SOLUTIONS
Objectives
At the end of the exercise the students should be able to:
1. define and classify solution;
2. identify the solute(s) and the solvent in a solution;
3. discuss the factors that affect the solubility of a substance;
4. state the different ways of increasing the rate of dissolution of a solute in a given solvent;
5. express qualitatively and quantitatively the concentration of solution;
6. convert one concentration unit to another;
7. calculate the amount (mass or volume) of a substance needed to prepare a solution; and
8. prepare solutions from initial component substances and by dilution of existing solutions.
A solution is a homogeneous mixture of two or more substances. It is characterized by its components. The substance
that determines the state of the solution is the solvent. Normally, the solvent is the component present in the greatest
quantity. All other substances in the solution are called the solutes. Solutions may be classified into six types depending
on the original states (solid, liquid, or gas) of the solution components. Table 1 gives examples of each of these types.
Table 1. Types of Solutions
SOLUTE SOLVENT STATE OF RESULTING SOLUTION EXAMPLES
Gas Gas Gas Air
Gas Liquid Liquid Soda water (CO2 in Water)
Gas Solid Solid H2 gas in Palladium
Liquid Liquid Liquid Ethanol in water
Solid Liquid Liquid NaCl in water
solid Solid Solid Brass (Cu/Zn), Solder (Sn/Pb)
Except for gaseous solutions, there is usually an upper limit to the amount of solute that will dissolve in a given amount
of solvent. When the limit has been reached, the solution can hold no more solute and is saturated. The concentration
of a saturated solution is the solubility of the substance in that particular solvent at a specified temperature.
Effect of Temperature and Pressure on Solubility
Nature of the Solute and Solvent. In general “like dissolves like”. A polar or ionic solute dissolves in a polar solvent, and
a non-polar solute dissolves in a non-polar solvent. Therefore, polar or ionic molecules like sugar and sodium
chloride, respectively, dissolve in water molecules as these are polar. On the other hand, non-polar molecules like
naphthalene dissolve in solvents like benzene and carbon tetrachloride as these are non-polar. The solubility of ionic
compounds is the result of the strong electrostatic interaction between the ions of the solute and the polar molecules
of the solvent. On the other hand, the solubility of non-polar solutes is the result of similar solute-solute, solute-solvent,
and solvent-solvent interactions.
Temperature. The solubility of solutes is dependent on temperature. When a solid dissolves in a liquid, a change in the
physical state of the solid analogous to melting takes place. Heat is required to break the bonds holding the
molecules in the solid together. At the same time, heat is given off during the formation of new solute-solvent
bonds.
CASE I: Decrease in solubility with temperature
If the heat given off in the dissolving process is greater than the heat required to break apart the solid, the net
dissolving reaction is exothermic (energy given off). The addition of more heat (increases temperature) inhibits the
dissolving reaction since excess heat is already being produced by the reaction (e.g. solubility of calcium oxide
decreases with the increase in temperature). This situation is not very common where an increase in temperature
produces a decrease in solubility.
CASE II: Increase in solubility with temperature
If the heat given off in the dissolving reaction is less than the heat required to break apart the solid, the net
dissolving reaction is endothermic (energy required). The addition of more heat facilitates the dissolving reaction by
providing energy to break bonds in the solid. This is the most common situation where an increase in temperature
produces an increase in solubility for solids. The use of first-aid instant cold packs is an application of this solubility
principle. A salt such as ammonium nitrate is dissolved in water after a sharp blow breaks the containers for each.
The dissolving reaction is endothermic - requires heat. Therefore the heat is drawn from the surroundings, the pack
feels cold.
CASE III: Solubility of Gases vs. Temperature
Gases are more soluble in cold solvent than in hot solvent. The reason for this gas solubility relationship with
temperature is very similar to the reason that vapor pressure increases with temperature. Increased temperature
causes an increase in kinetic energy. The higher kinetic energy causes more motion in molecules, which break
intermolecular bonds and escape from solution. This gas solubility relationship can be remembered if you think
about what happens to a "soda pop" as it stands around for a while at room temperature. The taste is very "flat"
since more of the "tangy" carbon dioxide bubbles have escaped.
2. Pressure. Liquids and solids exhibit practically no change of solubility with changes in pressure. Gases as might be
expected, increase in solubility with an increase in pressure. If the pressure is increased, the gas molecules are
"forced" into the solution since this will best relieve the pressure that has been applied. The blood of deep-sea
divers becomes saturated with air under the comparatively high pressures characteristic of the depths at which such
divers work. If this pressure is relieved too rapidly, as by too rapid an ascent to the surface, the air comes out of
solution rapidly and forms bubbles in the circulatory system of the afflicted diver. This condition, known as the
“bends”, affects nerve impulses as well as blood circulation and may be fatal. A solution to the problem involves the
use of an artificial atmosphere of helium and oxygen in place of air (which is largely nitrogen and oxygen). Helium is
much less soluble in blood and body fluids than nitrogen.
Factors Affecting the Rate of Dissolution
Dissolution is the process where a solute in gaseous, liquid, or solid phase dissolves in a solvent to form a solution. The
rate of dissolution is a measure of how fast a substance dissolves. It should be noted that the solubility of a substance
and rate of dissolution are entirely independent. Just because a substance may dissolve at a faster rate does not mean
that it is necessarily more soluble than the substance that dissolves at a slower rate. The rate of dissolution of a solid can
be increased by the following factors:
1. Powdering a solute will increase the surface area that is exposed or in contact with the solvent and thereby will
increase the rate of dissolution (e.g. a gram of an iodized salt dissolves faster in water than a gram of a rock salt).
2. Agitating (shaking or stirring) a system will bring more solvent into effective contact with the solute in a shorter
period of time and thereby increasing the rate of dissolution. Moreover, stirring may actually break up the solute
into smaller units and thereby producing the same effect as that of "crushing" the solute.
3. Warming will increase the rate of dissolution of a solute. Most ionic solutes behave in this way.
CONCENTRATION
Concentration of a solution is a measure of the relative amount of the components in a solution. It refers to the amount
of solute present in a given quantity of solution or solvent. It can be expressed either qualitatively or quantitatively.
Qualitative Expressions of Concentration
A solution can be qualitatively described as:
1. Dilute: a solution that contains a small proportion of solute relative to solvent, or
2. Concentrated: a solution that contains a large proportion of solute relative to solvent.
Semi-quantitative Expressions of Concentration
Solutions are characterized by the capacity of the solvent to dissolve a solute. A solution that contains the maximum
amount of a solute in a given solvent, at a specific temperature, is called a saturated solution. The concentration of this
solution corresponds to the solubility of the solute. For example, at 0oC, we can dissolve a maximum of 35.7 g of solid
NaCl in 100 mL of water (a saturated solution). Any additional solid NaCl that we add to the saturated solution simply
falls to the bottom of the container and does not dissolve.
When a solution contains less solute than that needed to form a saturated solution, it is said to be unsaturated. Thus, an
unsaturated solution can dissolve more solute. On the other hand, under suitable conditions it is possible to form a
solution that contains an amount of solute that exceeds its solubility at room temperature. Such solution is called as a
supersaturated solution. It can be prepared by saturating a solution at high temperature, removing the excess solute,
and then allowing the solution to cool undisturbed.
Quantitative Ways of Expressing Concentration
There are a number of ways to express the relative amounts of solute and solvent in a solution. The choice often
depends on convenience. For example, it is sometimes easier to measure the volume of a solution rather than the mass
of the solution. However, it should be noted that volume is temperature-dependent while mass is temperature-
independent. Some expressions for concentration such as % (w/v or v/v), molarity and normality are temperature-
dependent (i.e., the concentration of the solution changes as the temperature changes), whereas others such as% (w/w)
and molality are not. As temperature increases, volume of liquids expands, thus, molarity decreases. Conversely, as
temperature decreases, molarity increases. This is an important consideration for experiments in which the temperature
does not remain constant.
Percent solution
There are three types of percent solutions. All are parts of solute per 100 total parts of solution. Based on the following
definitions one may calculate the concentration of a solution or calculate how to make up a specific concentration.
1. Percent weight by weight (% w/w) or mass percentage is the percent mass of solute in a total mass of the
solution. Thus, a 10% (w/w) NaCl solution is made by weighing 10 g NaCl and dissolving it in 90 g of solvent,
making a the total of 100 g of solution.
% (w/w) of solute = mass of solute, g x 100 (Equation 1)
mass of solution, g
% (w/w) of solute = _ mass of solute, g x 100
mass of solute, g + mass of solvent, g
Note: Solutions of concentrated reagents, such as 37% hydrochloric acid and 85% phosphoric acid, are percent
solutions by mass. In general, percent solutions are by mass.
Exercise 1: A solution is prepared by dissolving 13.5 g of glucose in 0.100 kg of water. What is the mass percentage
of the solute in the solution?
Exercise 2: How many grams of NaCl and water are required to make 100 g of a 20% (w/w) NaCl solution?
2. Percent weight by volume (% w/v) is the percent weight of solute in a total volume of solution. Thus, a 4% (w/v)
NaCl solution is 4 g of NaCl in 100 mL of solution.
% (w/v) of solute = mass of solute, g x 100 (Equation 2)
volume of solution, ml
3. Percent volume by volume is the percent volume of solute in a total volume of solution. Thus, a 10% (v/v)
ethanol solution is 10 mL of ethanol in 100 mL of solution.
% (v/v) of solute = volume of solute, ml x 100 (Equation 3)
volume of solution, ml
Parts Per Million (ppm) and Parts Per Billion (ppb)
For very dilute solution, concentration is often expressed as parts per million (ppm), defined as:
ppm of solute = mass of solute, g x 106 (Equation 4a)
mass of solution, g
ppb of solute = mass of solute, g x 109 (Equation 4b)
mass of solution, g
A solution whose solute concentration is 1 ppm contains 1 g of solute for each million (106) grams of solution or,
equivalently, 1 mg solute per kilogram solution. Because the density of water is 1 g/mL, 1 kg of a dilute aqueous
solution will have a volume very close to 1L. Thus, 1 ppm also corresponds to 1 mg of solute per liter of solution. This
unit is often used for the acceptable maximum concentrations of toxic and carcinogenic substances. For example, the
maximum allowable concentration of arsenic in drinking water is 0.05 ppm, that is, 0.05 mg of arsenic per liter of water,
and <10 µg/L for Cd.
Mole fraction
Mole fraction of a component of a solution is the ratio of the number of moles of that component to the total number of
moles of all substances present in the solution. It is given by
mole fraction of solute = _ mole solute___ ___ (Equation 5)
mole solute + mole solvent
mole fraction of solute = mole solute
mole solution
mole of solute = mass of solute, g (Equation 6)
molar mass of solute, g/mol
Notes:
Molar mass is the mass of 1 mole of a substance in grams. It is numerically equal to the formula weight in atomic
mass unit.
The sum of the mol fraction of all components of a mixture is always equal to 1.
Molality
Molality (m) is defined as the number of moles of solute per kilogram of solvent.
molality, m = mole solute (Equation 7)
kilogram of solvent
mass of solute
= molar mass of solute
kilogram of solvent
Exercise 3: A solution of hydrochloric acid contains 36 % HCl by mass. Calculate the mole fractions of HCl and H 2O in
the solution, and the molality of HCl in the solution. (Hint: It is often helpful in problems involving mass
percentages to assume a certain total mass. Assume that there are exactly 100g solution. Thus, the solution
contains 36 g HCl, and (100 g – 36 g) = 64 g H2O).
Molarity
Molarity (M) is defined as the number of moles of solute per liter of solution.
molarity, M = mole solute (Equation 8)
Liter of solution
mass of solute
= molar mass of solute
Liter of solution
Normality
Normality (N) is defined as the number of gram-equivalent weights of the solute per liter of solution.
Normality, N = equivalent solute (Equation 9)
Liter of solution
equivalent solute = mass of solute, g (Equation 10)
equivalent weight
An equivalent weight is defined separately for neutralization and reduction-oxidation reactions. In general:
Equivalent weight = molar mass (Equation 11)
a
where the value of a depends upon the type of reaction considered.
Substance a
Acid # of H+
Base # of OH-
Salt Total valence of cation or anion
For neutralization reactions, equivalent weights are based on the fact that one H+ (aq) ion reacts with one OH-
(aq) ion: H+ (aq) + OH- (aq) H2O. One equivalent weight of an acid is the amount of the acid that supplies one
mole of H+ (aq) ions, and one equivalent weight of a base is the amount of the base that supplies one mole of OH- (aq)
ions. The value of a in Equation 11, therefore, is the number of moles of H + (aq) supplied by one mole of the acid or the
number of moles of OH- (aq) supplied by one mole of the base for the reaction being considered. As an example, the
value of “a” for HCl is one (1) while that of H2SO4 is two (2).
The normality (N) of a solution and its molarity (M) are related:
mass of solute
Normality = molar mass of solute
a _
Liter of solution
mass of solute
= molar mass of solute x a
Liter of solution
= moles of solute x a
Liter of solution
Normality = Molarity x a (Equation 12)
There is a disadvantage to basing a unit of concentration on the volume of solution, such as molarity and
normality. When the temperature changes, the volume of a solution expands or contracts and, therefore, a
concentration based on that volume changes. The molality of a given solution does not vary with temperature because
masses do not vary with temperature. Figure 1 shows the interconversion used in calculation of the molality and
molarity of solution.
Molality
(mol/ kg solvent)
Mass of solvent
Molar
mass
Mass of solute Moles of solute
Mass of solution
density
Volume of solution
Molarity
(mol/L solution)
Figure 1. Diagram of the interconversions used in calculations
of molarity and molality of solutions.
Exercise 4: Given that the density of a solution of 5.0 g toluene (C7H8) and 225 g of benzene is 0.876 g/ml, calculate
the molality and molarity of the solution. The molar mass of toluene is 92 g/mol.
Exercise 5: What is the molarity and normality of a solution which is prepared by dissolving 75.0 g of Ba(OH)2 in
water and diluting it to 0.5 L. The molar mass of Ba(OH) 2 is 171 g/mol.
Preparation of an Aqueous Solution
The following are the steps in the preparation of an aqueous solution:
1. Obtain an exact mass of the substance (solute) in a beaker or any other container. For more accurate weighing, use
an analytical balance.
2. Dissolve the solute with a small amount of the distilled or deionized water. If it would not dissolve readily, heat and
stir constantly the mixture until the solute dissolves.
3. Transfer the mixture to a clean and dry volumetric flask.
4. Using a wash bottle containing distilled or deionized water, thoroughly wash the beaker and add the washings to the
volumetric flask.
5. Add more water until flask is 2/3 full and swirl the flask to mix.
6. Once the solution is at room temperature, dilute to the mark with water and invert the flask at least 12 times to mix.
7. Transfer to the reagent bottle and label the bottle properly.
Dilution
Dilution is a commonly used practice in preparing a solution. Mixing orange juice, and preparing canned soup or
preparing a proper concentration of pesticide in a spray tank are all dilutions. In each case we are adding a solvent
(usually water) to a solute to lower the solute concentration. Dilution is therefore a process in which more solvent is
added to reduce the concentration of solute in the original solution.
When preparing a dilution, decide the volume and concentration of the resulting solution that you require. Use the
following equation to determine how much of the concentrated reagent is needed to prepare the diluted solution:
Coriginal solution x Voriginal solution = Cdiluted solution x Vdiluted solution (Equation 13)
where C is concentration and V is volume.
Slowly add the calculated volume of concentrated reagent to a proper-sized volumetric flask half filled with distilled or
deionized water and swirl the flask to mix. Once the solution is at room temperature, dilute to the mark with water and
invert the flask at least 12 times to mix.
Exercise 6: What volume of 10 M acetic acid is required to prepare 1.0 L of 0.50 M acetic acid?
