide 2
 Colligative Properties

All four colligative properties are independent of the nature of the

solute (B), but stem from the fact that the solute will lower the
chemical potential of the solvent (A):

Freezing Point Boiling Point

Depression Elevation

Chapter 7 : Slide 3
Vapor Pressure Lowering
pA* pB* ptot = pA + pB

pA = xApA* xA = Mole Fraction of A in mixture

pB = xBpB* xB = Mole Fraction of B in mixture

Raoult’s Law: ptot = xApA + xBpB

* *

In the special (but important) case that the solute, B, is non-volatile, it's
pure vapor pressure will be: pB*  0
In this case, Raoult's Law reduces to: ptot = pA = xApA*
For xA < 1, pA < pA*
Chapter 7 : Slide 4
 Vapor Pressure

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© 2009, Prentice-Hall, Inc.

 Raoult’s Law
PA = XAPA
where
– XA is the mole fraction of compound A, and
– PA is the normal vapor pressure of A at that
temperature.

NOTE: This is one of those times when you want

to make sure you have the vapor pressure of the
solvent. © 2009, Prentice-Hall, Inc.
 Vapor Pressure:
• Raoult’s Law: Psolution = XsolventPoH2O

12g Sucrose (C12H22O11)is dissolved in 250.0g water at

90 °C.
What is the vapor pressure of water over this solution?
(PoH2O = 525.8 mmHg- from data table)

• Ans. 524 mmHg

 Application of Raoult's Law: Determining the Molar Mass
of a compound.

Exer. 5.5b: The vapor pressure of 2-propanol (M=60) is 50.0 kPa at 339 oC,
but fell to 49.6 kPa when 8.7 g of an involatile organic compound was dissolved
in 250 g of 2-propanol.

Calculate the Molar Mass of the unknown compound.

xprop = 0.992
nX = 0.034 mol
MX = 260 g/mol

Chapter 7 : Slide 8
Boiling Point Elevation
Pure Solvent Solution

T = Tbo T = Tbo
p = pA* = 1 atm. P = xApA* < 1 atm.
Will no longer boil at Tbo. Must raise
temperature until P rises back to 1 atm.
As shown in the text (Justification 5.1, the change in the boiling point, Tb ,
can be expressed as a function of the solute molality, mB .
Tb = Tb - Tbo = KbmB

Note: The text notation for solute molality is: b

Freezing Point Depression

Pure Solvent Solution

T = Tfo T = Tfo
Rate(“pop off”) = Rate(“condense”) Rate(“pop off”) > Rate(“condense”)
Will no longer freeze at Tfo. Must lower
temperature until the two rates are equal.
As discussed in the text, the change in the freezing point, Tf ,
can be expressed as a function of the solute molality, mB .

Tf = Tfo - Tf = KfmB

Note: The text notation for solute molality is: b

 Tb = Tb - Tbo = KbmB
Tf = Tfo - Tf = KfmB

It can be shown that the Boiling Point Elevation Constant (aka the Ebullioscopic
constant) and the Freezing Point Depression Constant (Cryscopic constant) are
given by:

and

MA is the solvent Molar Mass

Tbo and Tfo are the pure solvent boiling and freezing temperatures
vapHo and fusHo are the solvent enthalpies of vaporization and fusion
Note that Kb and Kf depend solely upon solvent properties, and independent of
the particular solute.
Although Kf and Kb can be calculated from the above formulae, the tabulated
values in the literature are the empirical values, taken from experimental
determination using solutes of known Molar Mass.
Chapter 7 : Slide 11
 Solvent Kf Kb

H2O 1.86 K/m 0.51 K/m

Benzene 5.12 2.13
Phenol 7.27 3.04
CCl4 30 4.95

Note that Kf > Kb. This is because fusHo << vapHo

and

Generally, the tabulated constants, Kf and Kb , are the empirical values

determined from measurements with solutes of known Molar Mass.

Chapter 7 : Slide 12
Applications of freezing point depression and boiling point
elevation measurements.
1. Determination of solute Molar Mass
2. Determination of fractional dissociation and equilibrium constants
3. Determination of solute "activity coefficients" (coming up)

Exer. 5.6b: The addition of 5.0 g of an unknown compound to 250 g of

Napthalene lowered the freezing point of the solvent by 0.78 oC

Calculate the Molar Mass of the unknown compound.

Kf (Nap) = 6.94 K/m
mX = 0.112 m = 0.112 mol/kg
kg Nap = 0.25 kg
nX = 0.028 mol
MX = 180 g/mol

Chapter 7 : Slide 13
 Osmotic Pressure

Wine bladder

Lake

H 2O

Chapter 7 : Slide 14
 H2O

Semipermeable
Membrane

 = dgh
= Osmotic Pressure
Static Osmometry:
Allow the two chambers
to equilibrate.

Semipermeable
Membrane
Chapter 6: Slide 15 Chapter 7 : Slide 15
 P P+

H2O

Semipermeable
Membrane

Dynamic Osmometry: Apply pressure, , to prevent movement

of solvent between chambers.

Chapter 7 : Slide 16
 It can be
shown that:  V = nBRT

 = Osmotic Pressure
V = Volume of solution
nB = Moles of Solute
R = Gas Constant
T = Temperature (in K)

Alternate form:  = (nB/V) RT

 = [B]RT

[B] = Solute Molarity

Chapter 7 : Slide 17
A Sensitivity Comparison
Let's say that a sugar solution is prepared by dissolving 1 g of sucrose
(M = 342) in 1 L (1 kg) of water.
The Molarity (molality) of the solution is:

From Kf = 1.86 K/m, one has Tf = -0.005 oC

From Kb = 0.51 K/m, one has Tb = 100.0015 oC
Let's calculate  (25 oC)

In contrast to freezing point depression, and boiling point elevation, which

are too small to be measured experimentally, the osmotic pressure can be
measured very accurately.
Chapter 7 : Slide 18
Application: Determination of Molar Mass from Osmotic Pressure
We will show a straightforward method for determining Molar Masses from
measured values of . The method is very similar to that used to calculate
Molar Mass from Freezing Point Depression or Boiling Point Elevation.

Afterwards, I will comment on the method presented in the text, which

is useful if one wishes very accurate determinations, but is not straightforward.
Example: When 2.0 g of Hemoglobin (Hb) is dissolved in 100 mL
of solution, the osmotic pressure is 5.72 torr at 25 oC.
Calculate the Molar Mass of Hemoglobin. 1 kPa = 7.50 torr
R = 8.31 kPa-L/mol-K
Procedure:
1. Calculate the Molarity of the unknown, [X] from  = [X]RT
2. Determine the number of moles, nX , using [X] and the solution volume
3. Determine the Molar Mass from: MX =massX/nX

Chapter 7 : Slide 19
 Example: When 2.0 g of Hemoglobin (Hb) is dissolved in 100 mL
of solution, the osmotic pressure is 5.72 torr at 25 oC.
Calculate the Molar Mass of Hemoglobin. 1 kPa = 7.50 torr
Procedure: R = 8.31 kPa-L/mol-K
1. Calculate the Molarity of the unknown, [X] from  = [X]RT

2. Determine the number of moles, nX , using [X] and the solution volume

3. Determine the Molar Mass from: MX =massX/nX

Note: The Boiling Point elevation and Freezing Point depression of the above
solution would be immeasurably small. Therefore, these techniques are useless
to determine Molar Masses of polymers. Chapter 7 : Slide 20
Homework: When 3.0 g of an unknown compound is placed in 250 mL of
solution at 30 oC, the osmotic pressure is 62.4 kPa.
Calculate the Molar Mass of the unknown compound.
R = 8.31 kPa-L/mol-K
[X] = 2.48x10-2 mol/L
nX = 6.20x10-3 mol
MX = 480 g/mol

Note: The osmotic pressure,  = 62.4 kPa = 470 mm Hg  0.50 meters,

can be measured to 0.1 % accuracy very easily.

In contrast, the freezing point depression (in aqueous solution) would be

~0.05 oC, which could only be measured to approximately 10-20% accuracy.
Note, once again, that Osmotic Pressure measurements are much more
sensitive than the other colligative properties.

Chapter 7 : Slide 21
Very Accurate Determination of Molar Masses from 

Actually, the formula,  = [B]RT, is only accurate in dilute solution.

In more concentrated solutions, one has:

It is shown in the text that, writing  = gh (hydrostatic

pressure), and c = mass/Volume, one can derive the equation:

Then, an accurate value for MX can be obtained from the intercept of a plot
of h/c vs. c

Chapter 7 : Slide 22
 Real Solutions: Activities
Ideal Solutions
Earlier in the chapter, we showed that the solvent (A) and solute (B)
chemical potentials are given by:

Solvent:

Solute:

Real Solutions
In solutions which are not ideal, the relatively simple formulae for the solvent
and solute chemical potentials can be retained by replacing the mole fractions
by activities (ai):
Solvent:

Solute:
Chapter 7 : Slide 23
 Real Solutions: Activities
Real Solutions
In solutions which are not ideal, the relatively simple formulae for the solvent
and solute chemical potentials can be retained by replacing the mole fractions
by activities (ai):
Solvent:

Solute:

The activities can be related to the mole fractions by:

aA = A xA and aB = B xB.

A and B are the activity coefficients, and can be calculated from

thermodynamic measurements. Their deviation from i =1 characterizes
the extent of non-ideality in a system.

Chapter 7 : Slide 24
Solute Activities in terms of molalities - FYI
In a dilute solution, it is more common to characterize solutes by their
molality, rather than mole fraction in solution.
It is straightforward to show that, in a dilute solution, the molality, mB,**
and mole fraction, xB , are directly proportional:

(nB << nA in dilute solution)

If we assume an amount of solution containing 1 kg = 1000 g of solvent,

then: nB = mB and nA = 1000/MA (solvent Molar Mass).

**We note again that we use mB , rather than bB (text) to indicate molality.
Chapter 7 : Slide 25
The solute chemical potential of an ideal solution, written in terms of molality
rather than mole fraction, is:

B+ is different from the reference state, Bo ,

when using mole fractions.

For a non-ideal solute, we can then replace mB by the activity, aB= BmB

Chapter 7 : Slide 26
Activity Coefficients from Colligative Property Measurements

Earlier we discussed that the freezing point depression and boiling point elevation
of a solution (assumed ideal) are given by:

If the solution is non-ideal, the solute molality, mB , is replaced by its

activity, aB

Thus, the activity coefficient, B , can be determined by a comparison of

the measured colligative property with the value expected for an ideal solution:

Chapter 7 : Slide 27
Example: When 25 g of Napthalene (C10H8 , M = 128) is placed in
500 g of benzene (Kf = 5.12 oC/m. Tfo = 5.5 oC ), the freezing point of the
solution is 3.9 oC.
What is the activity coefficient of napthalene in this solution?

Chapter 7 : Slide 28
Colligative Properties of Electrolytes

Since these properties depend on the number of particles

dissolved, solutions of electrolytes (which dissociate in
solution) should show greater changes than those of
nonelectrolytes.

© 2009, Prentice-Hall, Inc.

 van’t Hoff Factor

• We modify the
previous equations by
multiplying by the
van’t Hoff factor, i.

Tf = Kf  m  i

© 2009, Prentice-Hall, Inc.

 van’t Hoff Factor

• Reassociation is more
likely at higher
concentration.
• Therefore, the number
of particles present is
concentration-
dependent.

© 2009, Prentice-Hall, Inc.

 Role of Electrolytes on Colligative
Properties:
• Van’t Hoff Factor: ΔTfp = Kfpmsolutei

• A 0.0711m aqueous solution of Sodium sulfate freezes at -0.32C.

What is the actual value (i) of the van’t Hoff factor? Kfp = 1.86
°C/m

Ans: i = 2.42