Chapter 12

Mixtures at the Molecular

Level: Properties of Solutions

Chemistry: The Molecular Nature

of Matter, 7E

Jespersen/Hyslop
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 Chapter 12: Solutions
Solution
▪ Homogeneous mixture
▪ Composed of solvent and solute(s)
Solvent
▪ More abundant component of mixture
Solute(s)
▪ Less abundant or other component(s) of mixture
e.g., Lactated Ringer’s solution
▪ NaCl, KCl, CaCl2, NaC3H5O3 in water

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 Why do Solutions Form?
Two driving forces behind formation of
solution
1. Disordering/Randomizing*
2. Intermolecular Forces
Whether or not a solution forms depends on
both opposing forces

*In the thermodynamics chapter this is called entropy and is

defined more precisely

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 Spontaneous Mixing
▪ Two gases mix
spontaneously
▪ Due to random motions
▪ Mix without outside
work
▪ Never separate
spontaneously
▪ Tendency of system
left to itself, to
become increasingly
Gas A Gas B
disordered
separate mixed
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 Intermolecular Forces
▪ Attractive forces between molecules in pure
substances (solvents and solutes) were
considered in the last chapter
▪ Now we consider the attractive forces
between a solvent molecule and a solute
molecule
▪ Strength of intermolecular attractive forces in
a mixture, compared to the pure substances,
will indicate if a mixture can form or if the
substances will remain separate
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 Formation of Solutions Depends
on Intermolecular Forces
▪ When mixed, for a solution to form,
▪ Solvent-to-solute attractions must be similar to
attractions between solute alone and solvent
alone
▪ Initially solute and solvent separate to make room
for each other
▪ Solute molecules held together by intermolecular
forces: energy added
▪ Solvent molecules held together by
intermolecular forces: energy added
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Formation of Solutions Depends
on Intermolecular Forces
▪ When the separated solute and solvent are mixed
to make a solution
▪ Solute molecules are attracted to solvent
molecules: energy released
▪ Solvent molecules are attracted to solute
molecules: energy released
▪ If there is a net release of energy, the
solution will form.

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 Miscible Liquids
Miscible liquids
▪ Two liquids that dissolve in one another in all
proportions
▪ Form solution
▪ Strengths of intermolecular attractions are similar in
solute and solvent
▪ Similar polarity
e.g., Ethanol and water

H H − +
Ethanol;
H C C O H polar bond
H H
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 Immiscible Liquids
▪ Two insoluble liquids
▪ Do not mix
▪ Get two separate phases
▪ Strengths of intermolecular forces are
different in solute and solvent
▪ Different polarity
e.g., Benzene and water H
H C H
C C Benzene;
C C no polar bond
H C H
H
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 9
 Rule of Thumb
▪ Like dissolves like
▪ Use polar solvent for polar solute
▪ Use nonpolar solvent for nonpolar solute
▪ When strengths of intermolecular
attractions are similar in solute and
solvent, solutions form because net energy
exchange is about the same

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 Learning Check
Which of the following are miscible in water?

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 Your Turn!
Which of the following molecules is most
soluble in hexane, C6H14?
A. NH3
B. CH3NH2
C. CH3OH
D. CH3CH3
E. H2O

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 12
 Your Turn!
Which of the following molecules is most
soluble in methanol CH3OH?
A. N(CH3)3
B. CH3NH2
C. CH3COCH3
D. CH3CH2CH2CH2CH2CH3
E. HOCH2CH2OH

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 13
Solutions of Solids in Liquids
▪ Basic principles remain the same when
solutes are solids
▪ Sodium chloride (NaCl)
▪ Ionic bonding
▪ Strong intermolecular forces
▪ Ions dissolve in water because ion-dipole forces
of water with ions strong enough to overcome
ion-ion attractions

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 Hydration of Solid Solute
▪ Ions at edges, fewer
ion-ion attractions
▪ Multiple ion-dipole
attractions formed with
water
▪ These overcome stronger
ion-ion electrostatic
attractions
▪ New ion at surface
▪ Process continues until
all ions in solution
▪ Hydration of ions
▪ Completely surrounded
by solvent
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 15
 Hydration vs. Solvation

▪ Hydration
▪ Ions surrounded by water molecules

▪ Solvation
▪ General term for surrounding solute particle by
solvent molecules

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Polar Molecules Dissolve in Water
▪ H2O reorients so
▪ Positive H atoms are near negative ends of solute
▪ Negative O atoms are near positive ends of solute

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 Solvation in Nonpolar Solvents?
▪ Wax is a mixture of long chain alkanes and
is nonpolar
▪ Benzene is a nonpolar solvent
▪ Benzene can dissolve waxes
▪ Weak London dispersion forces in both solute
and solvent. Weak London forces will form
between solute and solvent.
▪ Wax molecules
▪ Easily slip from solid
▪ Slide between benzene molecules
▪ Form new London forces between solvent and solute
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 18
 Heat of Solution
▪ Energy change associated with formation of
solution
▪ Difference in intermolecular forces between
isolated solute and solvent and mixture
▪ Cost of mixing
▪ Energy exchanged between system and
surroundings
Molar Enthalpy of Solution (Hsoln)
▪ Amount of enthalpy exchanged when one
mole of solute dissolves in a solvent at
constant pressure to make a solution

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 Heat of Solution
▪ Hsoln > 0 (positive)
▪ Costs energy to make solution
▪ Endothermic
▪ Increase in potential energy of system
▪ Hsoln < 0 (negative)
▪ Energy given off when solution is made
▪ Exothermic
▪ Decrease in potential energy of system
▪ Which occurs depends on your system

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 Modeling Formation of Solution
Formation of solution from solid and liquid
can be modeled as two-step process
▪ Step 1: Separate solute and solvent
molecules
▪ Break intermolecular forces
▪ Endothermic, increase in potential energy of
system, “cost”
▪ Step 2: Mix solute and solvent
▪ Come together
▪ Form new intermolecular forces
▪ Exothermic, decrease in potential energy of
system, “profit”
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 Two-Step Process
▪ Application of Hess’ Law
▪ Way to take two things we can measure and use
to calculate something we can’t directly measure
▪ Hsoln is path independent
▪ Method works because enthalpy is state function
▪ Hsoln = Hsoln + Hsolute + Hsolvent
▪ Overall, steps take us from
solid solute + liquid solvent → final solution
▪ These steps are not the way solution
would actually be made in lab

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 Enthalpy Diagram
1. Break up solid lattice
▪ Hlattice = lattice enthalpy
▪ Increase in potential energy
2. Dissolve gas in solvent
▪ HSolvation = solvation
enthalpy
▪ Decrease in potential energy
Hsolution = Hlattice + HSolvation
▪ Whether Hsolution is positive
or negative depends on two
steps
▪ In lab, solution formed
directly
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 23
Figure 12.5 Dissolving KI in H2O
Hlattice (KI) = 632 kJ mol–1
Hhydration (KI) = – 619 kJ mol–1


Hsolution = Hlatt + Hhydr

Hsoln = 632 kJ mol–1
– 619 kJ mol–1
Hsoln = +13 kJ mol–1
▪ Formation of KI(aq) is
endothermic

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 Dissolving NaBr in H2O
Hlattice (NaBr) = 728 kJ mol–1
Hhydration (NaBr) = –741 kJ mol–1
Hsolution = Hlatt + Hhydr

Hsoln = 728 kJ mol–1

– 741 kJ mol–1
Hsoln = – 13 kJ mol–1
▪ Formation of NaBr(aq) is
exothermic

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 Your Turn!
Of the following ions which would have the
most exothermic enthalpy of hydration?
A. Ga3+
B. Ca2+
C. Li+
D. Na+

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 26
 Solutions Containing Liquid Solute
Similar treatment but
with three step path
1. Solute expanded to gas
▪ H is positive
▪ Increase in potential
energy
2. Solvent expanded to
gas
▪ H is positive
▪ Increase in potential
energy
3. Solvation occurs
▪ H is negative
▪ Decrease in potential
energy Hsoln = Hsolute + Hsolvent + Hsolvation
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 27
 Ideal Solution
▪ One in which inter-
molecular attractive
forces are identical
▪ Hsoln = 0
e.g., Benzene in CCl4
▪ All London forces
▪ Hsoln ~ 0

▪ Step 1 + Step 2 = –Step 3

▪ or
Hsolute + Hsolvent = –Hsolvation
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 28
Gaseous Solutes in Liquid Solution
▪ Only very weak attractions exist between
gas molecules
▪ There are no intermolecular attractions in ideal
gases
▪ When making solution with gas solute
▪ Energy required to “expand solute” is
negligible
▪ Heat absorbed or released when gas
dissolves in liquid has two contributions:
1. Expansion of solvent Hsolvent
2. Solvation of gas Hsolvation
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 29
Gaseous Solutes in Liquid Solution

▪ Gas dissolves in ▪ Gas dissolves in H2O

organic solvent
▪ Generally exothermic
▪ Generally endothermic
▪ Hsolvation < 0
▪ Hsolvation > 0
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 30
 Your Turn!

The solubility of a substance increases with

increased temperature if:
A. ΔHsolution > 0
B. ΔHsolution < 0
C. ΔHsolution = 0

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 Your Turn!

In which of the following situations would the

Δhsolution be exothermic:
A. ΔHhydration > ΔHlattice
B. ΔHhydration< ΔHlattice
C. ΔHhydration = ΔHlattice

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 Solubility
▪ Mass of solute that forms saturated solution with
given mass of solvent at specified temperature
g solute
solubility =
100 g solvent
▪ If extra solute added to saturated solution, extra
solute will remain as separate phase
soluteundissolved solutedissolved

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Effect of Temperature on Solubility

▪ Generally substances become more soluble at

elevated temperatures
▪ Increased disorder in the solution is often the reason
for this

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 Solubility of Most Substances
Increases with Temperature
▪ Most substances
become more
soluble as T
increases
▪ Amount solubility
increases
▪ Varies considerably
▪ Depends on
substance

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Effect of T on Gas Solubility in Liquids
▪ Solubility of gases usually decreases as T increases

▪ Solubilities of Common Gases in Water

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 Henry’s Law
▪ Pressure-Solubility Law
▪ Concentration of gas in liquid at any given
temperature is directly proportional to partial
pressure of gas over solution
Cgas = kHPgas (T is constant)
Cgas = concentration of gas
Pgas = partial pressure of gas
kH = Henry’s Law constant
▪ Unique to each gas
▪ Tabulated
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 Henry’s Law
▪ True only at low concentrations and
pressures where gases do NOT react with
solvent
▪ Alternate form
C1 C2
=
P1 P2
▪ C1 and P1 refer to an initial set of conditions
▪ C2 and P2 refer to a final set of conditions

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Effect of Pressure on Gas Solubility

▪ Solubility increases as P increases

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Effect of Pressure on Gas Solubility
A. At some P, equilibrium exists between vapor phase and
solution
▪ ratein = rateout
B. Increase in P puts stress on equilibrium
▪ Increase in frequency of collisions so ratein > rateout
C. More gas dissolved
▪ rateout will increase until rateout = ratein again

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 40
 Ex. Using Henry’s Law
Calculate the concentration of CO2 in a soft drink
that is bottled with a partial pressure of CO2 of 5
atm over the liquid at 25 °C. The Henry’s Law
constant for CO2 in water at this temperature is
3.12  10–2 mol L–1 atm–1.
C CO = k H (CO2 )PCO
2 2

= (3.12 × 10–2 mol/L atm) × (5.0 atm)

= 0.156 mol/L  0.16 mol/L

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 41
 Ex. Using Henry’s Law
Calculate the concentration of CO2 in a soft drink
after the bottle is opened and equilibrates at 25 °C
under a partial pressure of CO2 of 4.0  10–4 atm.

C1 C2 P2C 1
= C2 =
P1 P2 P1

( 0.156 mol/L ) ( 4.0 ´ 10 -4

atm )
C2 =
5.0atm
C2 = 1.2  10–4 mol CO2/L
Compared to the concentration of CO2 at
5 atm: 0.16 mol CO2/L
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 42
 Learning Check

What is the concentration of dissolved nitrogen

in a solution that is saturated in N2 at 2.0 atm?
kH= 8.42 × 10−7 mol L–1 atm–1

• Cg=kHPg
• Cg= (8.42 × 10–7 mol L–1 atm–1) × 2.0
atm
• Cg=1.7 × 10–6 mol L–1

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 43
 Your Turn!
How many grams of oxygen gas at 1.0 atm will
dissolve in 10.0 L of water at 25 °C if Henry’s
constant is 1.3 × 10–3 mol L–1 atm–1 at this
temperature?
A. 0.42 g
B. 0.013 g
C. 0.042 g 1.0 atm O2 ´ .0013 mol O2 ´ 32.00 g ´ 10 L =0.416 g
L atm 1.00 mol 1
D. 0.21 g
E. 2.4 g

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 44
 Your Turn!
▪ The solubility of O2 in water is approximately
0.00380 g L-1 when the temperature is 25.0
°C and the partial pressure of gaseous

oxygen is 760 torr. What will the solubility of

oxygen be if the pressure is adjusted to 1000
torr?
A. 0.00289 g L-1 0.00380 g/L
=
X g/L

B. 0.00500 g L -1 760 torr 1000 torr

C. 1.49 g L-1 3.80

X= = 0.00500 g/L
D. 2.89 x 103 g L-1 760

E. 3.46 x 103 g L-1

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 45
 Solubility of Polar vs. Nonpolar Gases
▪ Gas molecules with polar bonds are much more
soluble in water than nonpolar molecules like oxygen
and nitrogen
▪ CO2, SO2, NH3 >> O2, N2, Ar
▪ Form H-bonds with H2O
▪ Some gases have increased solubility because they
react with H2O to some extent
e.g.,
CO2(aq) + H2O H2CO3(aq) H+(aq) + HCO3–(aq)
SO2(aq) + H2O H2SO3(aq) H+(aq) + HSO3–(aq)
NH3(aq) + H2O NH4+(aq) + OH–(aq)

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 46
 Case Study

When you open a bottle of

seltzer, it fizzes. How
should you store it to
increase the time before it
goes flat?

Gases are more soluble at

low temperature and high
pressure.

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 47
 Concentration
▪ What units we use depends on situation
▪ Stoichiometric calculations
▪ Molarity mol of solute
M =
L of solution
▪ Units: mol/L
Problem: M varies with temperature
▪ Volume varies with temperature
▪ Solutions expand and contract when heated
and cooled
▪ If temperature independent concentration is
needed, must use other units
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 48
 Temperature Independent
Concentration
1. Percent Concentrations
▪ Also called percent by mass or percent by
weight
mass of solute
percent by mass =  100%
mass of solution
▪ This is sometimes indicated %(w/w) where “w ”
stands for weight or mass
▪ The “(w/w)” is often omitted

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 49
 Ex. Percent by Mass
What is the percent by mass of NaCl in a
solution consisting of 12.5 g of NaCl and
75.0 g water?
mass of solute
percent by mass =  100%
mass of solution

12.5 g
percent by massNaCl = ´ 100%
12.5 g + 75.0 g

percent by massNaCl = 14.3% NaCl

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 50
 Learning Check
Seawater is typically 3.5% sea salt and has a density
of 1.03 g/mL. How many grams of sea salt would be
needed to prepare enough seawater solution to fill a
62.5 L aquarium?
▪What do we need to find?
▪ 62.5 L  ? g sea salt
▪What do we know?
▪ 3.5 g sea salt  100 g solution
▪ 1.03 g solution  1.00 mL solution
▪ 1000 mL  1.00 L
1000 mL 1.03 g soln 3.5 g sea salt
62.5 L   
1L 1.00 mL soln 100 g soln
= 2.2 × 103 g sea salt
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 51
More Temperature Independent
Concentration Units
Molality (m)
▪ Number of moles of solute per kilogram solvent
mol of solute
molality = m =
kg of solvent
▪ Also molal concentration
▪ Independent of temperature
▪ m vs. M
▪ Similar when d = 1.00 g/mL
▪ Different when d >> 1.00 g/mL or
d << 1.00 g/mL
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 52
 Ex. Concentration Calculation
If you prepare a solution by dissolving 25.38 g of I2 in
500.0 g of water, what is the molality (m) of the
solution?
▪ What do we need to find?
▪ 25.38 g  ? m
▪ What do we know?
▪ 253.8 g I2  1 mol I2
▪ m = mol solute/kg solvent
▪ 500.0 g  0.5000 kg
▪ Solve it 25.38 g I 2  1 mol I 2  1
253.8 g I 2 0.5000 kg water
= 0.2000 mol I2/kg water = 0.2000 m
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 53
 Ex. Concentration Calc’n. (cont)
What is the molarity (M) of this solution? The density
of this solution is 1.00 g/mL.
▪ What do we need to find?
▪ 25.38 g  ? M
▪ What do we know?
▪ 253.8 g I2  1 mol I2
▪ M = mol solute/L soln
▪ 1.00 g soln  1 mL soln
▪ Solve it
1 mol I2 1 1.00 g 1000 mL
25.38 g I2 ´ ´ ´ ´
253.8 g I2 525.38 g soln 1.00 mL 1L
= 0.1903 mol I2/ L soln = 0.1903 M
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 54
 Ex. M and m in CCl4
What is the molality (m) and molarity (M) of a solution
prepared by dissolving 25.38 g of I2 in 500.0 g of CCl4?
The density of this solution is 1.59 g/mL.
▪ What do we need to find?
▪ 25.38 g  ? m
▪ What do we know?
▪ 253.8 g I2  1 mol I2
▪ m = mol solute/kg solvent
▪ 500.0 g soln  0.5000 kg soln
▪ Solve it 1 mol I2 1 1000 g
25.38 g I2 ´ ´ ´
253.8 g I2 500.0 g CCl4 1 kg
= 0.2000 mol I2/kg CCl4= 0.2000 m
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 55
 Ex. M and m in CCl4 (cont)
What is the molarity (M) of this solution? The density
of this solution is 1.59 g/mL.
▪What do we need to find?
▪ 25.38 g  ? M
▪What do we know?
▪ 253.8 g I2  1 mol I2
▪ M = mol solute/L solution
▪ 1.59 g solution  1 mL solution
▪ g of solution = g I2 + g CCl4 = 500.0 g + 25.38 g
▪Solve it 1 mol I 1 1.59 g 1000 mL
25.38 g I2 ´ 2
´ ´ ´
253.8 g I2 525.38 g soln 1.00 mL 1L
= 0.3030 mol I2/L soln = 0.303 M
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 56
Converting between Concentrations
Calculate the molarity and the molality of a
40.0% HBr solution. The density of this solution
is 1.38 g/mL.
40.0 g HBr
40.0% HBr = wt%= ´ 100%
100 g solution
If we assume 100.0 g of solution, then 40.0 g of HBr.
mol HBr 40.0 g HBr
m= mol HBr= =0.494 mol HBr
kg of H2O 80.91 g HBr/mol
If 100 g solution, then
mass H2O = 100.0 g solution – 40.0 g HBr = 60.0 g H2O
mol HBr 0.494 mol HBr
m= = =8.24 m
kg H2O 0.0600 kg H2O
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 57
Converting between Concentrations
(cont.)
Now calculate molarity of 40% HBr

mol HBr
M=
L solution
mass 100 g
Volume solution= = = 72.46 mL
density 1.38 g/mL
mol HBr = 0.494 mol
0.494 mol HBr 1000 mL
M = ´ = 6.82 M
72.46 mL solution 1L
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 58
 Your Turn!
What is the molality of 50.0% (w/w) sodium
hydroxide solution?
A. 0.500 m
B. 1.25 m
C. 0.025 m
D. 25 m
E. 50 m
100.0 g soln = 50.0 g NaOH + 50.0 g water
50.0 g NaOH 1 mol NaOH 1000 g water
´ ´
50.0 g water 40.00 g NaOH 1 kg water
= 25 m
Molar Masses H2O: 18.02 g/mol ; NaOH: 40.00 g/mol
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 59
 Your Turn!
What is the molarity of the 50%(w/w) solution if its
density is 1.529 g/mL?
A. 19 M
B. 1.25 M
C. 1.9 M
D. 0.76 M

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 60
 Your Turn! - Solution

50 g NaOH
?M =
100 g solution

50 g NaOH æ 1 mol NaOH ö æ 1.529 g solution ö æ 1000 mL ö

= çç ÷÷ çç ÷÷ çç ÷÷
100 g solution è 40.0 g NaOH ø è mL solution ø è L ø

= 19 M

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 61
 Your Turn!
What mass of NH4Cl must be dissolved in 100 mL of
H2O to make a 0.250 M solution?
A. 1340 g
B. 21.40 g
C. 13.4 g
D. 1.34 g

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 62
 Your Turn! - Solution

0.250 moles NH4Cl æ 0.100 L ö æ 53.49 g NH4 Cl ö

= çç ÷÷ çç ÷
÷
1 L solution è 1 øè 1 Mole ø

= 1.34 g

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 63
More Temperature-Independent
Concentration Units
▪ Mole Fraction
# mol A
XA =
Total moles of all components
▪ Mole %

mol %A = X A ´ 100%

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 64
 Colligative Properties
▪ Physical properties of solutions
▪ Depend mostly on relative populations of particles
in mixtures
▪ Don’t depend on their chemical identities

Effects of solute on vapor pressure of solvents

▪ Solutes that can’t evaporate from solution are
called nonvolatile solutes

Fact: All solutions of nonvolatile solutes have lower

vapor pressures than their pure solvents
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 65
 Raoult’s Law
▪ Vapor pressure of solution, Psolution, equals
product of mole fraction of solvent, Xsolvent
and its vapor pressure when pure, Psolvent
▪ Applies for dilute solutions

Psolution = X solvent Psolvent 

Psolution = vapor pressure of the solution

X solvent = mole fraction of the solvent
Psolvent

= vapor pressure of pure solvent
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 66
 Alternate form of Raoult’s Law
▪ Plot of Psoln vs. Xsolvent
should be linear
▪ Slope = X solventPsolvent
▪ Intercept = 0
▪ Change in vapor
pressure can be
expressed as
DP = change in P = (Psolvent - Psolution )
▪ Usually more interested in how solute’s mole fraction
changes the vapor pressure of solvent
DP = X solutePsolvent
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 67
 Ex. Glycerin (using Raoult’s Law)
Glycerin, C3H8O3, is a nonvolatile nonelectrolyte with
a density of 1.26 g/mL at 25 °C. Calculate vapor
pressure at 25 °C of a solution made by adding 50.0
mL of glycerin to 500.0 mL of water. The vapor
pressure of pure water at 25 °C is 23.8 torr.
▪To solve use:
Psolution = X solventPsolvent

▪First we need Xsolvent, so we need to determine the

moles of glycerin and moles of water.

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 68
 Ex. Glycerin (cont.)
Mole glycerin
æ g ö æ 1 mol C H O ö
50.0 mL C3H8O3 ´ çç1.26 ÷÷ ´ ç 3 8 3 ÷

mL ø ç 92.1 g C H O ÷
è è 3 8 3ø

= 0.684 mol C3H8O3

Mole water æ 1 mol H O ö

æ g ö
500.0 mL H2O ´ çç1.00 ÷÷ ´ çç 2 ÷ = 27.75 mol H O
÷ 2
è mL ø è 18.02 g H O
2 ø
Mole fraction glycerin
27.75 mol
XC H O = = 0.976
3 8 3
27.75 mol + 0.684 mol
Psolution = c solventPsolvent
(
= 0.9759 ) ´ 23.8 torr = 23.2 torr
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 69
Why Nonvolatile Solute Lowers Vapor Pressure
A. Lots of solvent
molecules in liquid phase
▪ Rate of evaporation and
condensation high and
equal
B. Fewer solvent molecules
in liquid
▪ Rate of evaporation is
lower so rate of
condensation must be
lower which is achieved by
fewer gas particles
▪ At equilibrium, fewer gas
molecules give lower
pressure
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 70
 Solutions That Contain Two or
More Volatile Components
▪ Vapor contains two components
▪ Partial pressure of each component A and B is
given by Raoult’s Law
PA = X APA and PB = X B PB
▪ Total pressure of solution of components A and
B given by Dalton’s Law of Partial Pressures
Ptotal = PA + PB = X APA + X B PB
▪ Since XA + XB = 1 then 1 – XA = XB and we
can write
Ptotal = X APA + (1 - X A )PB
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 71
For Ideal, Two Component Solution
of Volatile Components
Ptotal = PA + PB = X APA + X BPB

PA = X APA PB = X P o
B B

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 72
 Ex. Benzene and Toluene
▪ Consider a mixture of benzene, C6H6, and
toluene, C7H8, containing 1.0 mol benzene
and 2.0 mol toluene. At 20 °C, the vapor
pressures of the pure substances are:
P °benzene = 75 torr and P °toluene = 22 torr
▪ Assuming the mixture obeys Raoult’s law,
what is the total pressure above this
solution?

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 73
Ex. Benzene and Toluene (cont.)
1. Calculate mole fractions of A and B
1.0 mol benzene
X benzene = = 0.33 benzene
1.0 mol + 2.0 mol
2.0 mol
X toluene = = 0.67 toluene
(1.0 + 2.0) mol
2. Calculate partial pressures of A and B
Pbenzene = X benzene ´ Pbenzene
o
= 0.33 ´ 75 torr = 25 torr
Ptoluene = X toluene ´ Ptoluene
o
= 0.67 ´ 22 torr = 15 torr
3. Calculate total pressure
Ptotal = Pbenzene + Ptoluene
= (25 + 15) torr = 40 torr
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 74
 Learning Check
The vapor pressure of 2-methylheptane is
233.95 torr at 55 °C. At the same
temperature, 3-ethylpentane has a vapor
pressure of 207.68 torr. What would be the
pressure of the mixture of 78.0 g
2-methylheptane and 15 g 3-ethylpentane?

2-methylheptane 3-ethylpentane
C8H18 C7H16
MM 114.23 g/mol MM 100.2 g/mol
Psolution = XAP oA + XBP oB
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 75
 Learning Check
78.0 g
mole 2-methylheptane = = 0.683 mol
114.23 g/mol
15.0 g
mole 3-ethylpentane = = 0.150 mol
100.2 g/mol

0.683 mol
X2-methylpentane = = 0.827
(0.683 mol + 0.150 mol)
0.150 mol
X3-ethylpentane = = 0.173
(0.683 mol + 0.150 mol)

P = ( 0.827´ 233.95 torr ) + ( 0.173´ 207.68 torr )

P = 230 torr
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 76
 Your Turn!
n-Hexane and n-heptane are miscible. If the vapor
pressure of pure hexane is 151.28 mm Hg, and
heptane is 45.67 at 25 °C, which equation can be
used to determine the mole fraction of hexane in the
mixture if the mixture’s vapor pressure is 145.5 mm
Hg?
A. X (151.28 mmHg) = 145.5 mmHg
B. X (151.28 mmHg) + (X )(45.67 mm Hg)
= 145.5 mmHg
C. X (151.28 mmHg) + (1 – X )(45.67 mm Hg)
= 145.5 mm Hg
D. None of these
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 77
 Solutes also Affect Freezing and
Boiling Points of Solutions
Facts:
▪ Freezing point of solution always lower than
pure solvent
▪ Boiling point of solution always higher than
pure solvent
Why?
▪ Consider the phase diagram of H2O
▪ Solid, liquid, gas phases in equilibrium
▪ Blue lines
▪ P vs. T
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 78
 Freezing Point Depression and
Boiling Point Elevation
Solution
▪ Observe increase in boiling point and decrease in
freezing point compared to pure solvent
▪ Both Tf and Tb depend on relative amounts of
solvent and solute
Colligative properties
▪ Boiling Point Elevation (Tb)
▪ Increase in boiling point of solution vs. pure solvent
▪ Freezing Point Depression (Tf )
▪ Decrease in freezing point of solution vs. pure solvent

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 79
Freezing Point Depression (Tf)

 T f = Kf m
where
Tf = (Tf – Tsoln)
m = concentration in Molality
Kf = molal freezing point depression constant
Units of °C/molal
Depend on solvent, see Table 12.4

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 80
 Boiling Point Elevation (Tb)

 T b = Kb m
where
Tb = (Tsoln – Tb)
m = concentration in Molality
Kb = molal boiling point elevation constant
Units of °C/m
Depend on solvent, see Table 12.4

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 81
 Table 12.3 Kf and Kb

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 82
 Ex. Freezing Point Depression
Estimate the freezing point of a permanent type of
antifreeze solution made up of 100.0 g ethylene
glycol, C2H6O2, (MM = 62.07 g/mol) and 100.0 g
H2O (MM = 18.02 g/mol).
1 mol C2H6O2
100.0 g C2H6O2 ´ = 1.611 mol C2H6O2
62.07 g C2H6O2

mol solute 1.611 mol C2H6O2

m= = = 16.11 m C2H6O2
kg solvent 0.100 kg water
Tf = Kfm = (1.86 °C/m) × 16.11 m = 30.0 °C
Tf = (Tfp – Tsoln)
30.0 °C = 0.0 °C – Tsoln
Tsoln = 0.0 °C – 30.0 °C = –30.0 °C
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 83
 Your Turn!
When 0.25 g of an unknown organic compound is
added to 25.0 g of cyclohexane, the freezing point of
cyclohexane is lowered by 1.6 °C. Kf for the solvent
is 20.2 °C m–1. Determine the molar mass of the
unknown.
A. 505 g/mol DTf = K f m
B. 32 g/mol é 0.250 g ù
ê ú
C. 315 g/mol o
C ë molar mass û
o
D. 126 g/mol 1.6 C = 20.2 ´
m 0.025 kg
MW = 126 g/mol

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 84
 Ex. Boiling Point Elevation
A 2.00 g sample of a substance was dissolved in 15.0 g
of CCl4. The boiling point of this solution was
determined to be 77.85 °C. Calculate the molar mass
of the compound.
[For CCl4, the Kb = 5.07 °C/m and BP = 76.50 °C]
DTb ( 77.85 - 76.50) °C
DTb = K bm m= = = 0.2684 m
Kb 5.07 °C / m
mol solute mol solute = 0.2684 m ´ 0.0150 kg CCl4
m=
kg solvent = 4.026 ´10-3 mol

2.00 g compound
molar mass = -3
= 497 g/mol
4.026 ´10 mole
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 85
 Learning Check
According to the Sierra™ Antifreeze literature,
the freezing point of a 40/60 solution of Sierra
antifreeze and water is – 4 °F. What is the
molality of the solution?
tF = 1.8 tC + 32
– 4 °F = 1.8 tC + 32
DTsolution = m ´ Kfp
tC = – 20. °C
T = Tf – Tsoln ( )
0 - (-20.) °C = m ´ 1.86 °C m –1

m = 11 m
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 86
 Learning Check
In the previous sample of a Sierra™ antifreeze
mixture, 100 mL is known to contain 42 g of the
antifreeze and 60. g of water. What is the molar mass
of the compound found in this antifreeze if it has a
freezing point of – 4 °F?
From before:
mol solute
m = 11 m m=
kg solvent
mol solute = 11 m ´ 0.060 kg solvent
= 0.66 mol solute
42 g solute
MM = MM solute = 64 g/mol
0.66 mol solute
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 87
 Your Turn!
If all of the following generic compounds have the
same Kb, which will cause a greater change in the
boiling point of a 0.25 m nonelectrolyte solution
(Assume all dissociate completely in solution)
A. MX
B. MX2
C. M2X3
D. MX3
E. Not enough information given

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 88
 Membranes and Permeability
Membranes
▪ Separators
▪ Example: cell walls
▪ Keep mixtures separated
Permeability
▪ Ability to pass substances
through membrane
Semipermeable
▪ Some substances pass,
others don’t
▪ Membranes are
semipermeable
▪ Selective
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 89
 Membranes and Permeability
▪ Degree of permeability depends on type of
membrane
▪ Some pass water only
▪ Some pass water and small ions only
▪ Membranes separating two solutions of different
concentration
▪ Two similar phenomena occur
▪ Depends on membrane
Dialysis
▪ When semipermeable membrane lets both H2O and
small solute particles through
▪ Membrane called dialyzing membrane
▪ Keeps out large molecules such as proteins
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 90
 Osmosis
Osmotic Membrane
▪ Semipermeable membrane that lets only solvent
molecules through
Osmosis
▪ Net shift of solvent molecules (usually water)
through an osmotic membrane
▪ Direction of flow in osmosis,
▪ Solvent flows from dilute to more concentrated side
▪ Flow of solvent molecules across osmotic membrane
▪ Increase in concentration of solute on dilute side
▪ Decrease in concentration of solute on more
concentrated side
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 91
 Osmosis and Osmotic Pressure

A. Initially, solution B separated from pure water, A, by

osmotic membrane. No osmosis occurred yet
B. After a while, volume of fluid in tube higher. Osmosis
has occurred.
C. Need back pressure to prevent osmosis = osmotic
pressure.
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 92
 Osmotic Pressure
▪ Exact back pressure needed to prevent osmotic
flow when one liquid is pure solvent.
Why does osmosis eventually stop?
▪ Extra weight of solvent as rises in column
generates this opposing pressure
▪ When enough solvent transfers to solution so that
when osmotic pressure is reached, flow stops
▪ If osmotic pressure is exceeded, then reverse
process occurs—solvent leaves solution
▪ Reverse osmosis—used to purify sea water

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 93
 Equation for Osmotic Pressure
▪ Similar to ideal gas law
V = nRT or  = MRT
▪  = osmotic pressure
▪ V = volume
▪ n = moles
▪ M = molarity of solution (n/V)
▪ T = Temperature in Kelvins
▪ R = Ideal gas constant
= 0.082057 L atm mol–1 K–1

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 94
 Osmometer
▪ Instrument to measure osmotic pressure
▪ Very important in solutions used for
biological samples
Isotonic solution
▪ Same salt concentration as cells
▪ Same osmotic pressure as cells
Hypertonic solution
▪ Higher salt concentration than cells
▪ Higher osmotic pressure than cells
▪ Will cause cells to shrink and dehydrate
Hypotonic solution
▪ Lower salt concentration than cells
▪ Lower osmotic pressure than cells
▪ Will cause cells to swell and burst
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 95
 Ex. Osmotic Pressure
Eye drops must be at the same osmotic pressure
as the human eye to prevent water from moving
into or out of the eye. A commercial eye drop
solution is 0.327 M in electrolyte particles. What is
the osmotic pressure in the human eye at 25 °C?

 = MRT T = 25 °C + 273.15
æ L atm ö
(
P = 0.327 M çç 0.08206
è
) ÷÷ 298 K = 8.00 atm
K mol ø
( )

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 96
 Ex. Using  to determine MM
The osmotic pressure of an aqueous solution of certain
protein was measured to determine its molar mass. The
solution contained 3.50 mg of protein in sufficient H2O to
form 5.00 mL of solution. The measured osmotic pressure
of this solution was 1.54 torr at 25 °C. Calculate the molar
mass of the protein.
æ 1 atm ö
1.54 torr çç ÷÷
P è 760 torr ø mol
M = = = 8.28 ´ 10 –5
RT (
0.08206 L atm mol–1 K –1 298 K L )
( )(
mol = 8.28 ´ 10–5 M 5.00 ´ 10–3 L = 4.14 ´ 10–7 mol )
g 3.50 ´ 10 –3 g 3
Molar mass = = = 8.45 ´ 10 g/mol
mol –7
4.14 ´ 10 mol
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 97
 Learning Check: Osmosis
A solution of 5% dextrose (C6H1206) in
water is placed into the osmometer shown
at right. It has a density of 1.0 g/mL. The
surroundings are filled with distilled water.
What is the expected osmotic pressure at
25 °C?
P = MRT
æ 5 g C H O ö æ mol C H O ö æ 1.0 g soln ö æ 1000 mL ö
ç 6 12 6 ÷ ç 6 12 6 ÷
÷÷ = M
ç 100 g solution ÷ ç 180.16 g ÷ çç mL soln ÷÷ çç L
è øè øè øè ø
æ 0.277 mol ö æ 0.082057 L atm ö
P = çç
è L
÷÷ çç
øè mol K
÷÷ 298 K
ø
( )
 = 7 atm
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 98
 Learning Check
For a typical blood plasma, the osmotic pressure at
body temperature (37 °C) is 5409 mm Hg. If the
dominant solute is serum protein, what is the
concentration of serum protein?
P = MRT
æ 1 atm ö
(5409 mm Hg çç
è 760 mm Hg ø
)
÷÷ = P

æ ? mol ö æ 0.082057 L atm ö

7.117 atm = çç
è L øè
÷÷ çç
mol K
÷÷ 310. K
ø
( )
Molarity = 0.280 M
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 99
 Your Turn!
Which aqueous solution has the highest
osmotic pressure.
A)0.100 molar Al(NO3)3 All solutions have the same
temperature so the only

B) 0.150 molar Ba(NO3)2

influence is number of ions.

C) 0.100 molar CaCl2

D) 0.150 molar NaCl
E) 0.200 molar NH3

Molar Mass H2S: 34.076 g/mol

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 100
Colligative Properties of Electrolyte
Solutions Differ
▪ Kf (H2O) = 1.86 °C/m
▪ Expect 1.00 m solution of NaCl to freeze at
–1.86 °C
▪ Actual freezing point = –3.37 °C
▪ About twice expected T
Why?
▪ Colligative properties depend on
concentration (number) of particles
▪ One NaCl dissociates to form two particles
NaCl(s) ⎯→ Na+(aq) + Cl–(aq)
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 101
 Colligative Properties of Electrolyte
Solutions Depend on Number of Ions
▪ Actual concentration of ions = 2.00 m
(Started with 1.00 m NaCl)
▪ Now use this to calculate T
▪ Tf = 1.86 °C/m  2.00 m = 3.72 °C
Or
▪ Tfinal = Tinitial – Tf = 0.00 – 3.72 °C
= – 3.72 °C
▪ Not exactly = to actual Tf = –3.37 °C
▪ This method for ions gives rough estimate if
you assume that all ions dissociate 100%.
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 102
Why isn’t this Exact for Electrolytes?
▪ Assumes 100% dissociation of ions
▪ Electrolytes don’t dissociate 100%, especially in
concentrated solutions
▪ Some ions exist in ion pairs
▪ Closely associated pairs of oppositely charged ions that
behave as a single particle in solution
▪ So, fewer particles than predicted
▪ Result: freezing point depression and boiling point
elevation not as great as expected
▪ As you go to more dilute solutions, electrolytes
more fully dissociated and observe freezing point
and boiling point closer to calculated value.
▪ Model works better at dilute concentrations
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 103
 van’t Hoff Factor = i
▪ Scales solute molality to correct number of
particles
▪ Measure of dissociation of electrolytes
▪ van’t Hoff factor is equivalent to percent
ionization
▪ In general, it varies with concentration (see
Table 12.5, page 613)
(DTf )measured
i=
(DTf )calcd as nonelectrolyte

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 104
 Table 12.5 van’t Hoff Factors vs.
Concentration

Note:
1. As concentration decreases, iobserved  iexpected
2. MgSO4 much less dissociated than NaCl or KCl
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 105
 Your Turn!
What is the van’t Hoff factor for FeCl3 if a solution of
81.1 g dissolved in 500 g H2O has a boiling point of
101.74 °C?
Dt
A. 4 i =
Kbm
B. 1 1.74°C
= = 3.4
C. 3.4 0.512 °C/m * 1.00 m
D. 2.7
E. Not enough information given

MM: FeCl3 = 162.2 g/mol; Kb=0.512 °C/m

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 106
 Nonelectrolytes
▪ Some molecular solutes produce weaker
colligative effects than predicted by their molal
concentrations
▪ Evidence of solute molecule clustering or
associating
O O H O
2 C6H5 C C6H5 C C C6H5
O H O H O
▪ Result: only half the number of particles
expected based on molality of solution, so Tf
only half of what expected
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 107
 Nonelectrolytes
O O H O
2 C6H5 C C6H5 C C C6H5
O H O H O

▪ Result: calculated molar mass double

what is expected
▪ Concentration of particles is about half of
what is expected and
▪ Tf only half of what expected
▪ So size of solute particles is important
▪ Common with organic acids and alcohols
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 108
 Learning Check
In preparing pasta, 2 L of water at 25 °C are combined
with about 15 g salt (NaCl, MM= 58.44 g/mol) and the
solution brought to a boil. What is the change in the
boiling point of the water?
ΔT = i m Kbp
mass of water = volume × density = 2000 mL × 1.0 g/mL
= 2000 g water = 2 kg
15 g NaCl
mol NaCl = –1
= 0.257 mol
58.44 g mol
mNaCl = 0.26 mol / 2 kg = 0.1 m
2 ion 0.1 m 0.51 °C
DT = ´ ´ ΔT = 0.1 °C
mol 1 m
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 109
 Case Study
Suppose you run out of salt. What mass of
sugar (C12H22O11, MM = 342.30 g/mol) added
to 2 L of water would raise the temperature of
water by 0.10 °C? ΔT=i m Kbp
æ ö æ 0.51 oC ö
0.10 oC = çç
1 ion
è mol ø
( )
÷÷ ´ x m ´ çç
è m ø
÷÷ molality = 0.196 m

mass of water = volume × density = 2000 mL × 1.0 g/mL

= 2000 g water = 2 kg 0.196 m = y mol / 2 kg
y = 0.392 mol
mass sucrose
0.392 mol = –1
mass of sucrose =130 g
342.30 g mol
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 110
Colligative Properties Summary
Colligative properties depend on number
of particles
▪ i = mapp/mmolecular
▪ Raoult’s Law
▪ Freezing point depression
▪ Boiling point elevation
▪ Osmotic pressure
Must look at solute and see if molecular
or ionic
▪ If molecular, i = 1
▪ If ionic, must include i > 1 in equations
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 111
 Colligative Properties
▪ Raoult’s law
Psolution = c solventPsolvent
o

▪ Freezing point depression

▪ Tf = iKf m
▪ Boiling point elevation
▪ Tb = iKb m
▪ Osmotic pressure
▪  = iMRT

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 112
 Heterogeneous Mixtures
Dispersions:
▪ 2 or more phases that are not homogeneous
▪ Many consumer products are of this type
Two major types
▪ Suspensions
▪ Large particles mixed in a solvent
▪ Two phases
▪ Colloidal dispersions
▪ Very small particles
▪ Do not settle or have separate phases
▪ Look like true solutions but scatter visible light

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 113
 Colloidal Dispersions
Tyndall effect
▪ Scattering of light observed in colloidal
dispersions

Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 114