CHEM 15 CHAPTER 6-1

CHEM 15 1. Strong electrolytes - substances which completely dissociates into ions.

Chapter 6 AQUEOUS SOLUTIONS AND COLLIGATIVE PROPERTIES e.g. salts, strong acids, strong bases

Consider the dissolution of sodium chloride in water: NaCl  Na  (aq)  Cl  (aq)

Solution - a homogenous mixture of two or more components that can be varied in composition.
It is formed when one substance disperses uniformly throughout another.
Components of a solution:
1. Solvent - the component present in greatest amount; the substance in which a solute
dissolves.
2. Solute - other components present in the solution; the substance dissolved.
Solubility - the maximum amount of solute that can be dissolved in a given amount of solvent at
specific temperature.
Aqueous solutions - a solution in which water is the solvent.
Solvation - interaction between solute and solvent molecules due to intermolecular forces of
attraction (IMFA). e.g. Na+ and Cl- ions surrounded by H2O molecules
Hydration - solvation when solvent is water.
Types of Solutions
a. Dilute - a solution with low solute concentration.
b. Concentrated - a solution with high solute concentration.
c. Saturated solution - a solution that contains the maximum amount of solute the solvent
can dissolve. Additional solute will no longer dissolve if added.
d. Unsaturated solution - a solution containing amount of solute less than its solubility. It has
the capacity to dissolve more solute.
e. Supersaturated solution - a solution containing an amount of solute greater than the
solubility; an unstable solution.
At higher temperature, solvents can hold more solute than at lower temperature. If a given
amount of solute is dissolved in a solvent at a higher temperature then allowed to cool
without being disturbed, the solute will remain in solution even though the solubility
decreases as the temperature is reduced. The solution is unstable though, and the solute will
fall out of solution if the solution is disturbed.
Classification of Solutions
A. Based on Elemental Composition
1. Organic solutions - solutions of compounds containing carbon except CO2, CO,
carbonates, and cyanides.
2. Inorganic solutions - solutions of compounds of the other elements including acids,
bases, and salts.
B. Based on Ionization/Electrolytic Property of Solute
Electrolytic property - the ability of the solution to conduct electricity.
Electrolytes - substances whose aqueous solutions contain ions and thus conduct electricity.
By ion-dipole interaction, the intermolecular force of attraction between the ions and water
which is dipolar, the ions are stabilized by the water molecules. The water molecules surround
the ions and hence, these ions are dispersed uniformly throughout the solution resulting to an
electrolytic solution.
2. Weak electrolytes - substances which produce small amounts of ions in solution;
partially dissociated into ions.
e.g. weak acids, weak bases
Consider the equilibrium: CH 3COOH(aq)  CH 3COO (aq)  H  (aq)
Acetic acid, CH3COOH ionizes to form acetate anion, CH3COO- and H+. While this
happens, some ions also combine to form back CH 3COOH. This results to partial
dissociation.
3. Nonelectrolytes - substances that does not dissociate into ions; form nonconducting
solutions.
e.g. most molecular compounds are nonelectrolytes
The Solution Process
The solute and solvent form a solution and both consist of particles attracting each other. For one
substance to dissolves in another, three events must occur:
1. Solute particles separate from each other - to overcome intermolecular interactions.
2. Solvent particles separate from each other - involve overcoming intermolecular interactions.
3. Solute and solvent particles mix - the particles attract each other.
Factors in Explaining Solubility
Three types of interactions to consider for solutions:
1. Solvent-solvent interaction
2. Solute-solute interaction
3. Solvent-solute interaction
Consider the solution process taking place in three distinct steps: (1) separation of solvent
molecules, (2) separation of solute molecules, and (3) mixing of solvent and solute molecules. If
solvent-solute interaction can't compete with solute-solute and solvent-solvent interactions then
the solute and the solvent remain separated.
 CHEM 15 CHAPTER 6-2
Factors Affecting Solubility
1. Temperature
1
For gases: T  The solubility of gases decreases with increasing T.
Solub ility

 A glass of soda quickly goes flat when they are allowed to warm.
 If a glass of cold tap water is warmed, bubbles of air are seen on the inside of the glass.
Figure 6.1 The dissolution process
At higher T, gas molecules are moving more quickly. They have a higher tendency to find the
surface and escape more quickly resulting to fewer gas molecules are in the liquid.
For liquid-liquid solutions, the rule is “like dissolves like.”
 Polar molecules will mix (miscible) with other polar molecules. For solids: T  Solubility As T increases, the solubility of solids increase.
 Nonpolar molecules will mix (miscible) with other nonpolar molecules.
 Polar molecules will not mix (immiscible) with nonpolar molecules. 2. Pressure - the soluility gas is increased as the pressure of the gas over the solvent
increases. By contrast, the solubility of solids and liquids are not appreciably affected by
For solid-liquid solutions, “like dissolves like” rule also applies. pressure.
Solvent Henry’s law - the solubility of a gas is proportional to partial pressure of the gas above
Solid solute
Polar Nonpolar liquid. For gases, increasing the pressure increases solubility.
Polar Soluble Insoluble
Nonpolar Insoluble Soluble C g  kPg where: Cg = solubility of the gas in solution
Ionic Check solubility rules Insoluble
k = Henry’s law constant
Pg = partial pressure of the gas over the solution
Note that you need to be able to determine whether a compound is polar or nonpolar given only
its formula – i.e. determine the Lewis structure and use VSEPR to determine shape then the The greater the gas pressure, the greater the number of moles of gas molecules are over the
polarity. solution. Since more gas molecules encounter the liquid surface, more gas molecules go into
the liquid phase.
Some solids will not dissolve in any solvent such as:
 Network covalent solids (eg. graphite, quartz) never dissolve in any solvent.
 Metals do not "dissolve" - they may react with but do not dissolve in solvents.

EXERCISE 6.1
1. Which of the following will be soluble in or miscible with water?
I2 NaCl Mg(OH)2
Br2(l) NH3 Cdiamond

2. Which of the following will be soluble in or miscible with hexane, a nonpolar liquid?
I2 NaCl Mg(OH)2
Figure 6.2 Illustration of the Henry’s law
Br2(l) NH3 Cdiamond

Practical applications of Henry’s law:

 Sodas cannot be as carbonated after being opened due to the decrease in pressure.
 Divers get the "bends" - air dissolved in blood and other bodily fluids bubbles out when
divers go from deep water (high pressure) to the surface (low pressure).
 CHEM 15 CHAPTER 6-3
Ways of Expressing Concentration of Solutions 7. Molarity, M
1. Mass percentage mol solute mol
Mass of solute m 
%w / w  x100 L soln L
Total mass of soln
Total mass of soln = mass of solvent + mass of solute

2. Volume percentage
Volume of solute
%v / v  x100
Total volume of soln
Total volume of soln = volume of solvent + volume of solute

3. Mass per volume percentage

Mass of solute (g)
%w / v  x100
Total volume of soln (mL)

4. Parts per million, ppm and parts per billion, ppb - for very dilute solutions

Mass of solute
ppm  x10 6
Total mass of soln
Figure 6.3 Diagram on the calculation between molality and molarity
mg solute mg solute
ppm  
kg soln L soln 8. Normality, N
No. of equivalent s of solute eq
ppb 
Mass of solute
x10 9 N 
Total mass of soln L soln L
g solute
ppb  Weight of solute MW g
L soln where: No. of equivalent s   
Equivalent weight of solute a eq
5. mole fraction, X No. of equivalent s
mol solute a (depends on the nature of the solute)
X  mol solute
total mol soln
When the solute acts as a/an:
Total mol soln = mol solute + mol solvent a. Acid or base
a = number of replaceable H+ or OH- per mole of an acid or base
6. Molality, m - a unit of concentration which is independent of the temperature. e.g. HCl a = 1 eq/mol EW = 36.46 g/eq
mol solute mol H2SO4 a = 2 eq/mol EW = 98.08 g/2 eq = 49.04 g/eq
m  NaOH a = 1 eq/mol
kg solvent kg Ba(OH)2 a = 2 eq/mol
 CHEM 15 CHAPTER 6-4
b. Salt 12. What volume of 0.125 N solution can be prepared from 15.0 g CuSO4?
a = total number of positive charge 13. Convert the following normal concentrations to molarity:
e.g. KCl K+ and Cl- a = 1 eq/mol a. 4.0 N H3PO4
Ca(NO3)2 Ca2+ and NO3- a = 2 eq/mol b. 5.0 N H2SO4
c. Reducing or oxidizing agent 14. Convert the following molar concentrations to normality:
a = total number of electrons gained or lost during redox reactions a. 0.02 M H2SO4
e.g. C2O42-  CO2 a = 2 eq/mol b. 0.50 M Na2CO3
MnO4-  Mn2+ a = 5 eq/mol 15. What volume of 12.0 M HCl must be used to prepare 300 mL of a 3.00 M solution?
16. What is the concentration of 0.800 L HNO3 solution prepared from 5.00 mL of 16.0 M HNO3?
17. What is the molality of a solution made by dissolving 36.5 g naphthalene, C10H8, in 420 g
Relationship of Molarity and Normality toluene, C7H8?

mol eq N M
M  and N , hence,   N  Ma Comparison of Concentration Units
L L eq mol Mole fractions - used for partial pressures of gases and for dealing with vapor pressures of
solutions.
Dilution Molarity - preferred over molality because it is easier to measure volume of a solution using
When a solution is diluted, the volume is increased by adding more solvent, the concentration calibrated glassware than to weigh the solvent.
decreases, but the total amount of solute remains constant. Molality - independent of temperature hence, is useful when an experiment is carried out over a
Dilution formula: M1V1 = M2V2 where: M1 = initial concentration range of temperatures. Since the volume varies with temperature, molarity varies with
M2 = final concentration temperature.
V1 = initial volume Mass percent - independent of temperature and the molar masses are not needed.
V2 = final volume Parts per million - used to express very low concentrations of solute such as impurities and
pollutants.
EXERCISE 6.2
1. A solution contains 15.0 g NaCl in 100 g water. What is the percentage by weight of NaCl in Quantitative Reaction in Solution: Neutralization Reaction
the solution? Neutralization reaction: acid  base  salt  water
2. A sample of vinegar is 5.00% acetic acid by weight. How much vinegar must you buy to have
80.0 g acetic acid?
HCl  NaOH  NaCl  H 2 O
3. A commercial bleaching solution contains 3.62 mass percent sodium hypochlorite, NaOCl. H 2 SO 4  2 NaOH  Na 2 SO 4  2 H 2 O
What is the mass of NaOCl in a bottle containing 2.50 g bleaching solution?
4. The Dead Sea contains 58.0 moles of Br- in 1.00 x 103 kg water. Calculate the concentration Notice that the mole of acid is not always equal to the mole base. But equivalents of acid is
in ppm of bromide ion in the Dead Sea. always equal to equivalents base.
5. The Salton Sea in California contains a relatively large amount of Li ions. Its concentration is
1.9 ppm. How many moles of Li+ are present in 10.0 L of water from Salton Sea?
Since eq of A  N AV A and eq of B  N BV B
6. What is the molality of a solution containing 0.850 g ammonia, NH3, in 125.0 g H2O?
7. Calculate the molality of an aqueous solution of NaCl of 0.250 kg of the solution contains 40.0 eq of A  eq of B
g NaCl? then N AV A  N BV B
8. Calculate the molarity of a solution prepared by dissolving 0.827 g NaCl in enough solvent to
produce 250 mL of solution?
9. How many grams of solid sample should be used to prepare a 500 mL of 0.10 M NaOH EXERCISE 6.3
solution if the solid is 95.0% pure NaOH? 1. A sample of citric acid (H3C6H5O2  3 H+) in fruit juices is analyzed by titrating with 0.1087 M
10. Concentrated sulfuric acid solution has a density of 1.84 g/mL and contains 98.3% H2SO4 by NaOH. If the sample requires 38.31 mL of NaOH, calculate the weight of citric acid.
weight. What is the molarity of this acid? 2. How many milliliters of 0.130 N HCl solution is required to neutralize 35.0 mL of 0.100 N
11. How would you prepare 750 mL of 0.200 N of K2Cr2O7 (a = 3 eq/mol)? NaOH?
3. What is the molarity of a 50.00 mL H2SO4 solution neutralized by 15.0 mL of 0.200 N KOH?
 CHEM 15 CHAPTER 6-5
 
PT  X P  X B P
A A B
Colligative properties - physical properties of nonvolatile, non-electrolytic solutions that are
dependent only on the quantity (concentration) of the solute but not on the kind (nature) of
2. Boiling Point Elevation
solute particles.
Because the vapor pressure of a solution is lower than that of the pure solvent at any
temperature, a solution boils at a higher temperature than the pure solvent.
1. Vapor Pressure Lowering or Depression
Raoult’s law - the elevation of the boiling point of a dilute nonvolatile solution is directly
When a liquid is placed in a sealed container, a certain amount will evaporate as vapor to
proportional to the molality of a non-electrolytic solutions.
completely occupy the container. The vapor exerts a pressure (vapor pressure) over the
liquid. The vapor pressure of a liquid depends on temperature, as temperature increases, the
vapor pressure also increases. Tb  K b m where: ΔTb = boiling point elevation
Kb = boiling point elevation constant
Nonvolatile - a substance that has no measureable vapor pressure. m = molality of the solution
Volatile - one that exhibits a vapor pressure. Tb(soln) = Tb(solvent) + Tb

When the vapor pressures of various solvents are compared with those of their solutions, it is 3. Freezing Point Depression
found that the addition of nonvolatile solute to a solvent always reduces the capacity of the Since the vapor pressure of the solution is lower than that of the solvent at any temperature,
solvent molecules to evaporate hence, the vapor pressure is lowered. the solution freezes at a lower temperature than the solvent.
1 Raoult’s law - the lowering of the freezing point of a dilute solution is directly proportional to
Concentration of solute  As the concentration of the solute increases, the molal concentration of the solution.
Psolute
the vapor pressure of the solute decreases.
T f  K f m where: ΔTf = freezing point depression
Kf = freezing point depression constant
m = molality of the solution
Tf(soln) = Tf(solvent) – Tf

Table 6.1 Table of constants

Substance Freezing Point, oC Kf, oC/m Boiling Point, oC Kb, oC/m
Acetic acid 16.6 3.90 118.1 3.07
Benzene 5.51 4.90 80.1 2.53
Figure 6.4 Vapor pressure lowering Water 0.00 1.86 100.0 0.512
CCl4 -22.8 31.8 76.8 5.03
Ethanol -117.3 1.99 78.5 1.22
Raoult’s law - predicts that when the mole fraction of the solute is increased, the vapor over
the solution will be reduced.
PA  X APA where: PA = vapor pressure of solution
XA = mole fraction of solvent
PA = vapor pressure of pure solvent
Ideal solution - a solution that obeys Raoult’s law; achieved at low solute concentrations.
Ideal solutions with two or more volatile components, A and B: Molecular Weight Determination
 
PA  X PA A and PB  X P B B mol g solute
PT  PA  PB m 
kg solvent (MW solute)(kg solvent)
 CHEM 15 CHAPTER 6-6
15. Camphor, C10H16O, melts at 179.8 C and has a particular freezing point depression constant,
T f  K f m Tb  K b m Kf = 40 C/m. When 0.186 g of an organic substance of unknown molar mass is dissolved in
22.01 g of liquid camphor, the freezing point of the mixture is found to 176.7 C. What is the
 g solute  K f 
  g solute  K b  approximate molar mass of the solute?
MW    MW     16. What is the composition of the vapor which is in equilibrium at 30 C with a benzene-toluene
 kg solvent  T f 
  kg solvent  Tb  solution with a mole fraction of benzene of (a) 0.400, (b) 0.600? (Pbenzene = 119 torr; Ptoluene
= 37.0 torr)
EXERCISE 6.4 17. What is the molecular mass of solute, A, if the osmotic pressure of a solution containing 10.0
1. Find the freezing point and boiling point of a solution containing 2.00 g of sucrose, C 12H22O11, g/L is 10.0 torr at 27 C?
dissolved in 100 g water. 18. Ethylene glycol, C2H6O2, is a nonvolatile electrolyte commonly used automotive antifreeze. A
2. A solution consists of 2.00% cortisone (MW = 630.4 g/mol) in acetic acid. Calculate the 25.0% by mass solution of ethylene glycol is used.
freezing point of this solution. a. What is the molality of this solution?
3. The freezing point of pure biphenyl is 70.03 C. The freezing point of 10 g biphenyl containing b. Calculate the boiling point and the freezing point of the solution if Kb = 0.512 °C/m and Kf
0.100 g naphthalene (MW = 128.1 g/mol) was found to be 69.40 C. Calculate the Kf of = 1.858°C/m for water.
biphenyl. 19. List the following aqueous solutions in order of increasing expected freezing and boiling
4. An aqueous solution contains 0.15 g unknown solute and 50.00 g H2O. If it freezes at -0.050 points: 0.050 m CaCl2, 0.15 m NaCl, 0.10 m HCl, 0.050 m HC2H3O2, and 0.10 m C12H11O22.
C, calculate (a) the MW of the solute and (b) the boiling point of the solution. 20. Which of the following will have the largest increase in boiling point upon addition of 1 kg
5. A solution contains 1 mol of benzene and 2 mol of toluene at 20oC. Predict the mole fraction water: 1 mol Co(NO3)2, 2 mol KCl, or 3 mol of ethylene glycol?
of benzene in the vapor phase. (P benzene = 75 torr; Ptoluene = 22 torr)
6. While antifreeze protects a car from freezing, it also protects it from overheating. Calculate
the freezing point depression of a solution of 100.0 g of ethylene glycol, C 2H6O2, antifreeze in 4. Osmotic Pressure, 
0.500 kg water. Semipermeable membrane - allows passage of certain molecules but not others. They
7. A solution of an unknown nonvolatile nonelectrolyte was prepared by dissolving 0.250 g in often permit the passage of small solvent molecules but block the passage of larger solute
40.0 g CCl4. The normal boiling point of the resultant solution increased by 0.357 C. molecules or ions. This is due to a network of tiny pores within the membrane.
Calculate the molar mass of the solute.
8. The vapor pressure of pure liquid solvent A is 0.80 atm. When a nonvolatile substance B is Consider a situation in which only solvent molecules are able to pass through a membrane. If
added to the solvent, its vapor pressure drops to 0.60 atm. What is the mole fraction of such a membrane is placed between two solutions of different concentration, solvent
component B in the solution? molecules move in both directions through the membrane. However, the concentration of the
9. Calculate the mole fraction of toluene in the vapor phase which is in equilibrium with a solvent is higher in the solution containing less solute than in the more concentrated one.
solution of benzene and toluene having a mole fraction of toluene 0.500. The vapor pressure Therefore, the rate of passage of solvent from less concentrated to the more concentrated
of pure benzene is 119 torr and that of toluene is 37.0 torr at the same temperature. solution is greater than the rate in the opposite direction. Thus, there is a net movement of
10. What is the freezing point of a 10% (by weight) solution of CH3OH in water? solvent molecules from less concentrated solution to more concentrated one. This process is
11. The osmotic pressure of blood is 7.65 at 37 C. How much glucose should be used per L of called osmosis. This is driven by the tendency to attain equal concentrations.
intravenous injection that is to have the same osmotic pressure as blood?
12. Arrange the following aqueous solutions in order of increasing freezing point:
a. 0.10 m C2H5OH d. 0.10 m Ba3(PO4)2
b. 0.10 m Na2SO4 e. 0.10 m KCl
c. 0.10 m Li3PO4
13. Glycerin, C3H8O, is a nonvolatile electrolyte with density of 1.26 g/mL. Calculate the vapor
pressure at 25 C of a solution made by adding 50.0 mL glycerin to 500.0 mL of water. The
vapor pressure of pure water at 25 C is 23.8 torr.
14. Calculate the freezing point of a solution containing 0.600 kg CHCl3 and 42 g of eucalyptol,
C10H18O, a fragrant substance found in leaves of eucalyptus trees. (Kf of CHCl3 = 4.68 C/m ;
FP = -63.5 C)
 CHEM 15 CHAPTER 6-7

Figure 6.6 Crenation and hemolysis

Colligative Properties of Electrolytic Solutions

The colligative properties for electrolyte solutions differ from that of nonelectrolytes since ions of
opposing charges have the tendency to stick together and form ion pairs. The formation of ion
pairs causes slight changes in , ΔTf, ΔTb, and vapor pressure. The van’t Hoff factor, i must be
introduced that gives a measure of the extent of dissociation of electrolytes.
Figure 6.5 Illustration of osmotic pressure T f (measured )
i
T f (calculated for nonelectro lyte )
Osmotic pressure - pressure required to prevent osmosis.
nRT
  MRT  where: M = molarity
V Ideally, the value of i for a particular electrolyte is indicated by the number of ions produced in
R = 0.0821 L·atm/K·mol solution. Ideal i values are applicable for dilute solutions and salts with low ionic charges.
T = absolute temperature
i = no. of ions per formula unit e.g. CaCl2: i = 3 (Ca2+ and 2 Cl-)
 When Papplied < , osmosis takes place in the normal way and water moves through the KNO3: i = 2 (K+ and NO3-)
membrane in the solution. Mg3N2: i = 5 (3 Mg2+ and 2 N3-)
 When Papplied > , reverse osmosis occurs wherein water molecules move through the
membrane from the solution to pure water. Hence, when dealing with an electrolyte solution, i must be introduced to the equations involved
in the calculation of the boiling point, freezing point, and osmotic pressure.
Types of solutions in terms of osmotic pressure:
1. Isotonic solutions - two solutions having equal concentrations hence, have the same Colloid - a dispersion of particles of one substance (the dispersed phase) throughout another
osmotic pressure and no osmosis occurs. substance (the continuous phase).
Tyndall effect - the scattering of light of by colloidal particles.
2. Hypotonic solution - less concentrated solution; a solution with lower osmotic pressure. Coagulation - process by which the dispersed phase of a colloid is made to aggregate and
Crenation - the cell shrivels which is caused by the movement of water from a hypotonic cell thereby separate from the continuous phase. An example is the curdling of milk when in sours
when it is placed in a solution which is hypertonic with respect to the intracellular solution. wherein lactose, the milk sugar, ferments to lactic acid.

3. Hypertonic solution - more concentrated solution.

Hemolysis - the rupturing of the cell caused by the movement of water into a hypertonic cell
when it is placed in a solution which is hypotonic with respect to the intracellular solution.
 CHEM 15 CHAPTER 6-8
Table 6.2 Types of solutions according to particle size H 3 PO4  2 NaOH  Na2 HPO4  2 H 2 O a = 2 eq/mol
Particle size,
Mixture
nm
Examples Characteristics H 3 PO4  NaOH  NaH 2 PO4  H 2 O a = 1 eq/mol
Solution 0.2 – 2.0 Air, seawater, Transparent to light, does not separate
wine on standing, nonfilterable
Colloid 2.0 – 1000 Butter, milk, Often murky, exhibits Tyndall effect, Arrhenius base - a substance that increases [OH–] ions when dissolved in water; a
substance that dissolves in H2O to produce OH- ions.
fog does not separate on standing,
nonfilterable NaOH (aq)  Na  (aq)  OH  (aq)
Suspension > 1000 Blood, paint Murky or opaque to light, separates on 
NH 4 OH (aq)  NH 4 (aq)  OH  (aq)
standing, filterable
Arrhenius theory - a neutralization reaction involves the combination of hydrogen ions and
hydroxide ions to form water.
Table 6.3 Types of colloids
H  (aq) OH  (aq)  H 2 O(l )
acid base

Limitations of this theory:

 It cannot explain why NH3 is a base.
 It does not recognize the role of the solvent during ionization.

2. Bronsted-Lowry Theory
Bronsted-Lowry acid - proton (H+) donor.
Bronsted-Lowry base - proton (H+) acceptor.

Proton transfer reactions - in a Bronsted-Lowry acid-base reaction, a proton is transferred

from an acid to a base.
HX (aq) A  (aq)  HA(aq)  X  (aq)
B- L acid B- L base
Acids and Bases

Weak bases: NH 3 (aq) H 2 O(l )  NH 4 (aq)  OH  (aq)
Theories on the Behavior of Acids and Bases base acid
1. Arrhenius’ Theory Since NH3 is a weak base, the reverse reaction can occur:
Arrhenius acid - a substance that increases [H+] when dissolved in water; a substance that 
dissolves in H2O to produce H+ or H3O+ ions. NH 4 (aq)  OH  (aq)  NH 3 (aq)  H 2 O(l )
The ionization of acids produces the hydronium ion, H3O+. But H 3O  H 2O  H  so The reaction is said to be reversible:

NH 3 (aq)  H 2 O  NH 4 (aq)  OH  (aq)
we abbreviate H3O+ to H+.
HCl(aq)  H 2 O(l )  H 3O  (aq)  Cl  (aq) Weak acids:

HC2 H 3O2 (aq)  H 2 O(l )  H 3O  (aq)  C 2 H 3O2 (aq)

HC2 H 3O2 (aq)  H 2 O(l )  H 3O  (aq)  C 2 H 3O2 (aq)
Reversible Acid-Base Reactions
Reversible reactions can proceed in both forward and reverse directions. In any acid-base
Polyprotic acids - contains more than one 2 replaceable H .
+
equilibrium, both the forward and the reverse reaction involve proton transfer. Consider the
For example: H 3 PO4  3NaOH  Na3 PO4  3H 2 O a = 3 eq/mol
general acid-base reaction: HX (aq)  H 2 O(l )  H 3O  (aq)  X (aq)
 CHEM 15 CHAPTER 6-9
For the forward direction, HX is the Bronsted-Lowry acid, H2O is the Bronsted-Lowry base. HCl  C2 H 5  O  C2 H 5  [C2 H 5  OH  C2 H 5 ]  Cl 
For the reverse direction, H3O+ is the Bronsted-Lowry acid, X–- is the Bronsted-Lowry base.

Conjugate Acid-Base Pairs
For the reaction above, when HX donates a proton to H2O it leaves behind X– which acts as a
base. An acid and base that differ only in the presence/absence of a proton are called
conjugate acid-base pairs. Thus, HX is the conjugate acid of X– and X– is the conjugate
base of HX, and H2O is the conjugate base of H3O+ and H3O+ is the conjugate acid of H2O.
3. Lewis’ Theory - emphasizes the shared electron pair rather than the proton.
Lewis acid - electron pair acceptor
Lewis base - electron pair donor
Reactions between Lewis acids and bases lead to formation of covalent bonds. The theory is
useful in explaining the formation of complex ions

Hence, for the reaction,


NH 3 (aq)  H 2 O  NH 4 (aq)  OH  (aq) Consider: NH 3  BF3  NH 3  BF3
In this reaction, NH3 is the electron pair donor (Lewis base) while BF3 is the electron pair
NH4+ is the conjugate acid of NH3 and OH- is the conjugate base of water. While for the

acceptor (Lewis acid) leading to the formation of a covalent bond between them.
reaction, HC2 H 3O2 (aq)  H 2 O(l )  H 3O  (aq)  C 2 H 3O2 (aq)
C2H3O2- is the conjugate base of HC2H3O2 and H3O+ is the conjugate acid of H2O.
Molecular Structure and Acid-Base Behavior
Strong acids: HCl, HBr, HI, HNO3, H2SO4, HClO4, HClO3 In terms of acid strength, HCl > HF
Strong bases: LiOH, NaOH, KOH, Ca(OH)2, Sr(OH)2, Ba(OH)2 ClCH2COOH > CH3COOH > CH3CH2CH3
Strong acids and bases dissociate completely into ions in solution. All other acids and bases 1
For binary acids: Bond strength 
are considered weak. Bond length
A substance that can both accept and donate a proton - i.e. act as an acid and as a base - is 1
For Group 7A binary acids: Bond length 
amphoteric. Water is amphoteric. Bond dissociation energy
HCl(aq)  H 2 O(l )  H 3O  (aq)  Cl  (aq) Water acts as a base.
  Acidity: HF < HCl < HBr <HI
NH 3 (aq)  H 2 O(l )  NH 4 (aq)  OH (aq) Water acts as an acid.
Bond length: 91.7 A < 127.4 A < 141.2 A < 160.9 A

Relative Strengths of Acids and Bases Within a period, consider the bond polarity and electronegativity of atoms bonded together. The
1. In every acid-base reaction, the position if equilibrium favors transfer of the proton from the greater the difference in electronegativity (∆EN), the higher the polarity and hence, the higher the
stronger acid to the stronger base. Consider the reaction: acidity of the compound.
HX (aq)  H 2 O(l )  H 3O  (aq)  X (aq)
Relationships: EN  Bond polarity  Acidity
If HX is a stronger acid than H3O+, then the forward reaction is favored over the reverse
reaction, and the equilibrium lies to the right.
Acidity: CH4 < NH3 < H2O < HF
2. The conjugate base of a strong acid is a weak base; and the conjugate acid of a strong base
∆EN: 0.4 < 0.9 < 1.4 < 1.9
is a weak acid.

Solvent effect - leveling effect of water on the strength of acids. Since water can act as a weak
ADDITIONAL EXERCISES
base, strong acids tend to have same strength in water.

1. The solubility of MnSO4  H2O in water at 20C is 70 g per 100 mL of water.
Consider: HClO4 (aq)  H 2 O(l )  H 3O  (aq)  ClO4 (aq) a. Is a 1.22 M MnSO4  H2O solution in water at 20C saturated, unsaturated, or
supersaturated?
HCl(aq)  H 2 O(l )  H 3O  (aq)  Cl  (aq) b. Given a solution of MnSO4  H2O of unknown concentration, what experiment could you
In water, HClO4 and HCl have the same acid strength. perform to determine whether it is saturated, unsaturated, or supersaturated?
2. a. Explain why carbonated beverages must be stored in sealed containers.
But in diethylether, (C2H5)2O solvent, HClO4 is the stronger acid. b. Once the beverage has been opened, why does it maintain some carbonation when
 refrigerated?
HClO4  C 2 H 5  O  C 2 H 5  [C 2 H 5  OH  C 2 H 5 ]  ClO4
 CHEM 15 CHAPTER 6-10
3. A 1.215 g sample of NaCl is dissolved in 65.483 g of water. What is the mass percent of NaCl
in the solution?
4. A 2.500 g sample of groundwater was found to contain 5.4 µg of Zn2+. What is the
concentration of Zn2+ in parts per million?
5. Calculate the molality of a sulfuric acid (MW = 98.086 g/mol) solution containing 25.6 g of
sulfuric acid in 195 g of water.
6. How would you prepare a 100.0 mL of 0.500 M KI starting with 2.00 M KI?
7. Calculate the molarity of an aqueous vinegar solution, which is 5.0% HC2H3O2 (MW = 60.06
g/mol) by mass.
8. Calculate the molarity of a 0.417 m glucose (C6H12O6, MW = 180.2 g/mol) solution if its
density is 1.16 g/mL.
9. Calculate the boiling point of a solution containing 1.25 mol of NaCl in 0.250 kg of water using
Kb = 0.52°C/m.
10. Calculate the freezing point of a solution containing 1.25 mol of NaCl in 0.250 kg of water
using Kf = 1.86°C/m.
11. List following aqueous solutions in order of increasing boiling point: 0.040 m glycerin, 0.20 m
KBr, and 0.030 m phenol.
12. List the following aqueous solutions in order of decreasing freezing point: 0.075 m glucose,
0.075 m LiBr, and 0.030 m Zn(NO3)2.
13. Lauryl alcohol is obtained from coconut oil and is used in making detergents. A solution of
5.00 g of lauryl alcohol in 0.100 kg benzene freezes at 4.1C. What is the molar mass of this
substance?
14. Adrenaline is the hormone that triggers release of extra glucose molecules in times of stress
or emergency. A solution of 0.64 g adrenaline in 36.0 g CCl4 causes an elevation of the boiling
point. What is the molar mass of this substance?
15. A 0.125 M sample of seawater was taken at 25°C. Calculate the osmotic pressure of the
seawater sample.