Chem 16 General Chemistry 1

11 Solutions

Dr. Gil C. Claudio

First Semester 2014-2015
Table of Contents

Contents
1 Types of Solutions

2 The Solution Process

2.1 Enthalpy of Solution . . . . . . . . . . . . . . . . . . . . . . . . .
2.2 Solution Formation and Equilibrium . . . . . . . . . . . . . . . .

2
2
4

3 Quantitative Ways of Expressing Concentration

4 Colligative Properties of Nonvolatile Nonelectrolyte Solutions

4.1 Vapor Pressures Lowering and Raoults Law . . . . . . . . . . .
4.2 Boiling Point Elevation and Freezing Point Depression . . . . .
4.3 Osmotic Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . .

7
7
8
9

5 The vant Hoff Factor

11

References
References of these notes
General Chemistry, 10th ed, by Ralph H. Petrucci, F. Geoffrey Herring,
Jeffy D. Madura, and Carey Bisonnette.
Chemistry: The Central Science, 13th ed., by Theodore L. Brown, H. Eugene
LeMay Jr., Bruce E. Bursten, Catherine J. Murphy, Patrick M. Woodward,
and Matthew W. Stoltzfus.

1 Types of Solutions
Solutions
A homogeneous mixture (solution) is a mixture of elements and/or
compounds that has a uniform composition and properties within a given
sample. However, the composition and properties may vary from one sample
to another.
The solvent is the component that is present in the greatest quantity or
that determines the state of matter in which a solution exists.
Other solution components, called solutes, are dissolved in the solvent.
A concentrated solution has a relatively large quantity of dissolved
solute(s), and a dilute solution has only a small quantity.
solid (alloys), liquid, and gaseous solutions

Some Common Solutions

PHMB 10e, Table 13.1, p 558
Solution
Gaseous solutions
Air
Natural gas
Liquid solutions
Seawater
Vinegar
Soda pop
Solid solutions
Yellow brass
Palladium Hydrogen

Components
N2 , O2 , et.al.
CH4 , C2 H6 , et.al.
H2 O, NaCl, et.al.
H2 O, CH3 COOH (acetic acid)
H2 O, CO2 , C12 H22 O11 (sucrose), et.al.
Cu, Zn
Pd, H2

2 The Solution Process

2.1

Enthalpy of Solution

Solute and Solvent IFAs

Three kinds of intermolecular interactions are involved in solution
formation:
1. Solute-solute interactions between solute particles must be overcome to
disperse the solute particles through the solvent.
2. Solvent-solvent interactions between solvent particles must be
overcome to make room for the solute particles in the solvent.
3. Solvent-solute interactions between the solvent and solute particles
occur as the particles mix.
Enthalpy of Solution
In the formation of some solutions, heat is given off to the
surroundings (exothermic, Hsoln < 0); in other cases, heat is absorbed
(endothermic,Hsoln > 0 ). We can look at the solution process in three steps.
(a)

pure solvent

(b)

pure solute

(c)

separated solvent
and solute molecules
pure solvent +
pure solute

separated
solvent molecules
separated
solute molecules

Ha > 0
Hb > 0

solution

Hc < 0

solution

Hsoln

Hsoln = Ha + Hb + Hc

Solute-Solvent Interactions 1: Ideal

Given the solvent (A) and the solute (B)
If A-A, B-B, and A-B IFAs are of the same type and of equal strength: the
solute and solvent molecules mix randomly, and homogeneous mixture
(or solution) results.
Properties of these solutions can generally be predicted from the
properties of the pure components, thus they are called ideal solutions.
Hsoln 0
e.g., mixtures of liquid hydrocarbons
2

Solute-Solvent Interactions 2: Nonideal

Given the solvent (A) and the solute (B)
If the attractive forces of A-B > A-A and A-B > B-B: a solution also forms.
Their properties generally cannot be predicted, thus they are called
nonideal,
A-B interactions release more heat than A-A and B-B, thus the solution
process is exothermic Hsoln < 0
e.g., solutions of acetone and chloroform, H-bonding possible in the
solution, but not in the pure liquids of both
Solute-Solvent Interactions 3: Nonideal
Given the solvent (A) and the solute (B)
If the attractive forces of A-B is slightly less than A-A and B-B, complete
mixing may still occur, but the solution formed is nonideal
The solution process is endothermic Hsoln > 0
e.g., mixtures of carbon disulfide (CS2 ), a nonpolar liquid, and acetone, a
polar liquid.
Solute-Solvent Interactions 4: Heterogenous
Given the solvent (A) and the solute (B)
If attractive forces of A-B A-A and A-B B-B, the components remain
segregated in a heterogeneous mixture
Dissolution does not occur to any significant extent.
e.g., octane and water
Predicting Solution Formation
PHMB 10e, Exampe 13-3, p 565
Predict whether or not a solution will form in each of the following
mixtures and whether the solution is likely to be ideal:
1. ethyl alcohol, CH3 CH2 OH, and water;
2. the hydrocarbons hexane, CH3 (CH2 )4 CH3 , and octane, CH3 (CH2 )6 CH3 ;
3. octanol, CH3 (CH2 )6 CH2 OH, and water.
ANSWERS
1. We expect ethyl alcohol and water to form nonideal solutions.
2. We expect a solution to form, and it should be nearly ideal.
3. We do not expect a solution to form.
Formation of Ionic Solutions
NaCl(s)

Na (g)

H2 O

H2 O

Cl (g)
NaCl(s)

Na+ (g) + Cl (g)

+

Na (aq)

H1 > 0
H2 < 0

Cl (aq)

H3 < 0

H2 O

Na+ (aq) + Cl (aq)

Hsoln

where
3

 H1 = - lattice energy
H2/3 = hydration energy of Na+ /Cl
Hsoln = H1 + H2 + H3
for NaCl, Hsoln +5 kJ/mol

2.2

Solution Formation and Equilibrium

Dynamic Equilibrium in Solutions

Crystallization, the opposite process of solution, occurs when solute
particles in solution collide with the surface of the solid and reattach.
dissolve

solution
solute + solvent

crystallize

When the rates of these opposing processes become equal, a dynamic

equilibrium is established.
Saturated Solutions
A saturated solution is one that contains the maximum quantity of solute
that is normally possible at the given temperature. An unsaturated solution
contains less solute than the solvent is capable of dissolving under the given
conditions.
A supersaturated solution contains more solute than normally expected
for a saturated solution, usually prepared from a solution that is saturated at
one temperature by changing its temperature to one where supersaturation
can occur.
Solubility
The solubility of a particular solute in a particular solvent is the maximum
amount of the solute that can dissolve in a given amount of the solvent at a
specified temperature, assuming that excess solute is present.
The extent to which one substance dissolves in another depends on the
nature of both substances. It also depends on temperature and, at least
for gases, on pressure.
Solubility: Solvent-Solute Interactions
In general, the stronger the attractions between solute and solvent
molecules, the greater the solubility of the solute in that solvent.
e.g., polar liquids tend to dissolve in polar solvents
Liquids that mix in all proportions (e.g., acetone and water) are miscible,
whereas those that do not dissolve in one another are immiscible.
Solubilities of Alcohols in H2 O and C6 H14
Solubilities of some alcohols in water and in hexane at 20 C, expressed in
mol alcohol/100 g solvent
alcohol
methanol CH3 OH
ethanol CH3 CH2 OH
propanol CH3 CH2 CH2 OH
butanol CH3 CH2 CH2 CH2 OH
pentanol CH3 CH2 CH2 CH2 CH2 OH
hexanol CH3 CH2 CH2 CH2 CH2 CH2 OH
4

solubility
in H2 O

0.11
0.030
0.0058

solubility
in C6 H14
0.12

Solubility of Gases: Pressure Effects

The solubility of a gas in any solvent is increased as the partial pressure of
the gas above the solvent increases.
The solubilities of solids and liquids are not appreciably affected by
pressure.
Henrys Law
The relationship between pressure and gas solubility is expressed by
Henrys law
C = k Pgas
where
C is the solubility of as gas in a particular solvent at a fixed T
Pgas is the partial pressure of the gas above
k is a proportionality constant
Using Henrys Law
PHMB 10e, Example 13-5, p 572
At 0 C and an O2 pressure of 1.00 atm, the aqueous solubility of O2 (g) is
48.9 mL O2 per liter. What is the molarity of O2 in a saturated water solution
when the O2 is under its normal partial pressure in air, 0.2095 atm?
ANSWER: 4.57 104 M O2
Solubility of Gases: Temperature Effects
We cannot make an all-inclusive generalization about the effect of
temperature on the solubilities of gases in solvents.
The solubilities of most gases in water decrease with an increase in
temperature.
For solutions of gases in organic solvents, the situation is often the
reverse.
The solubility behavior of the noble gases in water is more complex.
Solubility: Temperature Effects
The solubility of most solid solutes in water increases as the solution
temperature increases.
with some exceptions

3 Quantitative Ways of Expressing Concentration

Molarity
The molarity M of a solute in a solution is defined as
molarity =

moles of solute
L of solution

E.g., if you dissolve 0.500 mol Na2 CO3 in enough water to form 0.250 L
solution, the molarity of Na2 CO3 in the solution is 2.00 M.

Molality
Molality m is a solution concentration expressed as the amount of solute,
in moles, divided by the mass of solvent, in kg.
molality =

moles of solute
kg of solvent

E.g., if you mix 0.200 mol NaOH and 0.500 kg of water, the concentration of
the solution is 0.400 m in NaOH.
Molality and Molarity
Molarity M depends on the volume of solution, whereas molality m
depends on the mass of solvent.
When water is the solvent, the m M for dilute solutions because 1 kg
of solvent 1 kg of solution 1 L.
The molality of a given solution does not vary with temperature because
masses do not vary with temperature. Not true for molarity due to the
temperature dependent volume expansion of the solvent. Thus, molality
is often used when a solution is to be used over a range of temperatures.
Mole Fraction and Mole Percent
Mole fraction xi describes a mixture in terms of the fraction of all the
molecules that are of a particular type. It is the amount of one component,
in moles, divided by the total amount of all the substances in the mixture.
xi =

moles of component i
total amt of all solution components in moles

The sum of the mole fractions of all the solution components is 1.

xi + x j + x k + = 1
A mole percent is a mole fraction expressed on a percentage basis, that is, mole
fraction 100%.
Mass and Volume Percent
Mass percentage of a component in a solution is
mass % of a component =

mass of component in soln

100
total mass of soln

Volume percentage of a component of a solution is

volume % of a component =

volume of component in soln

100
total volume of soln

Another possibility is to express the mass of a solute and the volume of the
solution.
mass/volume % of a component =

mass of component in soln

100
total volume of soln

Parts per Million/Billion/Trillion

We often express the concentration of very dilute solutions in parts per
million (ppm), parts per billion (ppb), or parts per trillion (ppt).
Similar to mass % but use 106 (a million), 109 (a billion), or 1012 (trillion)
in place of 100 as a multiplier for the ratio of the mass of solute to the
mass of solution.
6

mass of component in soln

106
total mass of soln
1 ppm is 1 g of a solute in 106 g of solution or 1 mg solute per 1 kg solution (
1 L water solution).
ppm of a component =

1 ppm = 1 mg/L
1 ppb = 1 g/L
1 ppt = 1 ng/L
Concentration in Various Units
PHMB 10e, Example 13-1, pp 560-561
An ethanol-water solution is prepared by dissolving 10.00 mL of ethanol,
CH3 CH2 OH (d =0.789 g/mL), in a sufficient volume of water to produce
100.0 mL of a solution with a density of 0.982 g/mL. What is the concentration
of ethanol in this solution expressed as (a) volume percent; (b) mass percent;
(c) mass/volume percent; (d) mole fraction; (e) mole percent; (f) molarity; (g)
molality?
ANSWERS: (a) 10.0%; (b) 8.03%; (c) 7.89%; (d) 0.0330; (e) 3.30%; (f) 1.71
M CH3 CH2 OH; (g) 1.89 m CH3 CH2 OH
Converting Molarity to Mole Fraction
PHMB 10e, Example 13-2, p 561
Laboratory ammonia is 14.8 M NH3 (aq) with a density of 0.8980 g/mL.
What is xNH3 in this solution?
ANSWER: 0.292

4 Colligative
Properties
Nonelectrolyte Solutions

of

Nonvolatile

Colligative Properties
Colligative propertiesvapor pressure lowering, freezing point
depression, boiling point elevation, osmotic pressurehave values that
depend on the number of solute particles in a solution but not on their
identity.

4.1

Vapor Pressures Lowering and Raoults Law

Vapor Pressure Lowering

Given a homogeneous solution of a volatile liquid solvent and a nonvolatile
solute, the solvent molecules are stabilized in their liquid state by the mixing
and thus have a lower tendency to escape into the vapor state. Therefore,
the vapor pressure of the solvent is lower than the vapor pressure of the pure
solvent.
Raoults Law
Raoults law states that the vapor pressure of a solution component PA is
equal to the product of the vapor pressure of the pure liquid PA and its mole
fraction in solution x A
PA = x A PA
Strictly speaking, Raoults law applies only to ideal solutions and to all volatile
components of the solutions.
However, even in nonideal solutions, the law often works reasonably
well for the solvent in dilute solutions (e.g., xsolv > 0.98).
7

Vapor Pressure of a Solution

BLBMWS 13e, Exercise 13.7, pp 549-550
Glycerin C3 H8 O32 is a nonvolatile nonelectrolyte with a density of 1.26
g/mL at 25 C. Calculate the 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, and its density is 1.00 g/mL.
ANSWER: 23.2 torr
Ideal Solution of Volatile Liquids
If two volatile liquids (A and B) are mixed and form an ideal solution,
both liquids contribute to the total vapor pressure of the solution. The partial
pressures contributed by each follows Raoults law, and the total pressure is
the sum of the partial pressures
PA
PB
Ptotal

x A PA
x B PB

=
=
=

PA + PB

Vapor Pressures of Ideal Solutions

PHMB 10e, Example 13-6, p 574
The vapor pressures of pure benzene and pure toluene at 25 C are 95.1 and
28.4 mmHg, respectively. A solution is prepared in which the mole fractions
of benzene and toluene are both 0.500. What are the partial pressures of the
benzene and toluene above this solution? What is the total vapor pressure?
ANSWER: Pbenzene = 47.6 mmHg, Ptoluene = 14.2 mmHg, and Ptotal = 61.8
mmHg.

4.2

Boiling Point Elevation and Freezing Point Depression

Boiling Point Elevation

The normal boiling point of a liquid is the temperature at which its vapor
pressure equals 1 atm.
Because the solution has a lower vapor pressure than the pure solvent,
a higher temperature is required for the solution to achieve a vapor
pressure of 1 atm.
As a result, the boiling point of the solution is higher than that of the pure
solvent.
Boiling Point Elevation
The increase in the boiling point of a solution, relative to the pure solvent,
depends on the molality of the solute.
Tb = Tb (solution) Tb (solvent) = iKb m
where
m is the molality of the solute
Kb is the molal boiling point elevation constant for the solvent
and i is the vant Hoff factor, i = 1 for nonelectrolytes

Freezing Point Depression

The freezing point of a solution is the temperature at which the first crystals
of pure solvent form in equilibrium with the solution.
the freezing point of the solution is lower than that of the pure liquid.
Freezing Point Depression
The decrease in the freezing point of a solution, relative to the pure solvent,
depends on the molality of the solute.
T f = T f (solution) T f (solvent) = iK f m
where
m is the molality of the solute
K f is the molal freezing point depression constant for the solvent
and i is the vant Hoff factor, i = 1 for nonelectrolytes
Some Constants
Freezing-point depression and boiling-point elevation constants
solvent
Acetic acid
Benzene
Nitrobenzene
Phenol
Water
Ethanol
carbon tetrachloride
chloroform

normal FP
C
16.6
5.53
5.7
41
0.00
-114.6
-22.3
-63.5

Kf
C/m
3.90
5.12
8.1
7.27
1.86
1.99
29.8
4.68

normal BP
C
118
80.10
210.8
182
100.0
78.4
76.8
61.2

Kb
C/m
3.07
2.53
5.24
3.56
0.512
1.22
5.02
3.63

Calculation of BP and FP
BLBMWS 13e, Exercise 13.8, pp 553-554
Automotive antifreeze contains ethylene glycol, CH2 (OH)CH2 (OH) a
nonvolatile nonelectrolyte, in water. Calculate the boiling point and freezing
point of a 25.0% by mass solution of ethylene glycol in water.
ANSWERS: Tb = 2.7 C and T f = 10.0 C
Molar Mass from FP Depression
BLBMWS 13e, Exercise 13.10, p 557
A solution of an unknown nonvolatile nonelectrolyte was prepared by
dissolving 0.250 g of the substance in 40.0 g of CCl4 . The boiling point of the
resultant solution was 0.357 C higher than that of the pure solvent. For CCl4 ,
Kb = 5.02 C/m. Calculate the molar mass of the solute.
ANSWER: 88.0 g/mol

4.3

Osmotic Pressure

Osmosis and Osmotic Pressure

Osmosis is the net flow of solvent molecules through a semipermeable
membrane, from a more dilute solution (or from the pure solvent) into a more
concentrated solution.
Osmotic pressure is the pressure that would have to be applied to a
solution to stop the passage through a semipermeable membrane of solvent
molecules from the pure solvent.
9

Osmotic Pressure: Diagram

Final State

Inital State
P 1a

P 2a

P 1b

P 2b

water

semi-permeable membrane

dissolved salt

commons.wikimedia.org/wiki/File:Osmose en.svg

Osmotic Pressure: Equation

The osmotic pressure is given by
= iMRT
where
M is the concentration in molarity
R is the ideal gas constant
T is the absolute temperature
and i is the vant Hoff factor, i = 1 for nonelectrolytes
Relative Pressures
Given two solutions separated by a semipermeable membrane
If two solutions of identical osmotic pressure are separated by a
semipermeable membrane, no osmosis will occur. The two solutions are
isotonic with respect to each other.
If one solution is of lower osmotic pressure, it is hypotonic with respect
to the more concentrated solution.
The more concentrated solution is hypertonic with respect to the dilute
solution.
Osmosis in Blood Cells

commons.wikimedia.org/wiki/File:Osmotic pressure on blood cells diagram.svg

10

Osmosis in Plants

commons.wikimedia.org/wiki/File:Turgor pressure on plant cells diagram.svg

Osmotic Pressure Calculations

BLBMWS 13e, Exercise 13.9, p 556
The average osmotic pressure of blood is 7.7 atm at 25 C. What molarity of
glucose C6 H12 O6 will be isotonic with blood?
ANSWER: 0.31 M
Molar Mass from Osmotic Pressure
BLBMWS 13e, Exercise 13.11, p 557
The osmotic pressure of an aqueous solution of a certain protein was
measured to determine the proteins molar mass. The solution contained 3.50
mg of protein dissolved in sufficient water to form 5.00 mL of solution. The
osmotic pressure of the solution at 25 C was found to be 1.54 torr. Treating the
protein as a nonelectrolyte, calculate its molar mass.
ANSWER: 8.45 103 g/mol

5 The vant Hoff Factor

Ion Pairs in Electrolytes
The colligative properties of solutions depend on the total concentration of
solute particles, regardless of whether the particles are ions or molecules.
since NaCl Na+ (aq) + Cl (aq), then i = 2
expected T f for a 0.100 m NaCl solution is 0.372 C, but it is only
0.348 C.
The difference is due to electrostatic attractions between ions.
As the ions move about in solution, ions of opposite charge collide and
stick together for brief moments. While they are together, they behave
as a single particle called an ion pair.
The vant Hoff Factor
Instead of using i = number of separated ions, we can calculate the vant
Hoff Factor from freezing-point depression using
i=

T f (measured)
T f (calculated from nonelectrolyte)

11

Some vant Hoff Factors

Measured and expected vant Hoff factors for several substances at 25 C
compound
sucrose
NaCl
MgSO4
K2 SO4
Pb(NO3 )2

0.100 m
1.00
1.87
1.21
2.32
2.13

0.0100 m
1.00
1.94
1.53
2.70
2.63

12

0.00100 m
1.00
1.97
1.82
2.84
2.89

expected
1.00
2.00
2.00
3.00
3.00