Van’t Hoff Factor (i) ‫معامل فان هوف‬

• The number of moles of solute particles dissolved from

1 mole of solid solute.
• Examples:
NaCl(s) Na+(aq) + Cl-(aq) i=2
CaCl2(s)Ca2+(aq) + 2Cl-(aq) i=3
Na3PO4(s)3Na+(aq) + PO43-(aq) i=4
Sugar(s)  Sugar(aq) i=1
(any substance that doesn’t dissociate into ions in water
e.g. sugar, has i=1 )

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 Examples

Observed (i) values can be

Electrolyte i (expected) i (observed)
NaCl 2 1.9 only determined experimentally.
MgCl2 3 2.7 They are generally lower than
MgSO4 2 1.3 expected values due to
FeCl3 4 3.4
ion-paring in solution.
HCl 2 1.9
glucose 1.0 1.0

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 Ion Pairing

• At a given instant, a small percentage of the positive and

negative ions are paired and thus count as a single
particle (i) observed is lower than (i) expected.

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 Ion Pairing
• Ion pairing is most important in concentrated
solutions.
• As the solution becomes more dilute, the ions are
farther apart and less ion pairing occurs.
• Ion pairing occurs in all electrolyte solutions.
• Ion pairing is most important for highly charged
ions.

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Section 11.5
Boiling-Point Elevation and Freezing-Point
Depression
Colligative Properties
 Depend only on the number, not on the identity, of the
solute particles in solution:
‫ وليس عىل هويتها‬، ‫الت تعتمد فقط عىل عدد الجسيمات المذابة‬
‫الخصائص ي‬

 Boiling-point elevation ‫ارتفاع درجة الغليان‬

 Freezing-point depression ‫نقص نقطة التجمد‬
 Osmotic pressure ‫الضغط االسموزي‬

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Section 11.5
Boiling-Point Elevation and Freezing-Point
Depression
Boiling-Point Elevation
 Solute elevates (increases) boiling point of the solvent.
ΔT = iKbmsolute
ΔT = boiling-point elevation = (Tsolution-Tsolvent)
Kb = molal boiling-point elevation constant
msolute = molality of solute
i = Van’t Hoff factor

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Section 11.5
Boiling-Point Elevation and Freezing-Point
Depression
EXERCISE!

A solution was prepared by dissolving 25.00 g of

glucose in 200.0 g water. The molar mass of glucose is
180.16 g/mol. Kb is 0.51 ᶛC.kg/mol. What is the boiling
point of the resulting solution (in ᶛC)?
Solution: The Van’t Hoff factor of glucose (i)=1, Tsolvent =100 ᶛC
msolute = nsolute/Kg of solvent = (25÷180.16)/(0.200 Kg)=0.6938 m
ΔT = iKbmsolute Tsolution-Tsolvent =iKbmsolute
Tsolution- 100 = (1)(0.51) (0.6938)
Tsolution = 100.35 ᶛC
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Section 11.5
Boiling-Point Elevation and Freezing-Point
Depression
EXERCISE!
A solution was prepared by dissolving 18.00 g of a
certain sugar in 150.0 g water. Kb is 0.51 ᶛC.kg/mol. The
resulting solution was found to have a boing point of
100.34 ᶛC. Calculate the molar mass of the sugar used.
Solution: The Van’t Hoff factor of sugar (i)=1, Tsolvent =100 ᶛC
ΔT = iKbmsolute Tsolution-Tsolvent =iKbmsolute
100.34 - 100 = (1)(0.51) (msolute) msolute = 0.67
msolute = nsolute/Kg of solvent  nsolute = (0.67) (0.150 Kg) = 0.10 mol
nsolute = mass/MM MM = (18.00 g)/(0.1 mol) = 180 g/mol

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Section 11.5
Boiling-Point Elevation and Freezing-Point
Depression
Freezing-Point Depression
 When a solute is dissolved in a solvent, the freezing
point of the solution is lower than that of the pure
solvent.
ΔT = iKfmsolute
ΔT = freezing-point depression = (Tsolvent-Tsolution)
Kf = molal freezing-point depression constant
msolute = molality of solute
i = Van’t Hoff factor

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Section 11.5
Boiling-Point Elevation and Freezing-Point
Depression
EXERCISE!

What mass of ethylene glycol (MM=62.1) must be added to

10.0 L water to produce a solution that freezes at -23.3 ᶛC?
Assume density of water is 1.0 g/ml. Kf of water =1.86
Solution: purer water freezes at 0.0 ᶛC, (i) of ethylene glycol = 1
ΔT = Tsolvent-Tsolution = 0.0 – (-23.3)= +23.3 ᶛC
ΔT = iKfmsolute  23.3= (1) (1.86) msolute  msolute = 12.5 m
msolute=nsolute/Kg solvent nsolute = (12.5)(10.0 Kg)=125 mol
nsolute = mass/MM  mass = (125 mol)(62.1g/mol)=7762.5 g
Note: 10 L water ==10 Kg since density of water is given as 1.0 g/ml
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Section 11.6
Osmotic Pressure

 Osmosis – flow of pure solvent into a solution through a

semipermeable membrane.
  = iMRT
 = osmotic pressure (atm)
M = Molarity of the solution
R = gas law constant=0.082 L.atm/mol.K
T = temperature (Kelvin)
i = Van’t Hoff factor
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Section 11.6
Osmotic Pressure

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Section 11.6
Osmotic Pressure
EXERCISE

0.001 g protein was dissolved in water to make 1.00

ml solution. The osmotic pressure was 1.12 torr at 25
ᶛC. Calculate the MM of the protein.
Solution: (i) of protein =1, T=25+273=298K
π=1.12 torr ÷ (760 torr/1 atm)=1.47x10-3 atm
π=iMRTM=π/iRT=1.47x10-3/(1)(0.082)(298)=6.01x10-5 M
M=n/Vsoln Ln= (6.01x10-5)(1.00 ml÷1000)=6.01x10-8 mol
n=mass/MMMM=0.001 g/(6.01x10-8 mol)=1.66x104 g/mol
Section 11.6
Osmotic Pressure
EXERCISE

What concentration of NaCl in water is needed to

produce an aqueous solution isotonic with blood. For
blood π=7.70 atm at 25 ᶛC.
Solution: (i) of NaCl=2, T=25+273=298K, π=7.70 atm
π=iMRTM=π/iRT=7.70/(2)(0.082)(298)=0.1575 M

Note: isotonic means having same osmotic pressure

Section 11.6
Osmotic Pressure
EXERCISE

The observed osmotic pressure for 0.1 M solution of

Fe(NH4) 2(SO4) 2 is 10.8 atm at 25 ᶛC. Compare the
expected and experimental Van’t Hoff values.
Solution: expected i value can be obtained from
Fe(NH4) 2(SO4) 2Fe2+ + 2NH4+ +2SO42- i=5
experimental i value can be obtained from:
π=iMRTi=π/MRT=10.8/(0.1)(0.082)(298)= 4.4
∴ iexperimental (4.4) < i expected (5) due to ion-pairing
Section 11.6
Osmotic Pressure

EXERCISE!

When 33.4 mg of a non-electrolyte compound is

dissolved in water to make 10.0 mL solution at 25 ᶛC, the
solution has an osmotic pressure of 558 torr. Calculate
the molar mass of this compound.

Solution: Final answer: The molar mass is 111 g/mol.

Note: non-electrolyte compound means i=1

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