Department of Chemistry, College of Science & Technology, University of Liberia

LECTURE NOTES FOR CHEM 102 – GENERAL CHEMISTRY II

TOPIC 1: CHEMICAL KINETICS (CH.16)

1.1 Introduction – Reaction Rates and Influencing Factors

 Chemical kinetics, also known as reaction kinetics, is the study of rates of chemical processes, the
changes in concentrations of reactants (or products) as a function of time, as well as the stepwise
molecular events by which a reaction occurs.
 It deals with the experimental determination of reaction rates from which rate laws and rate
constants are derived.
 Four factors affecting the rate of a given reaction can be controlled.
 Concentration: Increase in the concentration of reactants causes increase in the collision
frequency of the reactant molecules, and therefore an increase in reaction rate.
 Physical State of the Reactants: The more finely divided a solid or liquid reactant, the
greater the surface area per unit volume, the more frequent the collision, and faster the
reaction occurs.
 Temperature: Molecules must collide with enough energy to react. Higher the temperature,
more frequent the collisions, and faster the reaction occurs.
 Catalyst: It speeds up a chemical reaction.

1.2 Expressing the Reaction Rate

 Reaction rate is the change in the amount/concentration of a reactant or product per unit time.
Reactant concentration decreases over time; product concentration increases over time.
 Reaction rate can be expressed thus:

 The change in product concentration and hence, the reaction rate, is expressed in terms of B:

Average, Instantaneous, and Initial Reaction Rates

 For the same reaction as above, by measuring the concentrations of the reactant A at different time
periods, we can follow the reaction rate by calculating average rate, instantaneous rate and initial rate.
 Average rate is the change in concentration of reactants (or products) divided by a finite time period.
 The table below consists of the concentrations of reactant A over a period of 200 seconds.

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 We can calculate the average rate over the entire 200 s and the average rate over two shorter periods –
one earlier and one later.
 The instantaneous rate (rate for a specific instant during the reaction) is obtained by calculating the
average rate over shorter and shorter time intervals. Hence, reaction rate is instantaneous rate. The
slope of a line tangent to the curve at a particular point gives the instantaneous rate at that time.
 The initial rate is the instantaneous rate occurring as soon as the reactants are mixed, that is, at t = 0.
 The mathematical expression for the rate of a particular reaction and the numerical value of the rate
depend on which substance serves as the reference.

 Reaction rates can be used to study reaction mechanisms.

Sample Problems

1. Write the rate expressions for each of the following reactions:

2. Because it has a nonpolluting combustion product (water vapor), hydrogen gas is used for fuel aboard
the space shuttles and in earthbound cars with prototype engines.

(a) Express the rate in terms in changes in [H2], [O2], and [H2O] with time.
(b) When [O2] is decreasing at 0.23 mol/L.s, at what rate is [H2O] increasing?

1.3 The Rate Law and its Components

 Rate law expresses the rate as a function of reactant concentrations, product concentrations and
temperature.
 For the general reaction,

the rate law is: rate = k[A]x[B]y

The proportionality constant k, called the rate constant, is specific for a given reaction at a given
temperature; it does not change as the reaction proceeds. The values of the exponents, x and y in the
rate law indicate the order of the reaction with respect to reactants A and B, respectively. The sum of
x and y is called the overall reaction order.
 The components of the rate law – rate, reaction orders and rate constant – must be determined
experimentally. This is technically called the differential rate law and it expresses how the rate
depends on concentration.

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 The experimental approach to finding the components of the rate law is to use concentration
measurements to find the initial rate from which the reaction orders and rate constant can be
calculated.
Sample Problems

1. Many gaseous reactions occur in car engines and exhaust systems. One of these is

(a) Use the above data to determine the individual and overall reaction orders. (b)Write the rate law
and calculate the rate constant.

2. Determine the specific rate constant for the reaction of NO and O 2 to yield NO2 given that the
concentrations of both NO and O 2 are 0.5 mol/L each, and the reaction rate is 0.10 molL -1min-1. The
order with respect to NO is 2, while the order with respect to O2 is 1.

1.4 The Integrated Rate Laws: Concentration Changes Over time

 The second type of rate law is called integrated rate law. The integrated rate law helps us to
understand how the concentrations of the species in a chemical reaction change with time.
 In a first-order reaction of the type

 From the differential rate law,

the form of the integrated rate law can be derived thus, making use of calculus:

where [A]o and [A]t are the concentrations of A at times 0 (not necessarily the beginning of the
reaction) and t, respectively.
 In a second-order reaction, the form of the differential rate law is

and the corresponding form of the integrated rate law using calculus is

 For the zero-order reaction, the form of the differential rate law is: rate = k([A]o)0 = k and the form
of the integrated rate law is: [A]t = -kt + [A]o.

Reaction Half-life
 The half-life of a reaction (t½) is the time required for the reactant concentration to drop to half of its
original. A half-life is expressed in time units appropriate for a given reaction and is characteristic of
that reaction at a given temperature.
 For a first-order reaction, the half-life is a constant, independent of reactant concentration.
t½ = 0.693/k.
 For a second order reaction, half-life is given by the expression:
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 For a zero-order reaction, half-life is given by the expression:

Sample Problems

1. At 1000oC, cyclobutane (C4H8) decomposes in a first-order reaction, with the very high rate constant
of 87 s-1, to two molecules of ethylene (C2H4). (a) If the initial concentration of C2H4 is 2.00 M, what is
the concentration after 0.010 s? (b) What fraction of C4H8 has decomposed in this time?
2. For the decomposition of hydrogen iodide, HI into gaseous hydrogen and iodine, the rate law for the
reaction is rate = K. (a) What is the concentration of HI after 30 minutes if the initial concentration is
0.5 M and the specific rate constant is 7.2 x 10-3 mol/L-min.? (b) What is the half-life (in seconds)?
3. Molecules of butadiene, C4H6, can couple to form C8H12. The rate law for the reaction is Rate =
K[C4H6]2. (a) If the rate constant is estimated to be 0.014 L.mol-1.s-1, what is the half-life of the
reaction (in seconds) when [C4H6]o is 0.016 M? (b) If the initial concentration of C4H6 is 0.016, how
much time (in seconds) must elapse for the concentration to drop to 0.0016 M?
4. A certain first-order reaction has a half-life of 20 mins. (a) Calculate the rate constant of this reaction.
(b) How much time is required for this reaction to be 75% complete? (c) What fraction remains after
50 mins?

1.5 The Effect of Temperature on Reaction Rate

 Temperature often has a major effect on reaction rate. For many reactions near room temperature, an
increase of 10oC causes a doubling or tripling of the rate.
 Temperature affects reaction rate by affecting the rate constant. This can be illustrated by calculations
from concentration and time data for the same reaction run at different temperatures.
 Arrhenius equation gives a key relationship between T and K: K = Ae-Ea/RT , where K = rate
constant; T = absolute temperature; R = universal gas constant; A = a constant (related to the
orientation of colliding particles; Ea = energy of activation of the reaction.
 A plot of ln k vs. 1/T gives a straight line with slope = -Ea/R.
 Therefore, the Arrhenius equation can be expressed in the form of a straight line formula:
ln k = ln A - Ea/R(1/T)
Since k and 1/T have linear relationship, Ea can also be calculated from two temperatures, T 1 and T2.
ln k1 = ln A - Ea/R (1/T1) and ln k2 = ln A - Ea/R (1/T2)

Subtracting ln k1 from ln k2, we get: ln (k2/k1) = - Ea/R(1/T2 - 1/T1)

Sample Problems

1. The decomposition of hydrogen iodide

has rate constants of 9.51 x 10-9 L/mol.s at 500K and 1.10 x 10-5 L/mol.s at 600 K. Find Ea.
2. Rate constants for the reaction

were measured at four different temperatures (data shown below). Determine the energy of activation
(in kJ/mol) for the reaction.

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1.6 Explaining the Effects of Concentration and Temperature

 Two major theories can be used to explain the observed effects of concentration and temperature on
reaction rate – the collision theory and the transition-state theory.

1.6.1 The Collision Theory

 The collision theory views the reaction rate as a result of particles colliding with a certain frequency
and minimum energy. Atoms, molecules and ions must collide with each other to react. Therefore, the
number of collisions per unit time provides an upper limit on how fast a reaction can take place. A
greater frequency of collisions leads to a higher reaction rate. Hence, rate α # of collisions per second.
 Increasing the temperature increases the collision frequency.
 Also, not every collision leads to a reaction. Only those collisions with enough energy to exceed Ea
can lead to reaction. Collisions that lead to product are known as effective collisions.
 Therefore, for collision to be effective, the collision must have sufficient energy and a particular
molecular orientation.
 A temperature rise enlarges the fraction of collisions with enough energy to exceed the activation
energy. At a given temperature, the fraction of molecular collisions (f) with energy greater than or
equal to the activation energy, Ea, is given by
f = e-Ea/RT
The magnitudes of both Ea and T affect the fraction of sufficiently energetic collisions.
 The effect of molecular orientation is contained in the term A of the Arrhenius equation, and this term
is called the frequency factor. Frequency factor, A = pZ, where p is the orientation probability factor
(also known as steric factor) and Z is the collision frequency.

1.6.2 The Transition-State Theory

 The transition state model focuses on the high-energy species that forms through an effective
collision. This high-energy, extremely unstable species is called the transition state or activated
complex.
 There is an energy barrier to all chemical reactions. These barriers affect the separation of atoms or
the transfer of an atom between molecular fragments. When the barriers to reactions are too high, the
reaction cannot occur at detectable rates because too few molecules acquire sufficient energy to cross
the barrier. Thus the reaction is either extremely slow or does not occur at all.
 Consider the energy diagrams below- assume that AB molecule decomposes into A and B. As the A-B
bond is broken, the energy increases. Later, the energy decreases as the electrons and other nuclei in
the A- and B-containing fragments rearrange. This is the case for the first diagram below.
 The energy at the maximum is called transition-state energy, ETS, because the system is in a
transition state between reactants and products. The difference in energy between the reactant and the
activated complex is the activation energy, Ea, defined as the minimum energy that a reacting system
must absorb from its environment in order to react.

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 Therefore, the transition state theory relates the reaction rates and the energy of the reactant particles
being converted to products.

Sample Problems

1. A key reaction in the uDraw a rough sketch of the energy profile for each of the following cases: (a)
ΔE = + 10 KJ/mol, Ea = 25 KJ/mol (b) ΔE = - 50 KJ/mol, Ea = 50 KJ/mol

2. The reaction 2 N2O5(g) 4 NO2(g) + O2(g) was studied at several temperatures and the following
K values were obtaipper atmosphere is

The Ea(fwd) is 19 kJ, and the ΔHrxn for the reaction as written is -392 kJ. Draw a reaction energy diagram
for this reaction, postulate a transition state, and calculate Ea(rev).

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CHEM 102 PROBLEM SET NO. 1

1. A reaction is carried out with water as the solvent. How does the addition of more water to the
reaction vessel affect the rate of the reaction? Explain.

2. The compound AX2 decomposes according to the equation 2 AX 2(g) 2 AX (g) + X2(g). In one
experiment, [AX2] was measured at various times and these data were obtained:

(a) Find the average rate over the entire experiment.

(b) Is the initial rate higher or lower than the rate in part (a)?

3. Express the rate of reaction in terms of the change in concentration of each of the reactants and
products:

When [B] is decreasing at 0.5 mol/L.s, how fast is [A] decreasing?

4. Reaction rate is expressed in terms of changes in concentration of reactants and products. Write a
balanced equation for

5. What are the units of the following if concentrations are expressed in mole per liter? (a)
Rate constant for zero-order rate law (b) Rate constant for first-order rate law (c) Rate constant for
second-order rate law (d) Rate constant for third-order rate law
6. By what factor does the rate change in each of the following cases (assuming constant
temperature)?
(a) A reaction is first order in reactant A, and [A] is doubled.
(b) A reaction is second order in reactant B, and the [B] is halved.
(c) A reaction is second order in reactant C, and [C] is tripled.
7. A reaction has the experimental rate law “initial rate = K[A]2”. Explain what happens to the rate
when the concentration of A is tripled, and when the concentration of A is halved?
8. For the reaction

the following data were obtained at constant temperature:

(a) What is the order with respect to each reactant? (b) Write the rate law. (c) Calculate k .
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9. For the simple decomposition reaction

rate = k[AB]2 and k = 0.2 L/mol.s. How long will it take for [AB] to reach one-third of its initial
concentration of 1.50 M?

10. In a first order decomposition reaction, 50.0% of a compound decomposes in 10.5 min. (a) What
is the rate constant of the reaction? (b) How long does it take for 75.0% of the compound to
decompose?
11. Consider the following general reaction and data:

(a) What is the reaction order with respect to each reactant?

(b) Calculate the rate constant. (c) Write the rate law for this reaction. (d) Express the rate in
terms of changes in concentration with time for each of the components.
12. After five half-lives, what fraction of reactant remains in a first order reaction?
13. The rate constant of a reaction is 4.7 x 10-3 s-1 at 25oC, and the activation energy is 33.6 kJ/mol.
What is k at 75oC?
14. The rate constant of a reaction is 4.50 x 10-5 L/mol.s at 195oC and 3.20 x 10-3 L/mol.s at 258oC.
What is the activation energy of the reaction?
15. For the reaction

Assuming a one-step reaction, (a) draw a reaction energy diagram; (b) calculate Ea(rev); and (c)
sketch a possible transition state if ABC is V-shaped.
16. Use the diagram below to answer the following questions:

(a) Is the reaction exothermic or endothermic?

(b) What is the value of ΔE for the forward reaction?

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(c) What is the activation energy in each direction?

17. At 25oC, what is the fraction of collisions with energy equal to or greater than an activation
energy of 100 kJ/mol?

18. For the reaction: H2(g) + I2(g) 2HI(g) where the rate law is K[H 2][I2], and the rate constants are
2.45 x 10 L/mol and 0.950 L/mol at 302oC and 508oC, respectively. (a) Calculate the values of Ea
-4

and A for the reaction. (b) Calculate the value of the rate constants at 375oC.

19. What must be the activation energy if the rate constant is doubled between 273 K and 373 K?

20. For a reaction, the constant A in the Arrhenius equation is 6.00 x 10 12 mol/L.s. and Ea = 100
KJ/mol. What is the rate constant at 400K?

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TOPIC 2: CHEMICAL EQUILIBRIUM – The Extent of Chemical Reactions (CH.17)

2.1 The Concept of Equilibrium – Equilibrium State and Equilibrium Constant

2.1.1 Equilibrium State

 Some chemical reactions are irreversible – they occur only in one direction (forward direction). All
the reactants are completely used up, and the reaction goes to completion. In such a case, a single
arrow is used in describing said reaction.

 However, most chemical reactions are reversible – they occur in both forward and backward
directions. None of the reactants is completely used up; so they do not go to completion. That means,
the conditions of the reaction can be maintained or changed so that the reactants are obtained from the
products. A double-headed arrow shows a reversible reaction.

 As an example of a reversible reaction, consider the following system at equilibrium:

 To prove that both forward and backward reactions occur, the intensity of the brown color is less. This
is because the decomposition of N 2O4 slows down as the number of N 2O4 molecules decreases. At the
same time, the number of NO 2 molecules increase and these molecules collide and combine to reform
N2O4. Eventually the system reaches equilibrium: the concentrations of N 2O4 and NO2 remain constant
because the forward and reverse reaction rates have become equal:

At equilibrium: ratefwd = raterev

rf

point of equilibrium

rb

 Therefore, chemical equilibrium is a state of balance in which the rates of forward and backward
reactions are exactly equal. Chemical equilibrium is dynamic – both reactions occur continually.

2.1.2 The Equilibrium Constant

 Using the N2O4-NO2 system

We can write the rate laws for both forward and reverse reactions based on kinetics.

Ratefwd = kfwd[N2O4]2eq and Raterev = kfwd[NO2]2eq

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 The ratio of constants gives rise to a new overall constant called equilibrium constant (K).

 In general, for a reaction system at equilibrium:

 The equilibrium constant, K or Keq is a number equal to a particular ratio of equilibrium

concentrations of products and reactants at a particular temperature. If Keq is calculated for
concentration, it is designated as Kc; if it is calculated for partial pressures of gases, it is designated as
Kp.

2.1.3 Some Facts About Equilibrium Constant Expressions

 The concentrations of pure solids, of pure liquids, and of solvents in dilute solutions never appear in
Keq expressions. This is because their concentrations are constant.
 If the stoichiometric coefficients of a balanced equation are multiplied by some factor, the new
equilibrium constant equals the old equilibrium constant raised to the power of the multiplication
factor. That is, K2 = (K1)a if the original stoichiometric coefficients are multiplied by a.
 The equilibrium constants for a reaction and its reverse are the reciprocals of one another.
K2 = 1/K1 or K1 = 1/K2
 Kp is related to Kc by the formula, Kp = Kc(RT)Δn(g) ,
where Δn(g) = [total # of moles of gaseous products] - [total # of moles of gaseous reactants]; R = gas
constant = 0.08205atmLK-1mol-1, and T = Kelvin temperature.

2.2 The Reaction Quotient and the Equilibrium Constant

 The equilibrium constant expression can also be written from the law of mass action (also known as
the law of chemical equilibrium), proposed by two (2) Norwegian chemists, Cato Guldberg and
Peter Waage. It states: At a given temperature, a chemical system reaches a state in which a particular
ratio of reactant and product concentrations has a constant value.

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 The particular ratio of concentration terms that we write for a given reaction is called the reaction
quotient, Q (also known as the mass-action expression).

 In general, for the equation,

 As the reaction proceeds toward the equilibrium state, there is a continual, smooth change in the
concentrations of reactants and products. So Q also changes until equilibrium is reached. At
equilibrium, Q = K.

 If Q < K, the reactant concentrations are higher than product concentrations. So the reaction proceeds
forward to convert some reactants to products. If Q > K, product concentrations are higher than
reactant concentrations. So the reaction proceeds backward to convert some products to reactants.

 Monitoring Q tells whether the system has reached equilibrium, how far away it is if it has not, and, in
which direction it is changing to reach equilibrium.

 If an overall reaction is the sum of two or more reactions, the overall reaction quotient (or equilibrium
constant) is the product of the reaction quotients (or equilibrium constants) for the stages.

Qoverall = Q1 x Q2 x Q3 x ………….
Koverall = K1 x K2 x K3 x ………….

Sample Problems

1. The following equilibrium concentrations were observed for the reaction:

[NH3] = 3.1 x 10-2 mol/L, [N2] = 8.5 x 10-1 mol/L, [H2] = 3.1 x 10-3 mol/L. Calculate the value of K
(a) for this reaction . (b) for the reverse reaction. (c) Calculate the value of K for the reaction:

2. The reaction for the formation of nitrosyl chloride was studied at 25oC.

PNOCl = 1.2 atm; PNO = 5.0 x 10-2 atm; PCl2 = 3.0 x 10-1 atm. (a) Calculate the value of Kp for this
reaction at 25oC. (b) Calculate KC.
3. A chemical engineer injects limestone (CaCO3) into the hot flue gas of a coal-burning power plant to
form lime (CaO), which scrubs SO2 from gas and forms gypsum (CaSO 4.2H2O). Find Kc for the
following reaction, if CO2 pressure is in atmospheres: 2.00 x 10-3 mol of Cl2(g) was found in the flask.

1. For the reaction

At a point during the reaction, [N 2O4] = 0.12 M and [NO2] = 0.55 M. all species and the value of K. Is
the reaction at equilibrium? If not, in which direction is it progressing?

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2.3 Solving Equilibrium Problems

 Two (2) types of problems are considered here:

 Solving for K given equilibrium quantities (concentrations or partial pressures).
 Solving for equilibrium quantities given K.

Sample Problems

1. At a certain temperature, a 1.00-L flask initially contained 0.298 mol of PCl 3(g) and 8.7 x 10-3 mol of
PCl5(g). After the system had reached equilibrium, 2.00 x 10 -3 mol of Cl2(g) was found in the flask.
Gaseous PCl5 decomposed thus:

Calculate the equilibrium concentrations of all species and the value of K.

2. In order to study hydrogen iodide decomposition, a researcher fills an evacuated 2.00-L flask with
0.200 mol of HI gas and allows the reaction to proceed at 453oC.

At equilibrium, [HI] = 0.078 M. Calculate Kc.

3. At 27oC and 1 atm, N2O4 is 20% dissociated into NO2. Find (a) Kp and (b) the % dissociation at 27 0C
and a total pressure of 0.10 atm.

4. Fuel engineers use the extent of the change from CO and H 2O to CO2 and H2 to regulate the
proportions of synthetic fuel mixtures. If 0.250 mol of CO and 0.250 mol of H 2O are placed in a 15-
mL flask at 90 K, what is the composition of the equilibrium mixture? At this temperature, K c is 1.56
for the equation

5. Phosgene is a potent chemical warfare agent that is now outlawed by international agreement. It
decomposes by the reaction

Calculate [CO], [Cl2], and [COCl2] when each of the following amounts of phosgene decomposes and
reaches equilibrium in a 10.0-L flask: (a) 5.00 mol of COCl2 (b) 0.100 mol of COCl2
6. The research and development unit of a chemical company is studying the reaction of CH4 and H2S,
two components of natural gas:

In one experiment, 1.00 mol of CH4, 1.00 mol of CS2, 2.00 mol of H2S, and 2.00 mol of H2 are mixed
in a 250-mL vessel at 900oC. At this temperature, Kc = 0.036.
(a) In which direction will the reaction proceed to reach equilibrium?
(b) If [CH4] = 5.56 M at equilibrium, what are the equilibrium concentrations of the other substances?

2.4 External Factors Affecting Equilibria – Le Chatelier’s Principle

 A system at equilibrium is able to return to equilibrium after a change in conditions moves it away
from that state. This drive to re-attain equilibrium is stated in Le Chatelier’s principle: when a
chemical system at equilibrium is disturbed, it re-attains equilibrium by undergoing a net reaction
which reduces the effect of the disturbance.

 Effect of change in concentration: If a reactant or product is added (i.e., increase in its

concentration), the system reacts to consume some of it by shifting away from the added substance. If
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a reactant or product is removed (i.e, decrease in its concentration), the system reacts to produce some
of it by shifting toward the removed component. In this case, Keq is not affected.

 Effect of a change in pressure (volume): Changes in pressure have significant effects only on
gaseous components. Pressure changes can occur in three ways:
 Changing the concentration of a gaseous component
 Adding an inert gas
 Changing the volume of the reaction vessel
For a system that contains gases at equilibrium, in which the amount (mol) of gas, ngas, changes
during the reaction:
 Adding an inert gas has no effect on the equilibrium position because the volume does not
change so that all reactant and product concentrations remain the same.
 If the volume becomes smaller (pressure is lower), the reaction shifts so that the total number
of gas molecules decreases.
 If the volume becomes larger (pressure is higher), the reaction shifts so that the total number
of gas molecules increases.
In this case again, Keq is not affected.

 Effect of change in temperature: If energy is added to the equilibrium system by heating, the shift
will be in the direction that absorbs energy. If energy is removed by cooling, the shift is in the
direction that releases energy. In this case, Keq is affected.

 Effect of catalyst: Catalyst has no effect on equilibrium systems. This is because both rf and rb are
affected.
.
SAMPLE PROBLEMS

1. For the equilibrium system

What happens to (a) [H2O] if O2 is added? (b) [H2S] if O2 is added? (c) [O2] if H2S is removed?
(d) [H2S] if sulfur is added?
2. How would you change the volume of each of the following reactions to increase the yield of the
products?

3. How does an increase in temperature affect the equilibrium concentration of the underlined substances
and K for each of the following reactions?

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 Department of Chemistry, College of Science & Technology, University of Liberia

CHEM 102 PROBLEM SET NO. 2

1. Distinguish between the terms equilibrium constant and reaction quotient.

2. If the reaction quotient is smaller than the equilibrium constant for a reaction such as

3. If there is no change in concentrations, why is the equilibrium state considered dynamic ?

4. Is K very large or very small for a reaction that goes essentially to completion? Explain.
5. At particular temperature, Kc = 1.6 x 10-2 for

Calculate Kc for each of the following reactions:

6. Calculate Kc for the following equilibria:

7. At 425oC, Kp = 4.18 x 10-9 for the reaction

In one experiment, 0.20 atm of HBr(g), 0.010 atm of H2(g), and 0.010 atm of Br2(g) are introduced into a
container. Is the reaction at equilibrium? If not, in which direction will it proceed?
8. Gaseous PCl5 decomposes according to the reaction

In one experiment, 0.15 mol of PCl5(g) was introduced into a 2.0-L container. Construc the reaction
table for this process.
9. When 2.0 moles of HI(g) are placed in a 1.0-L container at 25oC and allowed to dissociate according to
the equation:

it is found that 20% of HI(g) has dissociated at equilibrium. Calculate Kc and Kp.
10. For the following reaction, Kp = 6.5 x 104 at 308 K:

At equilibrium, PNO = 0.35 atm and PCl2 = 0.10 atm. What is the equilibrium partial pressure of
NOCl(g)?
11. Hydrogen iodide decomposes according to the reaction

A sealed 1.50-L container initially holds 0.00623 mol of H 2, 0.00414 mol I2, and 0.0244 mol of HI at
703 K. When equilibrium is reached, the concentration of H2 (g) is 0.00467 M. What are the
concentrations of HI(g) and I2(g)?

12. Ammonium a hydrogen sulfide decomposes according to the following reaction, for which Kp = 0.11
at 250oC:

If 55.0g of NH4HS(s) is placed in a sealed 5.0-L container, what is the partial pressure of NH 3 (g) at
equilibrium?

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13. At 46oC, Kp for the reaction

is 0.66. Compute the percent dissociation of N2O4 at this temperature and a total pressure of 380 torr.
What are the partial pressures of N2O4 and NO2 at equilibrium?
14. What will happen to the number of moles of SO 3 in equilibrium with SO2 and O2 in each of the

following cases for the reaction:

(a) Oxygen is added. (b) The volume is decreased. (c) The temperature is decreased. (d) A catalyst is
added. (e) Gaseous sulfur dioxide is removed. (f) Some argon is added.

15. (a) Predict the effect of increasing the container volume on the amounts of reactant and product in the
following reaction:

(b) How would you adjust the volume of the container in order to maximize product yield in each of
the following reactions?

(c) Predict the effect of increasing the temperature on the amount of product in the following
reaction:

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TOPIC 3: ACID-BASE (IONIC) EQUILIBRIA (CHS.18 & 19a)

 The general principles of chemical equilibrium apply equally to reactions of neutral molecules and to
reactions of ions. Ionic equilibrium is the application of chemical equilibrium to ionic reactions.

3.1 Acids and Bases in Water – The Arrhenius Theory

 In the Arrhenius theory, acids and bases are classified in terms of their formulas and their behavior in
water:
 An acid is a substance that has H in its formula and dissociates in water to yield hydronium
ions, H3O+. That is, HxB xH+ + Bx- . Example: HCl H+ + Cl-
 A base is a substance that has OH in its formula and dissociates in water to yield hydroxide
ions, OH-. That is, M(OH)y My+ + yOH- . Example: NaOH Na+ + OH-
 When an acid and a base react, they undergo neutralization. From the Arrhenius theory,
neutralization occurs when the H+ ion from the acid and the OH- ion from the base combine to form
H2O.
 However, this concept is limited since the acid and base must necessarily contain H and OH,
respectively, and the aqueous solutions of the acid and base are required.
 Acids and bases differ in their strength in water. Strength in this case means the amount of H3O+ or
OH- produced per mole of substance dissolved. We generally classify acids as either strong or weak.
 Acids and bases are electrolytes in water (i.e., they produce ions and conduct electricity in aqueous
solutions).
 Strong electrolytes dissociate completely; hence, strong acids or bases dissociate completely
into ions in water. In a dilute solution of the strong acid, virtually no acid molecules are
present after dissociation.

 Weak electrolytes dissociate partially; hence, weak acids or bases dissociate very slightly into
ions in water. In a dilute solution of the weak acid, a great majority of the acid molecules are
undissociated. Kc is very small since [H3O+] << [HA]o. That is, [HA]eq≈[HA]o. Therefore,
taking HCN (a weak acid) as an example, the dissociation process is expressed as:

 There is a specific equilibrium constant for acid dissociation; it is known as acid-dissociation (or
acid-ionization) constant, Ka.

 But [H2O] is so large that it is treated as a constant. Therefore, this constant, [H 2O] is
multiplied by Kc, giving a new constant, Ka.

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 Like any equilibrium constant, Ka is a number whose magnitude is temperature dependent and tells
how far to the right the reaction has proceeded to reach equilibrium.
 For solutions of the same initial HA concentration, the smaller the K a, the lower the percent
dissociation of HA and weaker is HA.
 For example, 1M HClO2 (Ka = 1.1 x 10-2), it is 10% dissociated; 1M CH3COOH (Ka = 1.8 x 10-5), it is
0.42% dissociated; 1M HCN (Ka = 6.2 x 10-10), it is 0.0025% dissociated.
 NB> 1M solution of acid with K a (≈ 10-2), percent dissociation ≈ 10%; 1M solution of acid with K a (≈
10-5), percent dissociation ≈ 0.42%; 1M solution of acid with K a (≈ 10-10), percent dissociation ≈
0.001%.

Classifying the Relative Strengths of Acids and Bases

 Qualitatively, acids and bases are classified as strong or weak. There is no fixed rule here; just
memorize the formula.
Strong Acids
 Hydrohalic acids: hydrochloric (HCl), hydrobromic (HBr) and hydroiodic (HI) acids
 Oxoacids: Nitric (HNO3), sulfuric (H2SO4) and perchloric (HClO4) acids
Weak Acids
 Hydrohalic acid: hydrofluoric acid (HF)
 Oxoacids (those in which the number of oxygen atom equals or exceeds the number of
ionizable protons by one): hypochlorous (HClO), nitrous (HNO2), phosphoric (H3PO4) and
phosphorous (H3PO3) acids
 Carboxylic acids (RCOOH): acetic (CH3COOH) and benzoic (C6H5COOH) acids
 Acids in which H is not bonded to halogen or oxygen: hydrocyanic acid (HCN),
hydrosulfuric acid (H2S)
Strong Bases
 Water-soluble compounds containing O2- or OH- ions {M2O,MOH, MgO or Mg(OH)2}:
NaOH, KOH, LiOH, Ca(OH)2, CaO, K2O, etc.
 Bases of the type MO or M(OH)2 are only slightly soluble in water, but the soluble portions
dissociate completely.
Weak Bases
 Many compounds with electron-rich N atom are weak bases. Examples are ammonia (NH 3)
and the amines {(CH3)2NH – dimethyl amine , etc.}.

Sample Problem
 Classify each of the following compounds as a strong acid, weak acid, strong base, or weak base:
(a) H2SeO4 (b) (CH3)2CHCOOH (c) KOH (d) (CH3)2CHNH2 (e) HClO3

3.2 Autoionization of Water and the pH Scale

 Water is an extremely weak electrolyte. Even deionized or distilled water shows electrical
conductivity to a very less extent. This is due to the fact that water itself dissociates into ions very
slightly in an equilibrium process known as autoionization.

Since [H2O] is constant,

Kc[H2O]2 = [H3O+][OH-] = Kw
Kw is known as the ion-product constant for water
At 25oC, Kw = 1.0 x 10-14 = [H3O+][OH-]; [H3O+] = [OH-] = (1.0 X 10-14)½ = 1.0 x 10-7 M
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 Autoionization of water results into the following:

 Change in [H3O+] causes an inverse change in [OH -] and vice versa. Higher [H 3O+] means
lower [OH-] and vice versa.
 Since both ions are present in all aqueous systems;
In acidic solutions: [H3O+] > [OH-]; in a neutral solution: [H 3O+] = [OH-]; in a basic solution:
[H3O+] < [OH-]

 The [H3O+] can be expressed using a numerical system called a p-scale (the negative of the common
logarithm of the number. In the case of [H 3O+] or [H+], we get pH. Therefore, pH is the negative
logarithm of [H3O+] or [H+].
pH = -log[H3O+] or [H+]; thus [H3O+] = 10-pH
 -
Also [OH ] can be expressed as pOH.
pOH = -log[OH-]; thus [OH-] = 10-pOH
 Similarly, pK = -log K
 An acidic solution has a lower pH (higher [H 3O+]) than a basic solution. An acidic solution has a
higher pOH (lower [OH-] than a basic solution.
 On the pH scale, pH < 7 means the solution is acidic; pH = 7 means the solution is neutral; pH > 7
means the solution is basic.
 Given that:
Kw = [H3O+][OH-] = 1.0 x 10-14 (at 25oC)
-log Kw = -log [H3O+] + (-log[OH-]) = -log (1.0 x 10-14)
pKw = pH + pOH = 14

Sample Problems

1. A research chemist adds a measured amount of HCl gas to pure water at 25 oC and obtains a solution
with [H3O+] = 3.0 x 10-4 M. Calculate [OH-]. Is this solution neutral, acidic or basic?
2. In an art restoration project, a conservator prepares copper-plate etching solution by diluting
concentrated HNO3 to 2.0 M, 0.30 M, and 0.0063 M HNO3. Calculate [H3O+], pH, [OH-] and pOH of
the three solutions at 25oC.
3. A solution of NaOH has a pH of 9.52, what is its pOH, [H3O+] and [OH-] at 25oC?

 In the laboratory, pH values are usually obtained with an acid-base indicator or more precisely, with
a pH meter.
 Acid-base indicators are organic molecules whose colors depend on the acidity or basicity of the
solution. pH or litmus paper consists of a paper strip impregnated with one or a mixture of indicators.
 The pH meter measures [H 3O+] by means of two electrodes immersed in the test solution. One
electrode provides a stable reference voltage; the other has an extremely thin, conducting, glass
membrane that separates a known internal [H3O+] from the unknown external [H3O+]. The difference
in [H3O+] creates a voltage difference across the membrane, which is measured and displayed in pH
units.

3.3 Proton Transfer and the Bronsted-Lowry Theory of Acids and Bases

 According to J.N. Bronsted and T.M. Lowry,

 An acid is a proton donor, any species that donates H+ ion. All Arrhenius acids are Bronsted-
Lowry acids.
 A base is a proton acceptor, any species that accepts a H+ ion. A Bronsted-Lowry base must
contain a lone pair of electrons to bind the H+ ions. Examples are NH3, CO32-, F-, OH-, etc.
 Bronsted-Lowry bases are not necessarily Arrhenius bases, but all Arrhenius bases are Bronsted-
Lowry bases.
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 Water is said to be amphiprotic – it can donate a proton to a base (acting as an acid), and accept a
proton from an acid (acting as a base).

 The interaction between a Bronsted-Lowry acid and a Bronsted-Lowry base yields a conjugate acid-
base pair.
 A conjugate acid is the species which results when the base has accepted a proton; hence, it
has one more H and one fewer minus charge than the base.
 A conjugate base is the species which results when the acid has donated a proton; hence, it
has one fewer H and one more minus charge than the base.

Sample Problems

1. The following reactions are important environmental processes. Identify the conjugate acid-base pairs.

2. Write the ionization reaction for NH 4+ (acting as an acid). Identify the Bronsted-Lowry acid, the
conjugate acid and the conjugate base.

 The net direction of an acid-base reaction depends on the relative strengths of the acids and bases
involved. A reaction proceeds to a greater extent in the direction in which a dtronger acid and a
stronger base form a weak conjugate acid-base pair.

Sample Problem

Predict the net direction and whether Kc is greater or less than 1 for each of the following reactions
(assume equal initial concentrations of all species):

3.4 Solving Problems Involving Weak-Acid Equilibria

 For a weak monoprotic acid, [H3O+] = [H3O+]from HA + [H3O+]from H2O ≈ [H3O+]from HA

Since [H3O+] from the autoionization of water is negligible. Since Ka is small, the acid dissociates to a
small extent; hence, change in concentration of HA is negligible.
[HA] = [HA]o + [HA]dissoc. ≈ [HA]o
 Therefore, for the reaction,

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 For polyprotic acids (acids with more than one ionizable proton), dissociation of proton from the acid
occurs one at a time, with each dissociation step having a different Ka.

 Consider H3PO4 for example:

 For a typical weak polyprotic acid, Ka1 > Ka2 > Ka3 . Therefore, the relative acid strengths are H3PO4 >
H2PO4- > HPO42- ; only the first dissociation step makes an important contribution to [H3O+].

Sample Problems

1. Phenylacetic acid (C6H5CH2COOH, simplified here as HPAc) builds up in the blood of persons with
phenylketonuria, an inherited disorder that, if untreated, causes mental retardation and death. A study
of the acid shows that the pH of 0.12M HPAc is 2.62. What is the Ka of HPAc?
2. Propanoic acid (CH3CH2COOH, simplified as HPr) is a carboxylic acid whose salts are used to retard
growth in foods. What is the [H3O+] of 0.10 M HPr (Ka = 1.3 x 10-5)?
3. Cyanic acid (HOCN) is an extremely acrid, unstable substance. What is the [H3O+] and pH of 0.10 M
HOCN (Ka = 3.5 x 10-4)?
4. Ascorbic acid (H2C2H6O6, simplified as H2Asc), known as vitamin C, is a diprotic acid (Ka1 = 1.0 x 10-
5
) and Ka2 = 5.0 x 10-12 found in citrus fruit. Calculate [H2Asc], [HAsc-], [Asc2-], and the pH of 0.050
M H2Asc.
3.5 Weak Bases and their Relation to Weak Acids

 Consider a weak base dissolving in water.

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 As in the case of the ionization of an acid, the base-dissociation or base-ionization constant, Kb is

expressed as:

 Ammonia and its derivatives (amines) and the anions of weak acids are two large classes of weak
bases.
 For a weak acid, HA, its anion dissociates thus:

 The relative concentrations of HA and A- determine the acidity or basicity of the solution:
 In an acid solution, [HA]>>[A-] and [H3O+]from HA >> [OH-]from H2O. So the solution is acidic.
 In the A- solution, [A-]>>[HA] and [OH-]>> [H3O+]from H2O. So the solution is basic.
 Ka of HA can be mathematically related to Kb of A- by treating the two dissociation reactions as a
reaction sequence and adding them together:

 The sum of acid-dissociation and base-dissociation reactions is the autoionization of water.

 Therefore, Ka x Kb = Kw

Sample Problems

1. Dimethylamine, (CH3)2NH, a key intermediate in detergent manufacture has a Kb of 5.9 x 10-4. What is
the pH of 1.5 M (CH3)2NH?
2. Sodium acetate (CH3COONa, simplified as NaAc) is used in photographic development and textile
dyeing. What is the pH of 0.25M NaAc? Ka of acetic acid (HAc) is 1.8 x 10-5?

3.6 Acid-Base Properties of Salt Solution

 When a salt dissolves, one or both of its ions may react with the water and affect the pH of the
solution. This interaction of salt and water is called hydrolysis. The salt may behave as a neutral, a
basic or an acidic solution when it is dissolved in water.
 Salts containing cations of strong bases and anions of strong acids yield neutral solutions
because these ions do not react with water. Examples of such salts are NaCl, KCl, NaNO 3 and
KNO3.
 Salts containing cations of weak bases and anions of strong acids yield acidic solutions
because the cation acts as a weak acid, and the anion does not react. Examples of such salts
include NH4Cl, AlCl3 and Fe(NO3)3. Certain highly charged metal ions such as Al 3+ and Fe3+
act as weak acids and react with water to yield acidic solutions.

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 Salts containing cations of strong bases and anions of weak acids yield basic solutions
because the anion acts as a weak base, and the cation does not react. Examples of such salts
are sodium acetate and sodium benzoate.
 If a salt consists of a cation that can act as a weak acid and an anion that can act as a weak
base, both ions react with water. In these cases, the overall acidity of the solution depends on
the relative acid strength (K a) or base strength (Kb) of the separated ions. For example, a
solution of NH4CN would be basic because the Kb of CN- > Ka of NH4+ as shown below:

The ions react with water; so Ka or Kb of the ions may be referred to as hydrolysis constant,
Kh.
Since Kh of CN- > Kh of NH4+, the reaction of CN- with water proceeds much further than the
reaction of NH4+ with water.

 Salts which contain cations of strong bases and anions of polyprotic acids are said to be
amphiprotic – they can react with water by either donating H + or accepting H+. An example
is Na2HPO4.

Sample Problems

1. Predict whether aqueous solutions of the following are acidic, basic, or neutral, and write an equation
for the reaction of any ion with water: (a) Potassium perchlorate, KClO 4 (b) Sodium benzoate,
C6H5COONa (c) chromium (III) nitrate, Cr(NO3)3 (d) zinc formate, Zn(HCOO)2.

2. The acid ionization (hydrolysis) constant of Zn2+ is 1.0 x 10-9.

(a) Calculate the pH of a 0.0010 M solution of ZnCl2.

(b) What is the base dissociation constant of Zn(OH)+?
3. Calculate the extent of (%) hydrolysis of a 0.0100 M solution of AlCl3; Ka for Al(H2O)63+ is 1.4 x 10-5.

4. Calculate the pH of a 0.100 M solution of NH 4OCN. Kb for NH3 is 1.75 x 10-5 and Ka for HOCN is 3.3
x 10-4.

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3.7 Equilibria of Acid-Base Buffer Systems

 An acid-base buffer is a solution that lessens the impact on pH from the addition of acid or base. To
withstand the addition of strong acid or strong base without significantly changing its pH, a buffer
have an acidic component that can react with the added OH - ion and a basic component that can react
with the added H3O+.
 The components of a buffer should be such that they do not react with each other. Usually said
components are the conjugate acid-base pair of a weak acid (or base).

3.7.1 The Common Ion Effect – How a Buffer works

 Buffers work through a phenomenon known as common-ion effect. The common-ion effect occurs
when a given ion is added to an equilibrium mixture that already contains that ion. and the position of
equilibrium shifts away from forming more of it. For example, consider the dissociation of acetic acid,
HAc in water:

 If some Ac- ion is added added (from soluble sodium acetate, NaAc), by Le Chatelier’s principle, the
equilibrium shifts away from the added component (Ac -), to the left. The effect is a decrease in the
[H3O+], thus lowering the extent of dissociation of HAc and an increase in the pH of HAc (making it
less acidic).
 Buffering works when there is a large excess of the acidic and basic components of the buffer that will
consume H3O+ ion or OH- ion.
 In a similar manner, when solid NH4Cl is added to NH3 solution, the NH4+ ions produced cause the
position of the NH3-H2O equilibrium to shift to the left. This reduces the equilibrium concentration of
OH- ions, and thus increases the pH of the solution.

Sample Problems

1. A solution contains 1.0 M HF (Ka = 7.2 x 10-4) and 1.0 M NaF. Calculate the percent dissociation of
HF. (NB. The percent dissociation of HF is 2.7% in a solution of 1.0 M HF alone.)
2. A solution of acetic acid (HAc) has concentration of 0.25 M. What is the pH of the solution after
adding enough sodium acetate (NaAc) to make the solution 0.10 M in the salt? (Ignore any change in
volume on adding the solid sodium acetate). Ka = 1.8 x 10-5.

Weak Acid/Salt Buffer

 After adding a strong acid of concentration, a, pH is slightly decreased, and after adding a strong base
of concentration, b, the pH is slightly increased.

Weak Base/Salt Buffer

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 After adding a strong acid of concentration, a, pOH is slightly increased (pH is slightly decreased),
and after adding a strong base of concentration, b, the pOH is slightly decreased (pH is slightly
increased).

The Handerson-Hasselbalch Equation

 For any weak acid, HA, the dissociation equation and Ka expressions are:

3.7.2 Buffer Capacity and Buffer Range

 Buffer capacity is a measure of the ability of a buffer to resist pH change. It depends on both the
absolute and relative component ratios.
 The more concentrated the components of a buffer, the greater the buffer capacity.
 Buffer range is the pH over which the buffer acts effectively, and it is related to the relative
component concentrations.

3.7.3 Preparing a Buffer

 Several steps are required to prepare a buffer of a desired pH:

 Choose the conjugate acid-base pair. The desired pH determines this choice. For an effective
buffer, pH ≈ pKa (i.e., ratio of component concentrations ≈ 1). Therefore, if for example, a
buffer of pH 3.9 is to be prepared, the pKa of the acid component should be ≈ 3.9. That is, Ka
= 10-3.9 ≈ 1.3 x 10-4. (Good choices include formic, lactic and glycolic acids.) Formic acid and
sodium formate are the most preferred buffer components.
 Calculate the ratio of buffer component concentrations. Using HCOOH and HCOONa, the
ratio of buffer component is;

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 Determine the buffer concentration. Use the stock concentration of acid and the final volume
of buffer to calculate the mole of the acid.
If stock concentration of acid = 0.5 M and final volume desired is 500 mL,

then, mole of of HCOOH = 0.5 L x 0.5 mol/L = 0.25 mol HCOOH

If 1 mole HCOOH ~ 1.4 mols HCOONa; then 0.25 mol HCOOH = (0.25 x 1.4)mol HCOONa
= 0.35 mol HCOONa

Therefore, mass of HCOONa = 0.35 mol HCOONa x 68g/mol = 23.8 g

 Mix the solution and adjust pH. Therefore, dissolve 23.8 g HCOONa in 0.5 M HCOOH and
dilute to 0.5L (500 mL).

Sample Problems

1. A solution contains 1.0 M HF (Ka = 7.2 x 10-14) and 1.0 M NaF. Calculate the % dissociation of HF.
(NB. The % dissociation of HF is 2.7 % in solution of 1.0 M HF alone.)
2. Calculate the pH:
(a) Of a buffer solution consisting of 0.50 M CH3COOH and 0.50 M CH3COONa.
(b) After adding 0.020 mol of solid NaOH to 1.0 L of the buffer solution in part (a).
(c) After adding 0.020 mol of HCl in 1.0 L of the buffer solution in part (a). K a of CH3COOH = 1.8 x
10-5. (Assume the additions cause negligible volume changes).

3. A buffer is made by adding 100 mL of 0.75 M lactic acid (K a = 1.4 x 10-4) and 50 mL of 0.25 M
sodium lactate. (a) What is the pH of the resulting buffer? (b) If 0.003 mole of HCl is added to the
above buffer, calculate the new pH and the change in pH.

4. An environmental chemist needs a carbonate buffer of pH 10.00 to study the effects of the acid rain in
limestone-rich soils. How many grams of Na 2CO3 must she add to 1.5 L of freshly prepared 0.20 M
NaHCO3 to make the buffer? Ka of HCO3- is 4.7 x 10-11.

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CHEM 102 PROBLEM SET NO. 3

1. Write the Ka expression for each of the following in water: (a) HCN (b) CH 3COOH (C) HSO4-
(d) HBrO2
2. (a) Which of the following are Arrhenius acids? (i) H 3PO3 (ii) Ca(OH)2 (iii) NaHSO4 (iv) CH4 (v)
H3N
(b) Which of the following are Arrhenius bases? (i) H 3AsO4 (ii) Ba(OH)2 (iii) HClO (iv) CH3OH
(v) H2NNH2
3. Classify each as a strong or weak acid or base: (i) H3AsO4 (ii) Sr(OH)2 (iii) HCOOH (iv) RbOH
4. (a) What is the pH of 0.0333M HNO3? Is the solution neutral, acidic or basic?
(b) What is the pH of 6.14 x 10-3M HI? Is the solution neutral, acidic or basic?
(c) What is the pOH of 1.59 x 10-3M HClO4? Is the solution neutral, acidic or basic?
5. (a) What are [H3O+],[OH-], and pOH with a pH of 9.85?
(b) How many moles of H3O+ or OH- must you add per liter of HA solution to adjust its pH from
3.15 to 3.65? Assume a negligible volume change.
6. In each equation, label the acids, bases and conjugate pairs:
7. A 0.15 M solution of butanoic acid, CH 3CH2CH2COOH, contains 1.51 x 10-3 M H3O+. What is the Ka
of butanoic acid?
8. Hydrofluoric acid, HF, has a Ka of 6.8 x 10-4. What are the [H3O+], [F-], and [OH-] in 0.75 M HF.
9. Chloroacetic acid, ClCH2COOH, has a pKa of 2.87. What are [H 3O+], pH, [ClCH2COO-], and
[ClCH2COOH] in 1.25 M ClCH2COOH?
10. In a 0.20 M solution, a weak acid is 3.0% dissociated. (a) Calculate the [H 3O+], pH, [OH-], and pOH of
the solution. (b) Calculate Ka of the acid.
11. Calculate the percent ionization of a 1.00 M solution of hydrocyanic acid, HCN (Ka = 6.2 x 10-10).
12. A 0.250-mol sample of HX is dissolved in enough water to form 655 mL of solution. If the pH of the
solution in 3.54, what is the Ka of HX?
13. What is the pH of a 0.25 M solution of ethanolamine? [Kb of HOCH2CH2NH2 = 3.2 x 10-5]
14. What is the pH of each of the following solutions?
(a) 0.150 M KCN? [Ka of HCN = 6.2 x 10 -14] (b) 0.40 M triethylammonium chloride,
(CH3CH2)3NHCl? [Kb for triethylamine, (CH3CH2)3N = 5.2 X 10-4]
15. (a) What is the pKb of ClO2-? [Ka of HClO2 = 1.1 x 10-2] (b) What is the pK b of dimethylammonium
ion, (CH3)2NH2+? [Kb of (CH3)2NH = 5.9 x 10-4]
16. K1 and K2 for oxalic acid, HC2O4 are 5.6 x 10-2 and 5.4 x 10-5. What is [OH-] in a 0.005 M solution of
Na2C2O4?
17. What are the [H3O+] and the pH of a buffer that consists of 0.55 M HNO 2 and 0.75 M KNO2 [Ka of
HNO2 = 7.1 x 10-4]
18. Find the pH of a buffer that consists of 0.25M NH3 and 0.15M NH4Cl [pKb of NH3= 4.75]
19. A buffer was prepared by dissolving 0.0200 mole of propionic acid and 0.015 mole of sodium
propionate in enough water to make 1 L of solution. (a) What is the pH of the buffer? [K a for
propionic acid is 1.3 x 10-5] (b) What would be the pH change if 1.0 x 10 -5 mol of HCl were added to
10cm3 of the buffer? (c) What would be the pH change if 1.0 x 10 -5 mole of NaOH were added to
10cm3 of the buffer?
20. What is the component concentration ratio, [Pr -]/[HPr], of a buffer that has a pH of 5.44 [K a of HPr =
1.3 x 10-5]?
21. Choose a specific acid-base conjugate pairs to make the following buffers: (a) pH 4.5 (b) pH 7.0
[Check Appendix C of the textbook, Silberberg Chemistry].
of butanoic acid?

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TOPIC 4: EQUILIBRIA OF SLIGHTLY SOLUBLE IONIC COMPOUNDS (CH. 19b)

4.1 Introduction: Ion-Product Expression (Qsp) and the Solubility-Product Constant (Ksp)

 When a soluble ionic compound dissolves in water, it dissociates completely into separate hydrated
cations and anions. Consider for example, lead(II) chloride, PbCl 2. When it is first added to the water,
no Pb2+ and Cl- ions are present. However, as he dissolving action proceeds, the concentrations of Pb 2+
and Cl- ions increase, and it becomes more and more likely that these ions will collide and reform the
solid phase.
 Thus, two competing processes occur simultaneously until equilibrium is reached:
 The dissolving of the ionic compound (solid0 in solution:

 The reforming of the solid ionic compound from its ions:

 All this is indicated by the observation that the solution contains not only the Pb 2+(aq) and Cl-(aq) ions
expected from complete dissociation, but also undissociated PbCl2(aq) molecules and PbCl+(aq).
 When the solid has dissolved to the greatest extent possible and no more solid dissolves, the solution
formed is said to be saturated.
 Assuming there is complete dissociation of a slightly soluble solute into its component ions, there is
equilibrium existing between the solid solute and the aqueous ions. So for a saturated solution of
lead(II) chloride in water, we have this equation:

 As with all other equilibrium systems, this one can be expressed by a reaction quotient, Qc:

 Since PbCl2 is a solid, its concentration is a constant. Combining this constant with Qc gives the ion-
product expression, Qsp. Thus Qsp = Qc[PbCl2] = [Pb2+][Cl-]2.
 The extent to which a solid dissolves is called its solubility, and this is expressed in mol/L. At
equilibrium, Qsp becomes Ksp, known as solubility-product constant. Thus, the product of the two
measures of the solubility is a constant. Hence, the term solubility product constant, Ksp.
 Therefore, the expression becomes: Ksp = [Pb2+][Cl-]2.
 In general, for a solution of a slightly soluble ionic compound, M pXq, composed of the ions Mn+ and
Xz-, the equilibrium condition is: Qsp = [Mn+]p[Xz-]q = Ksp.
 The value of Ksp indicates how far to the right the dissolution proceeds at equilibrium (saturation).
 There is a difference between the solubility of a given solid and its solubility product. The solubility
product is an equilibrium constant and has only one value for a given ionic compound at a given
temperature. Solubility (or molar solubility), on the other, is an equilibrium position and has an
infinite number of possible values at a given temperature, depending on the other conditions (such as
the presence of a common ion).
 The Ksp value provides a guide to relative solubility, as long as we compare compounds whose
formulas contain the same total number of ions. In such cases, Ksp = [cation][anion] = (S)(S) = S2 and
the higher the Ksp, the greater the solubility (S). Also, S = √Ksp = solubility.
 For example, compounds such as AgI(s) (Ksp = 1.5 x 10-16), CuI(s) (Ksp = 5.0 x 10-12) and CaSO4(s) (Ksp =
6.1 x 10-5), dissolve to produce two ions. Hence, the most soluble is the salt with the largest K sp.
CaSO4(s) > CuI(s) > AgI(s).
 However, if the compounds being compared produce different numbers of ions when they dissolve,
the Ksp values cannot be compared directly to determine relative solubilities. So one must calculate
the solubility of each compound using the same procedure as shown in sample problems 2-4.

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Sample Problems

1. Write the ion-product expression for each compound: (a) magnesium carbonate (b) iron(II) hydroxide
(c) calcium phosphate (d) silver sulfide
2. (a) Lead(II) sulfate (PbSO4) is a key component in lead-acid car batteries. Its solubility in water at
25oC is 4.25 x 10-3 g/100 mL. what is the Ksp of PbSO4?
(b) When lead(II) fluoride (PbF2) is shaken with pure water at 25oC, the solubility is found to be 0.64
g/L. Calculate the Ksp of PbF2.
3. Calcium hydroxide (slaked lime) is a major component of mortar, plaster and cement, and solutions of
Ca(OH)2 are used in industry as a cheap, strong base. Calculate the solubility of Ca(OH)2 in water if
the Ksp is 6.5 x 10-6.
4. Lead (II) chloride dissolves to a slight extent in water. If the lead ion concentration was found to be
1.62 x 10-2 mol/L, calculate the Ksp of PbCl2.

4.2 The Effects of a Common Ion and pH on Solubility

 Consider that lead(II) chromate, PbCrO4(s) is dissolved in water. A saturated solution has a Ksp value of
2.3 x 10-13. If the soluble salt, sodium chromate (Na 2CrO4) is added, the concentration of the common
ion, CrO42-, increases, and some of it combines with Pb2+ to more solid PbCrO4. From the Le
Chatelier’s principle, the overall effect is a shift in the position of equilibrium to the left, thus
decreasing the concentrations of the ions, and hence, the solubility of the solid:

 Therefore, the presence of a common ion decreases the solubility of a slightly soluble ionic compound.
 The pH of a solution can also affect the solubility of an ionic compound. If the compound contains the
anion of a weak acid, a decrease in pH by the addition of H3O+ (from a strong acid) increases its
solubility. For example, magnesium hydroxide dissolves according to the equilibrium:

 An increase in pH (addition of OH- ions) will, by common ion effect, force the equilibrium to the left,
decreasing the solubility of Mg(OH)2. On the other hand, an decrease in pH (addition of H + ions)
increases the solubility, because OH- ions are removed from solution by reacting with H + ions. The
equilibrium position moves to the right.

Sample Problems

1. In sample problem #4 of section 4.1, we calculated the solubility of Ca(OH) 2 in water. What is its
solubility in 0.10 M Ca(NO3)2? [Ksp of Ca(OH)2 is 6.5 x 10-6.
2. The solubility of AgCl in pure water is 1.3 x 10 -5 M. What is its solubility in seawater where the [Cl -]
is 0.55 M? (Ksp of AgCl = 1.8 x 10-10)
3. Calculate the solubility of Fe(OH)3 in mol/L (Ksp = 4 x 10-38) in each of the following: (a) water
(assume pH = 7.0 and constant) (b) a solution buffered at pH = 5.0 (c) a solution buffered at pH =
11.0

4.3 Precipitation – Predicting the Formation of a Precipitate: Qsp vs. Ksp

 Precipitation is one of two types of exchange reactions. Precipitation is an exchange reaction in which
one of the products is an insoluble compound.
 To predict whether a precipitate will be formed when solutions of two ionic compounds are mixed,
reaction quotient, Qsp is compared with Ksp.
 If Ksp = Qsp, the solution is saturated and at equilibrium; no change occurs.
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 Department of Chemistry, College of Science & Technology, University of Liberia

 If Ksp = Qsp, the solution is supersaturated and precipitate forms; precipitation continues
until the concentrations of the ions satisfy Ksp since the ions now have low solubility.
 If Q < Ksp, the solution is unsaturated and no precipitate forms; more of the solid can go into
solution since the ions now have high solubility.
 To prevent the precipitation of a slightly soluble ionic compound, some substance must be added
which will keep the concentration of one of the ions so low that the solubility product of the
compound is not attained.

Sample Problems

1. A common laboratory method for preparing a precipitate is to mix solutions containing the
components. Does a precipitate form when 100 mL of 0.36 M Ca(NO 3)2 is mixed with 200 mL of
0.060 M NaF? [Ksp of CaF2 = 3.2 x 10-11]
2. If the concentration of Ni2+ ion in water is 0.010 M, (a) what is the minimum concentration of S 2-
necessary to begin precipitating NiS, and (b) what will be the concentration of Ni 2+ when the S2-
concentration reaches 0.00010 M? Ksp for NiS is 3.0 x 10-21.
3. A solution is prepared by mixing 150 mL of 1.00 x 10 -2 M Mg(NO3)2 and 250 mL of 1.00 x 10-1 M
NaF. Calculate the concentrations of Mg2+ and F- at equilibrium with solid MgF2 (Ksp = 6.4 x 10-9).

4.4 Selective Precipitation of Ions

 We can often separate one ion in a solution from another by exploiting differences in the solubility of
their compounds with a given precipitating ion. This is selective precipitation and it involves adding
a solution of precipitating ion until Qsp value of the more soluble compound is almost equal to its Ksp
value. This method ensures that the Ksp value of the less soluble compound is exceeded as much as
possible. As a result, the maximum amount of the less soluble compound precipitates, but none of the
more soluble compound does.

Sample Problems

1. A solution consists of 0.20 M MgCl2 and 0.10 M CuCl2. Calculate the [OH-] that would separate the
metal ions as their hydroxides. Ksp of Mg(OH)2 is 6.3 x 10-10; Ksp of Cu(OH)2 is 2.2 x 10-20.

2. The [Ag+] of a solution is 4 x 10-3. Calculate the [Cl-] that must be exceeded before AgCl can
precipitate. The Ksp for AgCl at 25oC is 1.8 x 10-10.

3. Assume you have a solution that is 0.020 M in both Cd 2+ and Ni2+. When you add sulfide ions, CdS
and NiS will precipitate. (a) Which precipitates first? (b) Just before the second ion begins to
precipitate as an insoluble sulfide, what is the concentration in solution of the ion that precipitates
first? Ksp for CdS = 3.6 x 10-29; Ksp for NiS = 3.0 x 10-21.

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 Department of Chemistry, College of Science & Technology, University of Liberia

CHEM 102 PROBLEM SET NO. 4

1. Write the ion-product expressions for (a) silver carbonate (b) barium fluoride (c) copper(II) sulfide
2. The solubility of silver dichromate at 15oC is 8.3 x 10-3 g/100 mL solution. Calculate Ksp.
3. Find the molar solubility of SrCO3 (Ksp = 5.4 x 10-10) in (a) pure water (b) 0.13 M Sr(NO3)2.
4. Using Ksp values, tell which salt in each pair is more soluble in water. (a) AgCl and AgCN (b) ZnS
and PbS (c) MgCO3 and CaCO3 (d) Mg(OH)2 and Ca(OH)2 (e) HgS and FeS
5. Calculate the solubility of each of the following compounds/salts in mole/liter and gram/liter:
(a) Al(OH)3, Ksp = 2 x 10-32 (b) MgF2, Ksp = 6.4 x 10-9 (c) Ba(IO4)2, Ksp = 1.57 x 10-9 (d) CaSO4, Ksp
= 6.1 x 10-5 (e) MgNH4PO4, Ksp = 3 x 10-13
6. Calculate values of Ksp for the following ionic compounds using the given information:
(a) A sample of 4.8 x 10-5 mol calcium oxalate, CaC2O4 dissolves in 1.0 L of water to produce a
saturated solution.
(b) The concentration of Pb2+ ion in a solution saturated with PbBr2 is 2.14 x 10-2 M.
(c) The molar solubility of BiI3 is 1.32 x 10-5 mol/L.
(d) The solubility of iron(II) oxalate, FeC2O4 is 65.9 mg/L at 25oC.
7. If you mix 100 mL of a 0.0010 M solution of Na2CO3 with 100 mL of 0.0010 M BaCl2, will a
precipitate of BaCO3 form?
8. Suppose the concentration of aqueous nickel(II) ion in a solution is 1.5 x 10-6 M. If enough Na2CO3 is
added to make the solution 6.0 x 10-4 M in the CO32- ion, will precipitation of NiCO3 occur? Will it
occur if the [CO32-] is raised by a factor of 100? The Ksp of NiCO3 is 6.6 x 10-9.
9. If the concentration of Ba2+ in water is 1.0 x 10-3 M, what concentration of SO42- is necessary to just
begin precipitating BaSO4(s)? Ksp for BaSO4 is 1.1 x 10-10. If you have 100 mL of a 0.0010 M solution
of CO32- ion, how many grams of BaCl2 must be added to begin precipitating BaCO3? How many
grams of BaCl2 must be added to reduce the carbonate ion concentration to 1.0 x 10-6 M?
10. What are the concentrations of all of the ions in solution after 100.0 mL of 0.020 M Pb(NO3)2 and 100.0
mL of 0.020 M NaCl are mixed?

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Department of Chemistry, College of Science & Technology, University of Liberia

TOPIC 5: ELECTROCHEMISTRY (CH. 21)

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