COLLIGATIVE PROPERTIES

OBJECTIVES OF THE DAY:

1. Identify the Colligative properties of solutions
2. Describe the different Colligative properties of solution
COLLIGATIVE PROPERTIES
› Why add salt to cooking pasta?

› Why do we put salt on roads in the winter?

› Solute particles can affect the physical properties of a solvent.

COLLIGATIVE PROPERTIES
How are solutions different than pure liquids?
What happens when you add a solute to a liquid?
What is the freezing point of water? What is the boiling
point of water? What happens to the freezing point and
boiling point if salt or sugar is added to water?
COLLIGATIVE PROPERTIES
› In addition the vapor pressure of the liquid changes. Also,
something called the osmotic pressure of the liquid changes
and that is related to the process of osmosis.
COLLIGATIVE PROPERTIES OF SOLUTIONS
➢The freezing point, boiling point, vapor pressure , and osmotic
pressure are all related to one another, because the magnitude of
the change depends on the concentration of solute particles.
➢It is also dependent on the nature of the solvent. These
properties are not so much dependent on the nature of, or the
chemical properties of the solute that is dissolved, but simply on
the number of solute particles present, whether they are ions or
molecules doesn't make too much difference except in the
number.
➢It is the concentration that make the difference, not the nature.
Of course, that concentration does have to take into account
whether that solute dissociates and if so, how much.
➢Because of this they are all grouped together as a set of
properties, and they are called the colligative properties.
COLLIGATIVE PROPERTIES

Colligative Property
➢ A property of a solution that depends ONLY on the number of
the solute particles but not on their identity (whether they are
polar, nonpolar, small, large, etc).
There are four colligative properties to consider:
➢Vapor pressure lowering (Raoult’s Law)
➢Freezing point depression
➢Boiling point elevation
➢Osmotic pressure
COLLIGATIVE PROPERTIES
➢Vapor Pressure Reduction (lowering):
› Vapor Pressure – exists as liquid molecules enter the gas
phase
› A solvent in a closed container reaches a
state of dynamic equilibrium.
› The addition of any nonvolatile solute
(one with no measurable vapor pressure)
to any solvent reduces the vapor pressure
of the solvent
COLLIGATIVE PROPERTIES

Diagram 1 (above left) represents pure water. A tiny fraction of the H2O
molecules will escape into the vapor space, and if the top of the container is
closed, the pressure of water vapor builds up until equilibrium is achieved.
Once this happens, water molecules continue to pass between the liquid and
vapor in both directions, but at equal rates, so the partial pressure of H2O in
the vapor remains constant at a value known as the vapor pressure of
water at the particular temperature.
In the system on the right, a nonvolatile solute such as salt or sugar
replaced a fraction of the water molecules with a substance that has zero or
negligible vapor pressure. This has the effect of diluting the water, reducing
COLLIGATIVE PROPERTIES
➢Nonvolatile solutes reduce the ability of the surface solvent
molecules to escape the liquid. Vapor pressure is reduced.
➢The extent of vapor pressure lowering depends on the
amount of solute.
› Raoult’s Law quantifies the amount of vapor pressure
lowering that is observed.
COLLIGATIVE PROPERTIES
› Raoult’s Law:
PA = XAPOA
where PA = partial pressure of the solvent (A)
vapor above the solution (ie with the solute)

XA = mole fraction of the solvent (A)

PoA = vapor pressure of the pure solvent (A)

COLLIGATIVE PROPERTIES
1. The vapor pressure of water at 20°C is 17.5 torr. Calculate the
vapor pressure of an aqueous solution prepared by adding 36.0
g of glucose (C6H12O6) to 14.4 g of water.
ANSWER: 14.0 torr

2. A solution is made by mixing 12.0 g of C10H8 in 45.0 g of C6H6.

If the vapour pressure of pure C6H6 is 95.3 torr, what is the
vapour pressure of the solution?
ANSWER: 24
ASSIGNMENT
1. Estimate the vapor pressure of a 45 percent (W/W) solution
of ordinary cane sugar (C22O11H22, 342 g mol–1) in water. The
vapor pressure of pure water at this particular temperature is
26.0 torr.
2. The vapor pressure of water at 10° C is 9.2 torr. Estimate the
vapor pressure at this temperature of a solution prepared by
dissolving 1 mole of CaCl2 in 1 L of water.
Vapor Pressure of a Solution with at Non-Volatile
Solute
Solutes that are solids at room temperature are generally
considered non-volatile, meaning that the vapor pressure of the
solute (𝑃𝑜𝑠olute) is equal to zero. When the solute(s) is non-
volatile, then the vapor pressure of the solution arises only due
to the solvent.
Vapor Pressure of a Solution containing Volatile
Solute
In the case where both the solute and solvent are volatile, we
must consider the vapor pressure arising from both
components.

Calculate the mole fractions of the solvent and solute. Since we

cannot assume the vapor pressure of the pure solute is zero, so
determine for the vapor pressure arising from both the solute
and the solvent.
EXAMPLE:
Consider a solution containing 5.00 g of benzene (C6H6) in 50.00 g
toluene (C7H8) at 20 °C. Calculate the total vapor pressure, partial
pressure of benzene and partial pressure of toluene above the solution.
(𝑃 0𝑏enzene 𝑎t 20℃ = 75 𝑚mHg, 𝑃𝑜𝑡oluene 𝑎t 20℃ = 22 𝑚𝑚Hg)
STEPS:
1. Find the molar amount of each component in the mixture. Find the
mole fraction of the solute and solvent.
2. Find partial pressure of the benzene. (mole fraction of benzene in the
solution, multiplied by the vapor pressure of pure benzene).
3. Similarly, the partial pressure of toluene is proportional to the mole
fraction of toluene in the solution.
4. The total vapor pressure of the solution is the sum of the vapor
pressure arising from solute(s) and solvent.
SOLVE THE FOLLOWING:
1. A mixture of isopropanol and water has a vapor pressure of
35 mmHg at 24ºC. What is the mole fraction of each
component of the mixture? (𝑃 0𝑖sopropanol 𝑎t 24℃ =
40.0𝑚𝑚Hg, 𝑃𝑜𝑤ater 𝑎t 24℃ = 22.4 𝑚𝑚Hg).
2. What is the vapor pressure of vodka, which contains 34 %
(m/m) ethanol in water, at 20ºC? (𝑃 0 𝑤ater 𝑎t 20℃ = 17.5
𝑚𝑚Hg, 𝑃𝑜𝑒thanol 𝑎t 20℃ = 44.6 𝑚𝑚Hg)
SOLVE THE FOLLOWING:
3. What is the vapor pressure of a 55% (m/m) urea solution at
22 °C? Urea (CO(NH2)2) is a non-volatile solute and the vapor
pressure of pure water is 19.8 mmHg at 22 °C.
4. What is the mole fraction of solute in a solution that contains
a non-volatile solute if the vapor pressure of the solution is 109
mmHg and the vapor pressure of the pure solvent is 150.
mmHg?
5. Calculate the vapor pressure of a solution containing 92.1 g of
glycerin, C3H5(OH)3, and 184.4 g of ethanol, C2H5OH, at 40 °C.
The vapor pressure of ethanol is 0.178 atm at 40 °C. Glycerin is
essentially nonvolatile at this temperature.
Colligative Properties – BP Elevation
› The addition of a
nonvolatile solute
causes solutions to
have higher boiling
points than the pure
solvent.
◼ Higher temperature
is needed in order
for vapor pressure
to equal 1 atm.
Colligative Properties- BP Elevation
› The change in boiling point is proportional to the number of solute
particles present and can be related to the molality of the solution:

DTb = Kb.m or DTb = Tb (solution) –Tb (sovent)

where DTb = boiling point elevation
Kb = molal boiling point elevation constant
m = molality of solution

The value of Kb depends only on the identity of the solvent

Colligative Properties - BP Elevation
Example: Calculate the boiling point of an aqueous solution
that contains 20.0 mass % ethylene glycol (C2H6O2, a nonvolatile
liquid).
Solute =
Solvent =
Kb (solvent) =
DTb = Kb  m
FREEZING POINT DEPRESSION
› Normal Freezing Point: F.pt. of Substance @ 1atm
› When solute is added, F.pt. < Normal F.pt. F.pt. is depressed
when solute inhibits solvent from escaping.
› A purple dye was dissolved in water, and the solution was
frozen slowly. When a solution freezes, the solvent solidifies as
the pure substance. Thus, pure ice formed along the walls of
the tube, and the dye stayed in solution. The solution became
more concentrated as more and more solvent was frozen out,
and the resulting solution had a lower and lower freezing
point. When equilibrium was reached, pure, colorless ice had
formed along the walls of the tube with concentrated solution
in the center of the tube.
FREEZING POINT DEPRESSION

Freezing pt Depression eqn.

ΔTf = (Tf° -Tf) = m•kf
Where:
ΔTf = f.pt. depression
Tf° = f.pt. of pure solvent
Tf = f.pt. solvent in solution
m = molality ,
kf = f.pt. Constant
Freezing Pt Depression
Example: Calculate the freezing point depression
of a solution that contains 5.15 g of benzene
(C6H6) dissolved in 50.0 g of CCl4.
Given: mass solute =
DTf = Kf  m
mass solvent =
Kf solvent =

Find: DTf
Freezing Pt Depression
Solve the following:
1. What is the freezing point of a solution of 1.25
moles sugar dissolved in 0.750 grams water?
2. 96.5 g of NaCl are added to 650.0g of water.
What is the freezing pt. of this solution?
3. Calculate the freezing point of a solution made from 32.7 g of
propane, C3H8, dissolved in 137.0 g of benzene, C6H6. The freezing
point of benzene is 5.50° C and its Kf is 5.12° C/m.
4. What mass of ethylene glycol C2H6O2, must be added to 4.00 kg
of water to form a solution that freezes at -4.00⁰C?
OSMOSIS
OSMOSIS flow of molecules through
a semi-permeable membrane ;
NET movement of is toward solution
with higher solute concentration;
movement of solvent continues until
osmotic pressure builds up to stop it
OSMOTIC PRESSURE

movement continues until osmotic pressure builds up to stop it

Osmosis
› Some substances form semipermeable membranes, allowing
some smaller particles to pass through, but blocking other larger
particles.
› In biological systems, most semipermeable membranes allow
water to pass through, but solutes are not free to do so.
› If two solutions with identical concentration (isotonic solutions)
are separated by a semipermeable membrane, no net movement
of solvent occurs.
 Osmosis
› Osmosis plays an important role in
living systems:
– Membranes of red blood cells are
semipermeable.
› Placing a red blood cell in a
hypertonic solution (solute
concentration outside the cell is
greater than inside the cell) causes
water to flow out of the cell in a
process called crenation.
Osmosis
› Placing a red blood cell in a hypotonic solution (solute
concentration outside the cell is less than that inside
the cell) causes water to flow into the cell.
– The cell ruptures in a process called hemolysis.
Osmosis
› Other everyday examples of osmosis:

–A cucumber placed in brine solution loses water

and becomes a pickle.

–A limp carrot placed in water becomes firm

because water enters by osmosis.

–Eating large quantities of salty food causes

retention of water and swelling of tissues
(edema).
Osmotic Pressure
› Osmosis is a rate controlled phenomenon.
– The solvent is passing from the dilute solution into the concentrated
solution at a faster rate than in opposite direction, i.e. establishing an
equilibrium.
› The osmotic pressure is the pressure exerted by a column of the solvent in
an osmosis experiment.
 = MRT
where:  = osmotic pressure in atm
M = molar concentration of solution
L atm
R = 0.0821
mol K
T = absolute temperature
Osmotic Pressure
▪ For very dilute aqueous solutions, molarity and molality are
nearly equal.
▪ Mm

 = mRT
for dilute aqueous solutions only
OSMOTIC PRESSURE
1. Seawater contains 3.4 g NaCl per liter. Calculate the osmotic
pressure of seawater at 20°C
2. A 25 mL aqueous solution containing 0.420 g of hemoglobin
has an osmotic pressure of 4.6 torr at 27°C. What is the molar
mass of hemoglobin?
3. A 1.00 g sample of a biological material was dissolved in
enough water to give 1.00 x 102 mL of solution. The osmotic
pressure of the solution was 2.80 torr at 25⁰C. Calculate the
molar mass of the material
3. If a solution contains 10.5 g of sucrose (C12H22O11) per 100.
mL, what is its osmotic pressure at 25 oC. What concentration
of salt (NaCl) would exhibit the same osmotic pressure.

4. A 50.0 mL sample of an aqueous solution containing 1.08 g of

human serum albumin (HSA) has an osmotic pressure of 5.85
mmHg at 298 K. Calculate the molar mass of HSA.
Osmotic Pressure
› Osmotic pressures can be very large.
– For example, a 1 M sugar solution has an osmotic
pressure of 22.4 atm or 330 p.s.i.
› Since this is a large effect, the osmotic pressure
measurements can be used to determine the molar
masses of very large molecules such as:
1. Polymers
2. Biomolecules like
› proteins
› ribonucleotides
 Colligative Properties of Nonelectrolyte Solutions
Colligative properties are properties that depend only on the number of
solute particles in solution and not on the nature of the solute particles.

0
Vapor-Pressure Lowering P1 = X1 P 1

Boiling-Point Elevation DTb = Kb m

Freezing-Point Depression DTf = Kf m

Osmotic Pressure ()  = MRT

Colligative Properties of Electrolyte Solutions

For vapor pressure lowering: DP = i(Csolute x Posolvent)

For boiling point elevation: DTb = i(bm)

For freezing point depression: DTf = i(fm)

For osmotic pressure: Π = i(MRT)

An electrolyte is a substance that, when dissolved in water,
results in a solution that can conduct electricity.
A nonelectrolyte is a substance that, when dissolved, results
in a solution that does not conduct electricity.

nonelectrolyte weak electrolyte strong electrolyte

4.1
Colligative Properties of Solutions of Electrolytes
A 1 m solution of NaCl, an ionic compound, freezes at -3.37⁰C, instead
of -1.86⁰C, the expected freezing point of a 1 m molecular compound
dissolved in water. This much greater depression of the freezing point
by the salt - almost twice as much.
In a 1 m NaCl solution, the solute is dissociated.
NaCl(s) ---------> Na+(aq) + Cl-(aq)

So, 1 m NaCl actually has a 2 m concentration in dissolved solute

particles. Theoretically, then 1 m NaCl should freeze at 2 X (-1.86⁰C)
= -3.72⁰C.
Colligative Properties of Solutions of Electrolytes

Electrolytes depress the freezing point and elevate the boiling point
of a solvent more than expected.
Electrolytes produce more than 1 mol of solute particles for each
mole of compound dissolved
C12H22O11 ---------> C12H22O11(aq)
CaCl2 ---------> Ca2+(aq) + 2Cl-(aq)
NaCl ---------> Na+(aq) + Cl-(aq)
H2SO4(l) ---------> 2 H+(aq) + SO42-(aq)
 Colligative Properties of Electrolyte Solutions
0.1 m NaCl solution 0.1 m Na+ ions & 0.1 m Cl- ions
Colligative properties are properties that depend only on the number of solute particles
in solution and not on the nature of the solute particles.

0.1 m NaCl solution 0.2 m ions in solution

actual number of particles in soln after dissociation
van’t Hoff factor (i) =
number of formula units initially dissolved in soln

i should be

nonelectrolytes 1
NaCl 2

CaCl2 3
Colligative Properties of Solutions of Electrolytes

Colligative properties depend on the total concentration of solute

particles.

The changes in colligative properties caused by electrolytes will be

proportional to the total molality of all dissolved particles, not to
formula units.

For the same molal concentrations of sucrose and sodium chloride,

you would expect the effect on colligative properties to be twice as
large for sodium chloride as for sucrose.
Colligative Properties of Solutions of Electrolytes
Example:
Estimate the freezing point of a 0.106 m aqueous MgCl2, assuming
that it ionizes completely.
Solution: When MgCl2 dissolves in water it breaks up as follows:
MgCl2(s) ------> Mg2+(aq) + 2 Cl-(aq)
Colligative Properties of Solutions of Electrolytes
Solve:
What is the expected change in the freezing point of water in a
solution of 62.5 g of barium nitrate, Ba(NO3)2, in 1.00 kg of water?
 Change in Freezing Point
Which would you use for the streets of Bloomington
to lower the freezing point of ice and why?
Would the temperature make any difference in
your decision?
a) sand, SiO2
b) Rock salt, NaCl
c) Ice Melt, CaCl2
Colligative Properties of Electrolyte Solutions
Boiling-Point Elevation DTb = i Kb m

Freezing-Point Depression DTf = i Kf m

Osmotic Pressure ()  = iMRT

Colligative Properties of Solutions of Electrolytes
Vapor pressure on electrolyte solutions
In an electrolyte solution, the number of dissolved particles is larger
because the solute breaks apart into ions. The greater the number
of ions, the larger the impact on colligative properties will be.

Which would have the lowest vapor pressure at 25 oC?

a) 0.1 M solution of NaCl
b) 0.1 M solution of C6H12O6 (glucose)
c) 0.1 M solution of Al(NO3)3
Colligative Properties of Solutions of Electrolytes
1. Why are colligative properties of solutions of ionic compounds
usually more pronounced than those of solutions of the same
molarities of molecular compounds?
2. The vapor pressure of water at 20⁰C is 2.33 kPa. If the solute in a
solution made from 10.0 g of NaCl in 1.00 kg of water is 100%
dissociated (and is an ideal solution), what is the vapor pressure
of this solution at 20⁰C?
3. Which aqueous solution, if either, has the lower freezing point,
10% (w/w) NaCl or 10% (w/w) NaI?
4. Which aqueous solution, if either, has the higher boiling point,
0.50 m NaI or 0.50 m Na2CO3?
5. Which aqueous solution, if either, has the higher osmotic
pressure, 1.5% (w/w) glucose (C6H12O6, formula weight 180) or
1.5% (w/w) NaCl?