TABLE OF C ONTENTS

T YPES OF S OLUTIONS

C HEM 16 G ENERAL C HEMISTRY 1

T HE S OLUTION P ROCESS
Enthalpy of Solution
Solution Formation and Equilibrium

11 S OLUTIONS
Dr. Gil C. Claudio
University of the Philippines, Diliman

Q UANTITATIVE WAYS OF E XPRESSING C ONCENTRATION

C OLLIGATIVE P ROPERTIES OF N ONVOLATILE N ONELECTROLYTE S OLUT

Vapor Pressures Lowering and Raoults Law
Boiling Point Elevation and Freezing Point Depression
Osmotic Pressure

First Semester 2014-2015

T HE VAN T H OFF FACTOR

R EFERENCES

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.

S OLUTIONS
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

S OME C OMMON S OLUTIONS

S OLUTE AND S OLVENT IFA S

PHMB 10 E , TABLE 13.1, P 558

Solution
Gaseous solutions
Air
Natural gas
Liquid solutions
Seawater
Vinegar
Soda pop
Solid solutions
Yellow brass
Palladium Hydrogen

Three kinds of intermolecular interactions are involved in solution

formation:

Components
N2 , O2 , et.al.
CH4 , C2 H6 , et.al.

1. Solute-solute interactions between solute particles must be

overcome to disperse the solute particles through the solvent.

H2 O, NaCl, et.al.
H2 O, CH3 COOH (acetic acid)
H2 O, CO2 , C12 H22 O11 (sucrose), et.al.
Cu, Zn
Pd, H2

E NTHALPY OF S OLUTION

pure solvent

(b)

pure solute

(c)

separated solvent
and solute molecules
pure solvent +
pure solute

3. Solvent-solute interactions between the solvent and solute

particles occur as the particles mix.

S OLUTE -S OLVENT I NTERACTIONS 1: I DEAL

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)

2. Solvent-solvent interactions between solvent particles must

be overcome to make room for the solute particles in the
solvent.

separated
solvent molecules
separated
solute molecules

Hb > 0

solution

Hc < 0

solution

Hsoln

Hsoln = Ha + Hb + Hc

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.

Ha > 0

Hsoln 0

e.g., mixtures of liquid hydrocarbons

S OLUTE -S OLVENT I NTERACTIONS 2: N ONIDEAL

S OLUTE -S OLVENT I NTERACTIONS 3: N ONIDEAL

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

S OLUTE -S OLVENT I NTERACTIONS 4: H ETEROGENOUS

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.

P REDICTING S OLUTION F ORMATION

PHMB 10 E , E XAMPE 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:
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

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.

F ORMATION OF I ONIC S OLUTIONS

D YNAMIC E QUILIBRIUM IN S OLUTIONS

NaCl(s)

Na+ (g) + Cl (g)

H1 > 0

Na+ (g)

H O

Na+ (aq)

H2 < 0

H2 O

Cl (aq)

H2 O

Cl (g)
NaCl(s)

H3 < 0

Na (aq) + Cl (aq)

Crystallization, the opposite process of solution, occurs when

solute particles in solution collide with the surface of the solid and
reattach.

Hsoln

dissolve

solute + solvent

solution
crystallize

where

H1 = - lattice energy

H2/3 = hydration energy of Na+ /Cl

Hsoln = H1 + H2 + H3

for NaCl, Hsoln +5 kJ/mol

S ATURATED S OLUTIONS

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.

When the rates of these opposing processes become equal, a

dynamic equilibrium is established.

S OLUBILITY

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.

S OLUBILITY: S OLVENT-S OLUTE I NTERACTIONS

S OLUBILITIES OF A LCOHOLS IN H 2 O AND C 6 H 14

Solubilities of some alcohols in water and in hexane at 20 C,

expressed in mol alcohol/100 g solvent
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.

S OLUBILITY OF G ASES : P RESSURE E FFECTS

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.

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

solubility
in H2 O

0.11
0.030
0.0058

solubility
in C6 H14
0.12

H ENRY S L AW

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

U SING H ENRY S L AW

S OLUBILITY OF G ASES : T EMPERATURE E FFECTS

PHMB 10 E , E XAMPLE 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

S OLUBILITY: T EMPERATURE E FFECTS

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.

M OLARITY

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

The solubility of most solid solutes in water increases as the
solution temperature increases.

with some exceptions

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.

M OLALITY

M OLALITY AND M OLARITY

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.

M OLE F RACTION AND M OLE P ERCENT

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.

x i + xj + x k + = 1
A mole percent is a mole fraction expressed on a percentage
basis, that is, mole fraction 100%.

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.

M ASS AND V OLUME P ERCENT

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 M ILLION /B ILLION /T RILLION

C ONCENTRATION IN VARIOUS U NITS

PHMB 10 E , E XAMPLE 13-1, PP 560-561

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.
mass of component in soln
106
ppm of a component =
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).

1 ppm = 1 mg/L

1 ppb = 1 g/L

1 ppt = 1 ng/L

C ONVERTING M OLARITY TO M OLE F RACTION

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

C OLLIGATIVE P ROPERTIES

PHMB 10 E , E XAMPLE 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

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.

VAPOR P RESSURE L OWERING

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.

R AOULT S L AW

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 xA
PA = xA PA
Strictly speaking, Raoults law applies only to ideal solutions and
to all volatile components of the solutions.

VAPOR P RESSURE OF A S OLUTION

However, even in nonideal solutions, the law often works

reasonably well for the solvent in dilute solutions (e.g.,
xsolv > 0.98).

I DEAL S OLUTION OF V OLATILE L IQUIDS

BLBMWS 13 E , E XERCISE 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

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 = xA PA
PB

= xB PB

Ptotal = PA + PB

VAPOR P RESSURES OF I DEAL S OLUTIONS

B OILING P OINT E LEVATION

PHMB 10 E , E XAMPLE 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?

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.

ANSWER: Pbenzene = 47.6 mmHg, Ptoluene = 14.2 mmHg, and

Ptotal = 61.8 mmHg.

B OILING P OINT E LEVATION

F REEZING P OINT D EPRESSION

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

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.

F REEZING P OINT D EPRESSION

The decrease in the freezing point of a solution, relative to the

pure solvent, depends on the molality of the solute.
Tf = Tf (solution) Tf (solvent) = iKf m
where

m is the molality of the solute

Kf is the molal freezing point depression constant for the

solvent

and i is the vant Hoff factor, i = 1 for nonelectrolytes

S OME C ONSTANTS
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

C ALCULATION OF BP AND FP

M OLAR M ASS FROM FP D EPRESSION

BLBMWS 13 E , E XERCISE 13.8, PP 553-554

BLBMWS 13 E , E XERCISE 13.10, P 557

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 Tf = 10.0 C

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

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

O SMOSIS AND O SMOTIC P RESSURE

O SMOTIC P RESSURE : D IAGRAM

Final State

Inital State
P 1a

P 2a

P 1b

P 2b

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.
water

semi-permeable membrane

dissolved salt

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

O SMOTIC P RESSURE : E QUATION

The osmotic pressure is given by

R ELATIVE P RESSURES

Given two solutions separated by a semipermeable membrane

= iMRT

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.

M is the concentration in molarity

R is the ideal gas constant

If one solution is of lower osmotic pressure, it is hypotonic

with respect to the more concentrated solution.

T is the absolute temperature

and i is the vant Hoff factor, i = 1 for nonelectrolytes

The more concentrated solution is hypertonic with respect to

the dilute solution.

where

O SMOSIS IN B LOOD C ELLS

O SMOSIS IN P LANTS

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

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

O SMOTIC P RESSURE C ALCULATIONS

M OLAR M ASS FROM O SMOTIC P RESSURE

BLBMWS 13 E , E XERCISE 13.9, P 556

BLBMWS 13 E , E XERCISE 13.11, P 557

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

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

I ON PAIRS IN E LECTROLYTES

T HE VAN T H OFF FACTOR

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 Tf 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.

S OME VAN T H OFF 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

0.00100 m
1.00
1.97
1.82
2.84
2.89

expected
1.00
2.00
2.00
3.00
3.00

Instead of using i = number of separated ions, we can calculate

the vant Hoff Factor from freezing-point depression using
i=

Tf (measured)
Tf (calculated from nonelectrolyte)