Ch 12.

Properties of Solutions;
Mixtures of Substances at the
Molecular Level

Brady & Senese, 5th Ed.

Index
12.1. Substances mix spontaneously when there is no energy b
arrier to mixing
12.2. Heats of solution come from unbalanced intermolecular
attractions
12.3. A substance's solubility changes with temperature
12.4. Gases become more soluble at higher pressures
12.5. Molarity changes with temperature; molality, weight
percentages, and mole fractions do not
12.6. Solutes lower the vapor pressure of a solvent
12.7. Solutions have lower freezing points and higher boiling
points than pure solvents
12.8. Osmosis is flow of solvent through a semipermeable
membrane due to unequal concentrations
12.9. Ionic solutes affect colligative properties differently
than nonionic solutes
2

Mixing Processes
Mixing occurs due to interaction between
molecules like dissolves like
As partition is removed, molecules are able to
move freely and interact
Mixed state is statistically more probable

12.1. Substances mix spontaneously when there is no energy barrier

The Process Of Dissolution

Polar solutes dissolve in polar solvents
Non-polar solutes dissolve in non-polar solvents
Dipoles of solvent may induce dipoles in solute,
effecting dissolution

12.1. Substances mix spontaneously when there is no energy barrier

Miscibility of Liquids
Liquids that can dissolve
in one another are
miscible, while insoluble
liquids are immiscible
Ethanol and water are
miscible, while benzene
and water are not

12.1. Substances mix spontaneously when there is no energy barrier

Learning Check
Which of the following are miscible in water?

water

acetic acid

carbon
disulfide

ammonia

12.1. Substances mix spontaneously when there is no energy barrier

Your Turn!
Which of the following are likely to be miscible
with water?
A. CH3CH2CH2CH3
B. C6H6
C. CH3CO2H
D. All are expected to be miscible

12.1. Substances mix spontaneously when there is no energy barrier

Dissolution Of An Ionic Compound In Water

Positive end of the dipole
of the water surrounds the
anions of the ionic solid,
extracting them from the
lattice
Negative end of the dipole
orients toward the cations,
surrounding and extracting
them from the lattice

12.1. Substances mix spontaneously when there is no energy barrier

Dissolution Of A Polar Compound In Water

Dipole of the water interacts with the oppositely
charged dipoles of the solid, extracting them from
the crystal

12.1. Substances mix spontaneously when there is no energy barrier

Enthalpy (Heat) Of Solution

Heat of solution (soln ) is the energy
exchanged when a solute dissolves in a solvent at
constant pressure
Enthalpy is a state function: the pathway can be
written in any way and the result will be the same
When soln=0, solution is called an ideal
solution

12.2. Enthalpy of solution comes from unbalanced intermolecular attr 10

Dissolution Of An Ionic Solid

Visualized in steps:
step1: ionic solid
breaks apart into vapor
phase lattice energy
(U)
step 2: vapor phase
interacts with solvent
solvation energy
(Hsolv); if solvent is
water, (hydration)

soln (ion in water)= U + solvation

12.2. Heats of solution come from unbalanced intermolecular attracti

11

Dissolution: Liquid In Liquid

Step1: solute
expands
Step2: solvent
expands
Step 3 solute &
solvent mix
If the
soln=0, we
have an ideal
solution

soln = 1 + 2 + 3

12.2. Heats of solution come from unbalanced intermolecular attracti

12

Dissolution: Liquid in Liquid (Ideal)

12.2. Heats of solution come from unbalanced intermolecular attracti

13

Dissolution: Gas In Liquid

step1: expansion of solvent
step2: mixing
soln = 1 + 2

12.2. Heats of solution come from unbalanced intermolecular attracti

14

Your Turn!
What factor does not affect the value of Hsoln ?
A.
B.
C.
D.
E.

The polarities of solute and solvent

The size of the solute
The charge on the solute
The temperature of the solution
All affect the value

12.2. Heats of solution come from unbalanced intermolecular attracti

15

Saturated Solutions
Solute is at equilibrium
with the dissolved solute
Addition of more
dissolved solute results in
supersaturation and
precipitation of excess
solid
The presence of less solute
than the solubility results
in an unsaturated
solution
12.3. A substance's solubility changes with temperature

16

Solubility Varies With Temperature

Solubility may increase
or decrease with
increasing temperature
The extent to which
temperature has an
effect is specific to the
solute and solvent
Most gases are less
soluble in water at high
temperature, while most
solids are more soluble
12.3. A substance's solubility changes with temperature

17

Case Study: Dead Zones

During the industrial revolution, factories were built on
rivers so that the river water could be used as a coolant
for the machinery. The hot water was dumped back
into the river and cool water recirculated. After some
time, the rivers began to darken and many fish died.
The water was not found to be contaminated by the
machinery. What was the cause of the mysterious fish
kills?

increased temperature lowered amounts of

dissolved oxygen
12.3. A substance's solubility changes with temperature

18

Effects Of Temperature On Solubility

Solubility varies with temperature according to the enthalpy
of solvation
The efficiency of a solvation process (K) depends on the
enthalpy (H) in Joules, the ideal gas constant (R), and the
temperature (T) in Kelvin
If the dissolution process is endothermic ( is +),
increasing temperature results in greater efficiency

K1
H 1
1
ln( )
( )
K2
R T1 T 2

12.3. A substance's solubility changes with temperature

19

Your Turn!
The solubility of a substances increases with
increased temperature if:
A. Hsolution >0
B. Hsolution <0
C. Hsolution =0

12.3. A substance's solubility changes with temperature

20

Pressure Effects On Solubility Of Gases

Cg=kHPg
C = concentration of dissolved gas (M)
kH = Henrys Constant
P = pressure applied to system (mm Hg)
kH
(M/mm Hg)
N2
8.4210 -7
O2
CO2

1.6610-4
4.4810-5

Gases are all more soluble at higher pressures (the

cause of the bends)
12.4. Gases become more soluble at higher pressures

21

Learning Check
What is the concentration of dissolved nitrogen in a
solution that is saturated in N2 at 2.0 atm
kH= 8.4210 -7 (M / mm Hg)
Cg=kHPg
Cg= 8.4210 -7 (M / mm Hg) 2.0 atm 760 mmHg/atm
Cg=1.3 10-3 M

12.4. Gases become more soluble at higher pressures

22

Your Turn!

A.
B.
C.
D.

When you open a bottle of

seltzer, it fizzes. How should you
store it to increase the time before
it goes flat?
Heat it and pressurize it
Cool it and pressurize it
Heat it and reduce the pressure
Cool it and reduce the pressure

12.4. Gases become more soluble at higher pressures

23

Units Of Concentration
Molarity (M) = moles solute / L solution
changes with Temperature

Molality (m) = moles solute/kg solvent

mole fraction (X)
X = moles component/ total moles

Percent by mass (%)

(mass solute / mass solution)*100

12.5. Molarity changes with temperature; molality, weight percentage 24

Units Of Very Low Concentrations

Parts per million (ppm)
g solute/mL soln

Parts per billion (ppb)

ng solute/ mL soln

In extremely dilute solutions mostly solvent is

present
When the solvent is water (d1g/mL) thus for ppm
g solute/g soln
1/106 magnitude difference leads to the name 1 part
per 1 billion
12.5. Molarity changes with temperature; molality, weight percentage 25

Organize Your Thoughts!

All concentration units are a ratio of information
Develop a sense of the data that you have available
Solute Solvent

Solution

Solution
Volume

Mass
Mole
Reference MM
g/mol

MM
g/mol

d (g/mL)

12.5. Molarity changes with temperature; molality, weight percentage 26

Learning Check: What Does Molarity Tell Us?

M=moles solute/L solution. What are the m, X, %

and ppm concentration of a 1.0M solution of

KCl with a density of 0.99 g/mL
m = 1.1 X = 0.019 % =7.5 ppm=7.5(104)
Solute Solvent Solution Solution
Volume
KCl
(H2O)
Mass (g)
Mole
Reference

74.55

1.0
74.5510
g/mol

915.44
50.815
18.0153
g/mol

990
51.815

1L

0.99 (g/mL)

12.5. Molarity changes with temperature; molality, weight percentage 27

Learning Check: What Does Molality Tell Us?

m=moles solute/kg solvent.What are the M, X, %
and ppm concentration of 1.0 m KCl with a
density of 0.98 g/mL
M = 0.91 X = 0.018 % = 6.9 ppm =6.9104
Solute Solvent Solution Solution
Volume
KCl
(H2O)

Mass (g)
Mole
Reference

74.55

1000

1.0

55.51

74.5510
g/mol

18.0153
g/mol

1074.55
56.51
0.98 (g/mL)

1096 mL
=1.096 L

12.5. Molarity changes with temperature; molality, weight percentage 28

Learning Check: What Does Mole Fraction Mean?

Xsolute = moles solute/moles total. What are the M, m, % and
ppm concentration of a solution that has XKCl = 0.060
with a density of 0.87 g/mL
M =2.4 m = 3.5 % = 21 ppm =1.8105
Solute Solvent Solution Solution
Volume
KCl
(H2O)
Mass (g)

4.473

16.93

21.403

Mole

0.060

0.94

74.5510
g/mol

18.0153
g/mol

Reference

0.87 (g/mL)

24.601 mL
=.024601 L

12.5. Molarity changes with temperature; molality, weight percentage 29

Learning Check: What Does % Mass Tell Us

%=(mass solute/mass solution) x 100. What are the M, m, X and
ppm concentration of a 1.05 % KCl solution with a density of
1.15 g/mL
M =0.162 m = 0.142 X = 2.2610-4 ppm =1.21104
Solute Solvent Solution Solution
Volume
KCl
(H2O)
Mass (g)

1.05

Mole

.0140843 54.9255

Reference

74.5510
g/mol

98.95
18.0153
g/mol

100
55.0664

86.957 mL

1.15 (g/mL)

=.086957 L

12.5. Molarity changes with temperature; molality, weight percentage 30

Your turn!
Which of the following corresponds to a 3.5M
solution of NaCl with a density of 0.997 g/mL?
m

XNaCl

A.

0.0035

0.074

21

B.

3.5

0.080

0.21

C.

0.0035

0.074

0.21

D.

3.5

0.074

21

MM H2O: 18.0153; NaCl: 58.443

12.5. Molarity changes with temperature; molality, weight percentage 31

Raoults Law
Vapor pressure of a liquid varies as a function of
purity
X= mole fraction of solvent
P0= vapor pressure of pure solvent

Psolution=XsolventP0solvent
Psolution=XAP0A+XBPB0
Where A and B are both volatile components.

12.6. Solutes lower the vapor pressure of a solvent

32

Learning Check
The vapor pressure of 2-methylheptane is 233.95 torr at 55C.
3-ethylpentane has a vapor pressure of 207.68 at the same
temperature. What would be the pressure of the mixture of
78.0g 2-methylheptane and 15 g 3-ethylpentane?
Psolution=XAP0A+XBP0B
2-methylheptane
Chemical Formula: C8H18
Molecular Weight: 114.23

mole 2-methylheptane : 78.0g/114.23

g/mol = 0.68283 mol
mole 3-ethylpentane: 15g/100.2 g/mol
= 0.1497 mol

3-ethylpentane
Chemical Formula: C7H16
Molecular Weight: 100.2

X2-methylheptane=0.8202 ; X3-ethylpentane =10.8202 = 0.1798

P 0.8202 233.95 torr 0.1798 207.68 torr

P = 230 torr
12.6. Solutes lower the vapor pressure of a solvent

33

Learning Check
The vapor pressure of 2-methyl hexane is 37.986 torr at
15C. What would be the pressure of the mixture of
78.0g 2-methylhexane and 15 g naphthalene which is
nearly non-volatile at this temperature?
Psolution=XsolventP0solvent
naphthalene
Chemical
Formula:
C10H8
Molecular
Weight:
128.17

mol 2-methylhexane: 78.0g/100.2 g/mol

= 0.778443 mol

2-methylhexane
Chemical Formula: C7H16
Molecular Weight: 100.2

mol naphthalene: 15 g/128.17 g/mol =

0.11703
X2-methylhexane = 0.869309
Psolution = 0.869309 37.986 torr
P=33.02 torr

12.6. Solutes lower the vapor pressure of a solvent

34

Your Turn!
n-hexane and n-heptane are miscible in a large degree and
both volatile. If the vapor pressure of pure hexane is
151.28 mm Hg and heptane is 45.67 at 25, which
equation can be used to determine the mole fraction of
hexane in the mixture if the mixtures 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

12.6. Solutes lower the vapor pressure of a solvent

35

Solute Effects On Phase Changes:

Regardless of the identity of the dissolved particles, the
presence of an impurity will result in a change in the
boiling point and freezing point.
The effect is solely dependent on the nature of the
solvent, a factor labeled K, and the concentration of
particles present (m)
T=mK
boiling point elevation T=Tmix-Tpure
freezing Point Depression T=Tpure-Tmix

12.7. Solutions have lower freezing points and higher boiling points

36

Effects Of Impurities On Phase Changes

12.7. Solutions have lower freezing points and higher boiling points

37

Some BP/FP Constants

Solvent

Normal Kbp
BP (C) (C/m)

Normal
FP(C)

Kfp
(C/m)

Water

100.00

+.51

0.0

1.86

Acetic Acid

1118.3

+3.07

16.6

3.57

Benzene

80.2

+2.53

5.45

5.07

Camphor

207

+5.611

178.4

37.7

Chloroform

61.20

+3.63

Cyclohexane

80.7

2.69

6.5

20.0

12.7. Solutions have lower freezing points and higher boiling points

38

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?
-4F = 1.8 (C) + 32
-20. C

Tsolution m Kfp

1.86 C
(0 ( 20.) C ? m
m
11=m

12.7. Solutions have lower freezing points and higher boiling points

39

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 -4F?
from before:
-4F = 1.8 (C) + 32 =-20. C

mol solute
10.75 m
0.060 kg solvent

Tsolution m Kfp

0.6452 mol solute

1.86 C

(0 ( 20.) C ? m
m

650 g/mol solute

10.75=m
12.7. Solutions have lower freezing points and higher boiling points

40

Learning Check:
In the previous sample of a Sierra antifreeze mixture,
the freezing point is -4F? What will be its boiling
point?
from before:

-4F = 1.8 (C) + 32 =-20. C

Tfreezing solution m Kfp
and

T boilingsolution m Kbp

If it is the same concentration,

Tfreezing solution
T boilingsolution
m
Kfp
Kbp

TFreezing Point Kfp

m
TBoiling Point Kbp
(0 C - (-20 C)) 1.86 C/ m

Tmix - 100 C
0.51 C/ m
T=105 C

12.7. Solutions have lower freezing points and higher boiling points

41

Your Turn!
Beer is known to be around a 5% ethanol (C2H5OH)
solution with a density of 1.05 g/mL. What is its
expected boiling point?( Kf=0.51/m)
A.
B.
C.
D.
E.

100C
101C
102C
103C
Not enough information given

MM: H2O=18.0153; C2H5OH=46.069

12.7. Solutions have lower freezing points and higher boiling points

42

Osmosis
When two solutions are separated by a semi-permeable
membrane, solvent molecules flow from areas of low
concentration to areas of high concentration
As this occurs, the height of liquid rises in the higher
concentration solution, building up Osmotic pressure
()

12.8. Osmosis is flow of solvent through a semipermeable membrane 43

Relative Concentration Terms In Osmosis

Hypotonic solutions have lower ion
concentrations than the cells.
Hypertonic solutions have higher ion
concentrations than the cells
Isotonic solutions have the same ion
concentration as the cells

12.8. Osmosis is flow of solvent through a semipermeable membrane 44

Osmosis
=MRT
the concentration, is in molarity, M
T=Temperature, in Kelvin
R=Ideal Gas Constant, 0.082057 Latm/molK

The basis for kidney function, rising sap, and

dialysis

12.8. Osmosis is flow of solvent through a semipermeable membrane 45

Learning Check: Osmosis

A solution of D5W, 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 25C?

MRT

5g C6H12O6 1.0g soln mol C6H12O6 1000mL

M
100g solution mL soln
180.16g
L
0.277 mol 0.082057 L atm

298K
L
mol K

7 atm
12.8. Osmosis is flow of solvent through a semipermeable membrane 46

Learning Check
For a typical blood plasma, the osmotic pressure at body
temperature (37C) is 5409 mm Hg. If the dominant
solute is serum protein, what is the concentration of
serum protein?

MRT

5409 mm Hg

1atm

760 mm Hg

? mol 0.082057 L atm

7.117 atm

310.15K
L
mol K

0.280 mol
M
L

12.8. Osmosis is flow of solvent through a semipermeable membrane 47

Dialysis
Pores on the semi-permeable membrane may be of
varied size
In dialysis, the pores are fairly large, allowing transfer
of solvent, ions, and small proteins
Larger cells, such as red blood cells are prevented
from passing through the pores
The dialysis bath may be enriched in substances
lacking in the blood, and is hypotonic in waste
products in the blood
Exchange of vital components may be made

12.8. Osmosis is flow of solvent through a semipermeable membrane 48

Your Turn!
Suppose that your tap water has 250 ppb of dissolved
H2S , and that its density is about 1.0 g/mL. What
is its osmotic pressure at 25C?
A. 0.00058 atm
B. 0.064 atm
C. 0.059 atm
0.21 atm
D. None of these

MM: H2S =34.076

12.8. Osmosis is flow of solvent through a semipermeable membrane 49

Ionic Solutes Affect Colligative Properties

Differently Than Non-ionic Solutes
substances that ionize make more particles in a solution
than their own concentration suggests
i is a factor that demonstrates how many ions are formed
per formula unit or molecule
the apparent molality of particles is then im.
Tmeasured
Tcalculated assuming no ionization
Tmeasured
i
Tcalculated

imK
mK

12.9. Ionic solutes affect colligative properties differently than nonio

50

Learning Check
In preparing pasta, 2 L of water at 25C are combined
with about 15 g salt (NaCl, MM= 58.44g/mol) and
the solution brought to a boil. What is the expected
boiling point of the water?
T=imKbp
mass of water =volume density
=2000 mL 1.0 g/mL

m=0.25667 mol / 2kg

=2000g water = 2 kg

=0.123

mol NaCl = 15g / 58.44 g/mol

mol NaCl = 0.25667

T 100 C

2 ion 0.123m 0.51 C

mol
1
m

T=100.1 C
12.9. Ionic solutes affect colligative properties differently than nonio

51

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?
mass of water =volume density
=2000 mL 1.0 g/mL
=2000g water = 2 kg
0.196 m=? mol / 2kg
0.39215mol

T=imKbp

1 molec
0.51 C

0.10 C
?m
mol
m

m=.196
0.39215 mol = ?g / 342.30 g/mol
mass sucrose =130 g

12.9. Ionic solutes affect colligative properties differently than nonio

52