Chemistry: A Molecular Approach, 2nd Ed.

Nivaldo Tro

Chapter 12 Solutions

Roy Kennedy Massachusetts Bay Community College Wellesley Hills, MA

Copyright 2011 Pearson Education, Inc.

 Homogeneous mixtures are called solutions The component of the solution that changes state is
called the solute The component that keeps its state is called the solvent
if both components start in the same state, the major component is the solvent

Solutions

Tro: Chemistry: A Molecular Approach, 2/e

Copyright 2011 Pearson Education, Inc.

 Most processes occur because the

Mixing and the Solution Process: Entropy

end result has less potential energy But formation of a solution does not necessarily lower the potential energy of the system When two ideal gases are put into the same container, they spontaneously mix

The gases mix because the energy

of the system is lowered through the release of entropy
Tro: Chemistry: A Molecular Approach, 2/e 3 Copyright 2011 Pearson Education, Inc.

even though the difference in attractive forces is negligible

Solution Interactions

Tro: Chemistry: A Molecular Approach, 2/e

Copyright 2011 Pearson Education, Inc.

Solubility
There is usually a limit to the solubility of one
substance in another
gases are always soluble in each other two liquids that are mutually soluble are said to be miscible

The maximum amount of solute that can be

dissolved in a given amount of solvent is called the solubility The solubility of one substance in another varies with temperature and pressure
5 Copyright 2011 Pearson Education, Inc.

alcohol and water are miscible oil and water are immiscible

Tro: Chemistry: A Molecular Approach, 2/e

Will It Dissolve?
Chemists Rule of Thumb
Like Dissolves Like

A chemical will dissolve in a solvent if it has a

similar structure to the solvent
when the solvent and solute structures are similar, the solvent molecules will attract the solute particles at least as well as the solute particles are attracted to each other

Polar molecules and ionic compounds will be

more soluble in polar solvents Nonpolar molecules will be more soluble in nonpolar solvents
6 Copyright 2011 Pearson Education, Inc.

Tro: Chemistry: A Molecular Approach, 2/e

Classifying Solvents

Tro: Chemistry: A Molecular Approach, 2/e

Copyright 2011 Pearson Education, Inc.

Practice Explain the solubility trends seen in the table below

Tro: Chemistry: A Molecular Approach, 2/e

Copyright 2011 Pearson Education, Inc.

Heat of Solution When some compounds, such as NaOH,

dissolve in water, a lot of heat is released
the container gets hot

When other compounds, such as NH4NO3,

dissolve in water, heat is absorbed from the surroundings
the container gets cold

Why is this?
Tro: Chemistry: A Molecular Approach, 2/e 9 Copyright 2011 Pearson Education, Inc.

Energetics of Solution Formation: the Enthalpy of Solution

To make a solution you must
1. overcome all attractions between the solute particles; therefore DHsolute is endothermic 2. overcome some attractions between solvent molecules; therefore DHsolvent is endothermic 3. form new attractions between solute particles and solvent molecules; therefore DHmix is exothermic The overall DH for making a solution depends on the relative sizes of the DH for these three processes DHsoln = DHsolute + DHsolvent + DHmix
Tro: Chemistry: A Molecular Approach, 2/e 10 Copyright 2011 Pearson Education, Inc.

Energetics of Solution Formation

If the total energy cost for breaking attractions between particles in the pure solute and pure solvent is greater less than the energy released in than the energy released in making the new attractions between the solute and solvent, the overall process will be endothermic exothermic
Copyright 2011 Pearson Education, Inc.

Tro: Chemistry: A Molecular Approach, 2/e

11

Ion-Dipole Interactions
When ions dissolve in water they become
hydrated
each ion is surrounded by water molecules

The formation of these ion-dipole attractions

causes the heat of hydration to be very exothermic

Tro: Chemistry: A Molecular Approach, 2/e

12

Copyright 2011 Pearson Education, Inc.

Heat of Hydration

DHsolution = DHhydration DHlattice energy

Tro: Chemistry: A Molecular Approach, 2/e 13 Copyright 2011 Pearson Education, Inc.

Comparing Heat of Solution to Heat of Hydration

Because the lattice energy is always exothermic, the
size and sign on the DHsoln tells us something about DHhydration If the heat of solution is large and endothermic, then the amount of energy it costs to separate the ions is more than the energy released from hydrating the ions DHhydration < DHlattice when DHsoln is (+) If the heat of solution is large and exothermic, then the amount of energy it costs to separate the ions is less than the energy released from hydrating the ions DHhydration > DHlattice when DHsoln is ()
Tro: Chemistry: A Molecular Approach, 2/e 14 Copyright 2011 Pearson Education, Inc.

Solution Equilibrium

Tro: Chemistry: A Molecular Approach, 2/e

15

Copyright 2011 Pearson Education, Inc.

Solubility Limit
A solution that has reached it solubility limit is said
to be saturated. The saturated solution has dynamic equilibrium between solute and solvent.
if you add more solute it will not dissolve the saturation concentration depends on the temperature
and pressure of gases

A solution that has less solute than saturation is

said to be unsaturated
more solute will dissolve at this temperature

A solution that has more solute than saturation is

said to be supersaturated
Tro: Chemistry: A Molecular Approach, 2/e 16 Copyright 2011 Pearson Education, Inc.

Adding a Crystal of NaC2H3O2 to a Supersaturated Solution

Tro: Chemistry: A Molecular Approach, 2/e

17

Copyright 2011 Pearson Education, Inc.

Temperature Dependence of Solubility of Solids in Water

Solubility is generally given in grams of solute that

will dissolve in 100 g of water (i.e. percentage) For most solids, the solubility of the solid increases as the temperature increases
when DHsolution is endothermic

Tro: Chemistry: A Molecular Approach, 2/e

18

Copyright 2011 Pearson Education, Inc.

Solubility Curves

Tro: Chemistry: A Molecular Approach, 2/e

19

Copyright 2011 Pearson Education, Inc.

Concentrations (see Handout Table 12.5)

Solutions have variable composition To describe a solution, you need to describe the
components and their relative amounts Concentration = amount of solute in a given amount of solution
occasionally amount of solvent

Tro: Chemistry: A Molecular Approach, 2/e

20

Copyright 2011 Pearson Education, Inc.

Molarity and Dissociation

The molarity of the ionic compound allows you
to determine the molarity of the dissolved ions CaCl2(aq) = Ca2+(aq) + 2 Cl(aq) A 1.0 M CaCl2(aq) solution contains 1.0 moles of CaCl2 in each liter of solution
1 L = 1.0 moles CaCl2, 2 L = 2.0 moles CaCl2

Because each CaCl2 dissociates to give one

Ca2+, a 1.0 M CaCl2 solution is 1.0 M Ca2+ a 1.0 M CaCl2 solution is 2.0 M Cl
21

1 L = 1.0 moles Ca2+, 2 L = 2.0 moles Ca2+

Because each CaCl2 dissociates to give 2 Cl,

1 L = 2.0 moles Cl, 2 L = 4.0 moles Cl
Tro: Chemistry: A Molecular Approach, 2/e Copyright 2011 Pearson Education, Inc.

Percent Concentration

Tro: Chemistry: A Molecular Approach, 2/e

22

Copyright 2011 Pearson Education, Inc.

Parts Per Million Concentration

Tro: Chemistry: A Molecular Approach, 2/e

23

Copyright 2011 Pearson Education, Inc.

Using Concentrations as Conversion Factors

Concentrations show the relationship between the
amount of solute and the amount of solvent
12%(m/m) sugar(aq) means 12 g sugar 100 g solution
or 12 kg sugar 100 kg solution; or 12 lbs. 100 lbs. solution

5.5%(m/v) Ag in Hg means 5.5 g Ag 100 mL solution 22%(v/v) alcohol(aq) means 22 mL EtOH 100 mL solution

The concentration can then be used to convert the

amount of solute into the amount of solution, or vice- versa
Tro: Chemistry: A Molecular Approach, 2/e 24 Copyright 2011 Pearson Education, Inc.

Example 12.3: What volume of 10.5% by mass soda contains 78.5 g of sugar?
Given: 78.5 g sugar Find: volume, mL Conceptual g solute Plan:

g soln

mL soln

Relationships: 100 g soln = 10.5 g sugar, 1 mL soln = 1.04 g

Solve:

Check: the unit is correct, the magnitude seems reasonable

as the mass of sugar 10% the volume of solution
25

Tro: Chemistry: A Molecular Approach, 2/e

Copyright 2011 Pearson Education, Inc.

 The mole fraction is the fraction of the moles

of one component in the total moles of all the components of the solution Total of all the mole fractions in a solution = 1 Unitless The mole percentage is the percentage of the moles of one component in the total moles of all the components of the solution
= mole fraction x 100%

Solution Concentrations Mole Fraction, XA

Tro: Chemistry: A Molecular Approach, 2/e

26

Copyright 2011 Pearson Education, Inc.

Example 12.4a: What is the molarity of a solution prepared by mixing 17.2 g of C2H6O2 with 0.500 kg of H2O to make 515 mL of solution?
Given: 17.2 g C2H6C2H0.500 kg H2O,H2O, mL soln 0.2771 mol O2, 6O2, 0.500 kg 515 0.515 L Find: M Conceptual g C2H6O2 Plan:

mol C2H6O2 L soln M

mL soln

Relationships: M = mol/L, 1 mol C2H6O2 = 62.07 g, 1 mL = 0.001 L

Solve:

Check: the unit is correct, the magnitude is

reasonable
Tro: Chemistry: A Molecular Approach, 2/e 27 Copyright 2011 Pearson Education, Inc.

Example 12.4b: What is the molality of a solution prepared by mixing 17.2 g of C2H6O2 with 0.500 kg of H2O to make 515 mL of solution?
Given: 17.2 g C2H6O2, 0.500 kg H2O, 515 mL soln Find: m Conceptual g C2H6O2 Plan:

mol C2H6O2 kg H2O m

Relationships: m = mol/kg, 1 mol C2H6O2 = 62.07 g

Solve:

Check: the unit is correct, the magnitude is

reasonable
Tro: Chemistry: A Molecular Approach, 2/e 28 Copyright 2011 Pearson Education, Inc.

Example 12.4c: What is the percent by mass of a solution prepared by mixing 17.2 g of C2H6O2 with 0.500 kg of H2O to make 515 mL of solution?
Given: 17.2 g C2H6O2, 0.500 kg H2O, 515 mL soln Find: %(m/m) Conceptual Plan:

g C2H6O2 g solvent g soln %

Relationships: 1 kg = 1000 g
Solve:

Check: the unit is correct, the magnitude is

reasonable
Tro: Chemistry: A Molecular Approach, 2/e 29 Copyright 2011 Pearson Education, Inc.

Example 12.4d: What is the mole percent of a solution prepared by mixing 17.2 g of C2H6O2 with 0.500 kg of H2O to make 515 mL of solution?
Given: 17.2 g C2H6O2, 0.500 kg H2O, 515 mL soln Find: c% Conceptual g C2H6O2 Plan:

mol C2H6O2
mol H2O

g H2O
Solve:

c%

Relationships: c = molA/moltot, 1 mol C2H6O2 = 62.07g, 1 mol H2O=18.02 g

Check: the unit is correct, the magnitude is

reasonable
Tro: Chemistry: A Molecular Approach, 2/e 30 Copyright 2011 Pearson Education, Inc.

Converting Concentration Units

1. Write the given concentration as a ratio 2. Separate the numerator and denominator
separate into the solute part and solution part

3. Convert the solute part into the required unit 4. Convert the solution part into the required unit 5. Use the definitions to calculate the new concentration units

Tro: Chemistry: A Molecular Approach, 2/e

31

Copyright 2011 Pearson Education, Inc.

Example 12.5: What is the molarity of 6.55% by mass glucose (C6H12O6) solution?
Given: 6.55 g C6H12O6,H12O6 0.09709 L 6.55%(m/m) 2 6O2 0.03636 mol C6 100 ,g soln Find: M Conceptual g C6H12O6 Plan:

mol C6H12O6 mL L soln

M

g soln

Relationships: M =mol/L, 1mol C6H12O6=180.16g, 1mL=0.001L, 1mL=1.03g

Solve:

Check: the unit is correct, the magnitude is

reasonable
Tro: Chemistry: A Molecular Approach, 2/e 32 Copyright 2011 Pearson Education, Inc.

Vapor Pressure of Solutions

The vapor pressure of a solvent above a
solution is lower than the vapor pressure of the pure solvent
the solute particles replace some of the solvent molecules at the surface
Eventually, equilibrium is reAddition of a nonvolatile established, but withsolvent of solute The pure the smaller reduces a rate number of vaporamoleculesvapor establishes liquid vaporization, decreasing the therefore the vapor pressure will equilibrium amount of vapor be lower
Tro: Chemistry: A Molecular Approach, 2/e 33 Copyright 2011 Pearson Education, Inc.

Thirsty Solutions
Beakers with equal When equilibrium is liquid levels of pure established, the liquid solvent and a level in the solution solution are placed beaker is higher than in a solution level in the bell jar. Solvent molecules evaporate the pure solvent from the thirsty beaker each one and fill the bell jar, solution grabs and establishing an holds solvent vapor equilibrium with more effectively the liquids in the beakers.
Tro: Chemistry: A Molecular Approach, 2/e 34 Copyright 2011 Pearson Education, Inc.

Vapor Pressure Lowering

The vapor pressure of a solvent in a solution is
always lower than the vapor pressure of the pure solvent The vapor pressure of the solution is directly proportional to the amount of the solvent in the solution The difference between the vapor pressure of the pure solvent and the vapor pressure of the solvent in solution is called the vapor pressure lowering DP = Psolvent Psolution = csolute Psolvent
35 Copyright 2011 Pearson Education, Inc.

Tro: Chemistry: A Molecular Approach, 2/e

Tro: Chemistry: A Molecular Approach, 2/e

36

Copyright 2011 Pearson Education, Inc.

Freezing Salt Water

Pure water freezes at 0 C. At this temperature,

ice and liquid water are in dynamic equilibrium. Adding salt disrupts the equilibrium. The salt particles dissolve in the water, but do not attach easily to the solid ice. When an aqueous solution containing a dissolved solid solute freezes slowly, the ice that forms does not normally contain much of the solute. To return the system to equilibrium, the temperature must be lowered sufficiently to make the water molecules slow down enough so that more can attach themselves to the ice.
37 Copyright 2011 Pearson Education, Inc.

Tro: Chemistry: A Molecular Approach, 2/e

Freezing Point Depression

The freezing point of a solution is lower than the
freezing point of the pure solvent
therefore the melting point of the solid solution is lower

The difference between the freezing point of the

solution and freezing point of the pure solvent is directly proportional to the molal concentration of solute particles

The proportionality constant is called the Freezing

Point Depression Constant, Kf
the value of Kf depends on the solvent the units of Kf are C/m
Tro: Chemistry: A Molecular Approach, 2/e 38 Copyright 2011 Pearson Education, Inc.

(FPsolvent FPsolution) = DTf = mKf

Boiling Point Elevation

The boiling point of a solution is higher than the
boiling point of the pure solvent
for a nonvolatile solute

The difference between the boiling point of the

solution and boiling point of the pure solvent is directly proportional to the molal concentration of solute particles (BPsolution BPsolvent) = DTb = mKb The proportionality constant is called the Boiling Point Elevation Constant, Kb
the value of Kb depends on the solvent the units of Kb are C/m
Tro: Chemistry: A Molecular Approach, 2/e 39 Copyright 2011 Pearson Education, Inc.