Properties of Solutions

When a mixture is homogeneous-it is called a solution.

17.1 Solution Composition

Mass percent is the percent solute by mass in the solution.
 grams of solute 
mass percent     100%
 grams of solution 
volume of solute
volume percent   100%
volume of solution

When liquids are mixed, the liquid present in the largest amount is
called solvent.
nA
mole fraction of component A =  A 
nA  nB
moles of solute
molality (m) 
kilograms of solvent
moles of solute
molarity (M) 
volume of solution (L)
Since the volume slightly changes with temperature, molarity is
dependent of temperature.

17.2 The Thermodynamics of Solution Formation

Pesticide DDT is fat-soluble  has been banned.
The solubilities of various vitamins  dosage
The insolubility of BaSO4  X-ray of the gastrointestinal tract

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 What factors affect solubility?
Polar solvents dissolve polar solutes;
Nonpolar solvents dissolve nonpolar solutes.
H3: exothermic < 0

H1 ; H2 : endothermic > 0

Enthalpy of solution: Hsoln = H1 + H2 + H3

endothermic

exothermic

Hsoln: H3>H1+H2 Hsoln: H3<H1+H2

exothermic < 0 endothermic > 0

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 NaCl(s)  Na+(g) + Cl-(g) H1o = -Hlatticeo = 786 kJ/mol
H2O(l) + Na (g) + Cl (g)  Na (aq) + Cl (aq)
+ - + -

Hhydo = H2o + H3o = -783 kJ/mol

NaCl(s)  Na+(aq) + Cl-(aq) Hsolno = Hhydo + H1o = 3 kJ/mol
Spontaneous: G = H –T S < 0 S1, S2, S3 and Ssoln > 0
Ssoln provides the principal driving force.
Not spontaneous: G = H –T S > 0 Hsolno > 0, Ssoln < 0

Ordering effect
The hydration of the ions
More charge density
Size and charge

Water form a cage to isolate the nonpolar solute form the bulk water
molecules. Water around the edge of the hole form even more
hydrogen bonds than normal found in bulk water molecule.
Ssoln0 is negative value, more order.
Unfavorable entropy results from cage formation is an important
reason why nonpolar solutes are insoluble in water

17.3 Factors Affecting Solubility

Structure Effects
Vitamins can be divided into two classes: fat-soluble (vitamins A,
D, E, and K) and water-soluble (vitamins B and C).

Describe nonpolar materials like vitamin A as hydrophobic

(water-fearing) and polar substances like vitamin C as hydrophilic
(water-loving).

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 vitamins A

vitamins C

Fat-soluble Water-soluble
Nonpolar materials as hydrophobic; polar materials as hydrophilic.
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Pressure Effects
Henry’s law: P = kH
The amount of gas dissolved in a solution is directly
proportional to the pressure of the gas above the solution.

Henry’s law is not obey by HCl gas in water since the dissociation
reaction : HCl(g)  H+(aq) + Cl-(aq)

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Temperature Effects for Aqueous Solutions

The dissolving rate increases

at higher temperature, but the
solubility may increase or
decrease with increasing
temperature.
The temperature dependent of
solubility:
The sign of Hosoln
By experiment

Sugar, KNO3, NaNO3, NaBr,

KBr, KCl
Na2SO4, Ce2(SO4)3,

The solubility of a gas in water decreases with increasing temperature.

Water as industrial cooling

Thermal pollution
Higher than ambient temperature
Lower O2 solubility
Less density; float
Blocking normal oxygen absorption

Boiler scale
CO32- + CO2 + H2O  2 HCO3-
2 HCO3-  CO32- + CO2 + H2O
CO32- + Ca2+  CaCO3
Reduce the efficiency of heat
transfer and blockage of pipes.

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 Reduce the efficiency of heat transfer and blockage of pipes..

1-hexyl-3-methylimidazolium 1-butyl-3-methylimidazolium
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17.4 The Vapor Pressure of Solutions

Nonvolatile solute:
No tendency to escape form solution into the vapor phase.

A nonvolatile solute lowers the vapor pressure of a solvents.

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 Raoult’s law (ideal solution):

Psoln = solvent Po solvent

solvent : mole fraction of solvent
Po solvent: the vapor pressure of the pure solvent

Example 17.1
20.0 g urea in 125 g of water. Psoln = 22.67 torr;
Po water = 23.76 torr. Calculate the molar mass of urea.
Pso ln 22.67 nH 2O
 H 2O    0.9541 
PH 2O 23.76 nH 2O  nurea
125
18 6.94
  w
nurea  0.335 
 nurea 6.94  nurea
125
M
18 w 20.0
6.94  6.62 M   59.7
nurea   0.335 nurea 0.335
0.9541
(NH2)2CO: 60.0

The lowering of vapor pressure depends on the number of solute

particles present in the solution. (1 mole of NaCl twice as expected)

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PTotal  PA  PB   A  PA   B  PB
0 0
Positive Negative

exothermic endothermic
Positive

Negative

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17.5 Boiling-Point Elevation and Freezing-Point Depression
Freezing-point depression, boiling-point elevation, and osmotic
pressure are called colligative properties, which depend on the
number and not on the identity, of the solute particles in an ideal
solution.

The water in the solution has a lower vapor pressure than that of pure ice.

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T = Kb msolute Kb: the molal boiling-point elevation constant
msolute: the molality of the solute

T = Kf msolute Kf: the molal freezing -point depression constant

A nonvolatile solute lowers the vapor pressure, and elevates the

boiling point, of solvent. T = Kb msolute
Kb: the molal boiling-point elevation constant
msolute: the molality of the solute

Example 17.2
18.00 g glucose in 150.0 g of water, Tb = 100.34 0C at 1 atm

T  100.34  100.0  0.34  K bmsolute

T 0.34 n
msolute    0.67  solute
K b 0.51 0.15
w 18
nsolute  0.67  0.15  
MW MW
MW  180 g / mol

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 The vapor pressure of ice
decreases more rapidly than
that of liquid water as
temperature decreases.
The freezing point is depressed.

T = Kf m solute
Solvent Solution msolute: the molality of the solute
Kf: the molal freezing -point depression constant
Example 17.3
-10.00F(-23.30C), ethylene glycol, C2H6O2, in 10.L H2O (d=1g/mL)
T 23.3 nsolute
msolute    12.5 
K f 1.86 10.0  1000  1
1000
w w
nsolute  125   ; w  7.76  103 g
MW 62.1

17.6 Osmotic Pressure

A semipermeable membrane allows solvent but not solute molecules
to pass through.

Osmosis: this flow of solvent into the solution through the

semipermeable membrane

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 Osmosis can be prevented by applying a pressure to the solution.
The pressure that just stops the osmosis is equal to the osmotic
pressure of the solution.

Osmosis pressure:
there is a greater pressure on the solution than on the pure solvent.
 = MRT
M: the molarity of the solution

PV  nRT
n
P RT  MRT
V
Example 17.4
1.0010-3 g in 1.00 mL water;  = 1.12 torr at 250C (1 torr = 1 mmHg)
1.12
  MRT   M (0.08206)( 25  273)
760
1.00  103
1.47  103  MW (0.08206)( 298)
1.00  103
(0.08206)( 298)
MW 
1.47  103
 1.66  104 g / mol

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Dialysis: the membrane allows transfer of both solvent and small solute

Application of dialysis:
Artificial kidney machines
to purify the blood
A cellophane tube as the
semipermeable membrane
Dialyzing solution:
The same concentration of
ions and small molecules as
blood  keep in blood
None of the waste products
The function of an artificial kidney  wash out

Isotonic solutions: have identical osmotic pressure

Fluids administered intravenously must be isotonic with body fluids.

Isotonic hypotonic hypertonic

b) Hypotonic solution:: has an osmotic pressure lower than that of
cell fluids, the cell will rupture because of a net
transfer of water into the cells.  lysis
c) Hypertonic solution: has an osmotic pressure higher than that of
cell fluids, the cell will shrivel because of a net transfer
of water out of the cells.  crenation 26

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 van’t Hoff equation:  = i MRT  = 7.7 atm at 250C NaCl(aq), i=2

Example 17.5   iMRT  7.7  iM (0.08206)( 298)

7.7
iM   0.315
(0.08206)( 298)
0.315
M  0.1575
2

Reverse osmosis: if a solution in

contact with pure solvent across
a semipermeable membrane is
subjected to an external pressure
larger than its osmotic pressure.

The pressure causes a net flow of solvent from the solution to the solvent.
Reverse osmosis: the desalination (removal of dissolved salts)

Reverse osmosis,
The desalination

seawater
hypertonic
not drinkable

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17.7 Colligative Properties of Electrolysis Solution
T = Kb msolute; T = Kf msolute ;  = MRT
T = i Kb msolute; T =i Kf msolute ;  = i MRT
0.10 m glucose, T = Kf m solute = 1.86  0.10 = 0.186 0C
0.10 m NaCl(aq), T = 2 Kf m solute = 2  1.86  0.10 = 0.362 0C
n particle
van’t Hoff factor (i): i 
nsolute
NaCl: i = 2 (Na+, Cl-)
K2SO4: i = 3 ( 2 K+, SO42-)
Fe3(PO4)2; i = 5 ( 3 Fe2+, 2 PO43-)
0.10 m NaCl: i = 1.87
0.0010 m NaCl: i = 1.97 29

Ion pairing:
The concentration of electrolyte
Charge of ions
Example 17.6
0.10 M Fe(NH4)2(SO4)2:
 = 10.8 atm at 250C
i(expected) = 5

Fe(NH4)2(SO4)2  Fe2+ + 2 NH4+ + 2 SO42-

  iMRT
 10.8
i 
MRT 0.1  0.08206  298
 4.42

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 17.8 Colloids
Tyndall effect: the scattering of light by particles
The true solution: the ions and molecules dispersed in the solution
are too small to scatter the light
A colloidal dispersion or a colloid: a suspension of tiny particles in
some medium, which will scatter the light

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Electrostatic repulsion
Not easily aggregate to form particles that are large enough to precipitate

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Coagulation: the destruction of a colloid by heating or by adding an
electrolyte

When smoke is passed through an

electrostatic precipitator, the suspended
solids are removed.

The charged plates attract the colloidal particles

because of their ion layers and thus remove
them from the smoke.

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