Acid–Base Equilibria

Study/Review Guide
Arrhenius Acids and Bases
• Acids taste sour and cause certain dyes to change color.
• Bases taste bitter and feel soapy.
• Arrhenius concept of acids and bases:
• An acid is a substance that, when dissolved in water, increases the concentration of H+ ions.
• Example: HCl is an acid.
• An Arrhenius base is a substance that, when dissolved in water, increases the concentration of
OH– ions.
• Example: NaOH is a base.
• This definition is quite narrow in scope because it limits us to aqueous solutions.

Brønsted-Lowry Acids and Bases

• We can use a broader, more general definition for acids and bases that is based on the fact that acid-
base reactions involve proton transfers.

The H+ Ion in Water

• The H+(aq) ion is simply a proton (the nucleus of a hydrogen atom without its valence electron).
• In water, clusters of hydrated H+(aq) ions form.
• The simplest cluster is H3O+(aq).
• We call this a hydronium ion.
• Larger clusters are also possible (such as H 5O2+ and H9O4+).
• Generally, we use the expressions H+(aq) and H3O+(aq) interchangeably.
Proton-Transfer Reactions
• We will focus our attention on H+(aq).
• According to the Arrhenius definitions, an acid increases [H +] and a base increases [OH–].
• Another definition of acids and bases was proposed by Brønsted and Lowry.
• In the Brønsted-Lowry system, a Brønsted-Lowry acid is a species that donates H+, and a Brønsted-
Lowry base is a species that accepts H+.
• Therefore, a Brønsted-Lowry base does not need to contain OH –.
• NH3 is a Brønsted-Lowry base, but not an Arrhenius base.
• The transfer of a proton always involves both an acid (donor) and a base (acceptor).
• Consider NH3(aq) + H2O(l)  NH4+(aq) + OH–(aq).
• H2O donates a proton to ammonia.
• Therefore, water is acting as an acid.
• NH3 accepts a proton from water.
• Therefore, ammonia is acting as a base.
• An amphiprotic substance can behave either as an acid or as a base.
• Thus, water is an example of an amphiprotic species.
Conjugate Acid-Base Pairs
• Whatever is left of the acid after the proton is donated is called its conjugate base.
• Similarly, a conjugate acid is formed by adding a proton to the base.
• Consider HX(aq) + H2O(l)  H3O+(aq) + X–(aq).
• HX and X– differ only in the presence or absence of a proton.
• They are said to be a conjugate acid-base pair.

1
 • X– is called the conjugate base.
• After HX an (acid) loses its proton, it is converted into X– (a base).
• Therefore, HX and X– are a conjugate acid-base pair.
• After H2O (a base) gains a proton, it is converted into H3O+ (an acid).
• H3O+ is the conjugate acid.
• Therefore, H2O and H3O+ are a conjugate acid-base pair.
Relative Strengths of Acids and Bases
• The stronger an acid is, the weaker its conjugate base will be.
• We can categorize acids and bases according to their behavior in water.
• 1. Strong acids completely transfer their protons to water.
• No undissociated molecules remain in solution.
• Their conjugate bases have negligible tendencies to become protonated.
• An example is HCl.
• 2. Weak acids only partially dissociate in aqueous solution.
• They exist in solution as a mixture of molecules and component ions.
• Their conjugate bases show a slight tendency to abstract protons from water.
• These conjugate bases are weak bases.
• Example: Acetic acid is a weak acid; acetate ion (conjugate base) is a weak base.
• 3. Substances with negligible acidity do not transfer a proton to water.
• An example is CH4.
• The conjugate base of a substance with negligible acidity is a strong base.
• In every acid-base reaction, the position of the equilibrium favors the transfer of a proton from the
stronger acid to the stronger base.
• H+ is the strongest acid that can exist in equilibrium in aqueous solution.
• OH– is the strongest base that can exist in equilibrium in aqueous solution.
• Hydronium ions and hydroxide ions are the strongest possible acid and base, respectively, that
can exist in aqueous solution.
• Stronger acids react with water to produce hydronium ions, and stronger bases react with
water to form hydroxide ions.
• This effect is known as the leveling effect of water.

The Autoionization of Water

• In pure water the following equilibrium is established:
2H2O(l)  H3O+(aq) + OH–(aq)
• This process is called the autoionization of water.
The Ion Product of Water
• We can write an equilibrium constant expression for the autoionization of water.
• Because H2O(l) is a pure liquid, we exclude it from the expression:
Kc = [H3O+][OH–] = Kw
• Kw is called the ion-product constant.
• At 25 °C, the ion-product constant of water is
1.0  10–14 = Kw = [H3O+][OH–]
• This applies to pure water as well as to aqueous solutions.
• A solution is neutral if [OH–] = [H3O+].
• If [H3O+] > [OH–], the solution is acidic.
• If [H3O+] < [OH–], the solution is basic.
The pH Scale
• In most solutions [H+] is quite small.
• We express [H+] in terms of pH.
pH = −log[H+] = −log[H3O+]
• The expressions [H+] and [H3O+] are used interchangeably.
• Note that this is a logarithmic scale.
• Thus, a change in [H+] by a factor of 10 causes the pH to change by 1 unit.
• Most pH values fall between 0 and 14.
• In neutral solutions at 25 °C, pH = 7.00.
• In acidic solutions, [H+] > 1.0  10–7M, so pH < 7.00.
• As the pH decreases, the acidity of the solution increases.
• In basic solutions, [H+] < 1.0  10–7M, so pH > 7.00.
• As the pH increases, the basicity of the solution increases (acidity decreases).
pOH and Other “p” Scales
• We can use a similar system to describe [OH–].
pOH = −log[OH–]
• Recall that the value of Kw at 25 °C is 1.0  10–14.
• Thus, we can describe a relationship between pH and pOH:
−log[H+]+ (−log[OH–]) = pH + pOH = −logKw = 14.00
Measuring pH
• The most accurate way to measure pH is to use a pH meter.
• A pH meter consists of a pair of electrodes connected to a meter that measures small voltages.
• A voltage that varies with pH is generated when the electrodes are placed in a solution.
• This voltage is read by the meter, which is calibrated to display pH.
• Dyes that change color as pH changes are also useful.
• They are called acid-base indicators.
• Indicators are less precise than pH meters.
• Many indicators do not have a sharp color change as a function of pH.
• Most acid-base indicators can exist as either an acid or a base.
• These two forms have different colors.
• The relative concentration of the two different forms is sensitive to the pH of the solution.
• Thus, if we know the pH at which the indicator turns color, we can use this color change to
determine whether a solution has a higher or a lower pH than this value.
• Some natural products can be used as indicators. (Tea is colorless in acid and brown in base; red
cabbage extract is another natural indicator.)

Strong Acids and Bases

Strong Acids
• The most common strong acids are HCl, HBr, HI, HNO 3, HClO3, HClO4, and H2SO4.
• Strong acids are strong electrolytes.
• All strong acids ionize completely in solution.
• For example, nitric acid completely ionizes in water:
HNO3(aq) + H2O(l) → H3O+(aq) + NO3–(aq)
• Since H and H3O are used interchangeably, we write
+ +

HNO3(aq) → H+(aq) + NO3–(aq)

• Note that we do not use equilibrium arrows for this equation because the reaction lies
entirely to the right.
• In solutions the strong acid is usually the only significant source of H+.
• Therefore, the pH of a solution of a monoprotic acid may usually be calculated directly from the
initial molarity of the acid.
• Caution: If the molarity of the acid is less than 10–6 M, then the autoionization of water needs to
be taken into account.
Strong Bases
• The most common strong bases are ionic hydroxides of the alkali metals or the heavier alkaline earth
metals (e.g., NaOH, KOH, and Sr(OH)2 are all strong bases).
• Strong bases are strong electrolytes and dissociate completely in solution.
• For example,
NaOH(aq) → Na+(aq) + OH–(aq)
• The pOH (and thus the pH) of a strong base may be calculated using the initial molarity of the base.
• Not all bases contain the OH– ion.
• Ionic metal oxides, for example, are basic.
• They are thus able to abstract a proton from water and generate OH –:
O2–(aq) + H2O(l) → 2OH–(aq)

Weak Acids
• Weak acids are only partially ionized in aqueous solution.
• There is a mixture of ions and un-ionized acid in solution.
• Therefore, weak acids are in equilibrium:
HA(aq) + H2O(l)  H3O+(aq) + A–(aq)
or
HA(aq)  H+(aq) + A–(aq)
• We can write an equilibrium constant expression for this dissociation:
[H3O + ][A − ] [H + ][A − ]
Ka = or K a =
[HA] [HA]
• Ka is called the acid-dissociation constant.
• Note that the subscript “a” indicates that this is the equilibrium constant for the dissociation
(ionization) of an acid.
• Note that [H2O] is omitted from the Ka expression. (H2O is a pure liquid.)
• The larger Ka, the stronger the acid.
• Ka is larger since there are more ions present at equilibrium relative to un-ionized molecules.
• If Ka >> 1, then the acid is completely ionized and the acid is a strong acid.
Calculating Ka from pH
• In order to find the value of Ka, we need to know all of the equilibrium concentrations.
• The pH gives the equilibrium concentration of H +.
• Thus, to find Ka we use the pH to find the equilibrium concentration of H + and then use the
stoichiometric coefficients of the balanced equation to help us determine the equilibrium
concentration of the other species.
• We then substitute these equilibrium concentrations into the equilibrium constant
expression and solve for Ka.
Percent Ionization
• Another measure of acid strength is percent ionization.
• Consider the reaction
HA(aq)  H+(aq) + A–(aq)
 [A − ]equilibrium
% ionization = 100%
[HA]initial
• Percent ionization relates the equilibrium H+ concentration, [H+]equilibrium, to the initial HA
concentration, [HA]initial.
• The higher the percent ionization, the stronger the acid.
• However, we need to keep in mind that percent ionization of a weak acid decreases as the
molarity of the solution increases.
Using Ka to Calculate pH
• Using Ka, we can calculate the concentration of H+ (and hence the pH).
• Write the balanced chemical equation, clearly showing the equilibrium.
• Write the equilibrium expression. Look up the value for Ka (in a table).
• Write down the initial and equilibrium concentrations for everything except pure water.
• We usually assume that the equilibrium concentration of H + is x.
• Substitute into the equilibrium constant expression and solve.
• Remember to convert x to pH if necessary.
• What do we do if we are faced with having to solve a quadratic equation in order to determine x?
• Often this cannot be avoided.
• However, if the Ka value is quite small, we can make a simplifying assumption.
• Assume that x is negligible compared with the initial concentration of the acid.
• This will simplify the calculation.
• It is always necessary to check the validity of any assumption.
• Once we have the value of x, check to see how large it is compared with the initial
concentration.
• If x < 5% of the initial concentration, the assumption is probably a good one.
• As a general rule, if x > 5% of the initial concentration, then it may be best to solve the
quadratic equation or to use successive approximations.
• You should ALWAYS check the validity of any simplifying assumptions after you have
finished solving a problem!
• Weak acids are only partially ionized.
• Percent ionization is another method used to assess acid strength.
• The concentration of H+ will increase as the concentration of acid increases; however
these two concentrations are not directly proportional.
• Percent ionization decreases as the concentration of the acid increases
Polyprotic Acids
• Polyprotic acids have more than one ionizable proton.
• The protons are removed in successive steps.
• Consider the weak acid H2SO3 (sulfurous acid):
H2SO3(aq)  H+(aq) + HSO3–(aq) Ka1 = 1.7  10–2
HSO3–(aq)  H+(aq) + SO32–(aq) Ka2 = 6.4  10–8
where Ka1 is the dissociation constant for the first proton released, Ka2 for the second, etc.
• It is always easier to remove the first proton than the second proton in a polyprotic acid.
• Therefore, Ka1 > Ka2 > Ka3, etc.
• The majority of the H+(aq) at equilibrium usually comes from the first ionization (i.e., the Ka1
equilibrium).
• If the successive Ka values differ by a factor of less than or equal to103, we can usually get a good
approximation of the pH of a solution of a polyprotic acid by considering only the first ionization.
• H2SO4 is a special case.
• The first ionization step involves complete ionization.
 • The second ionization is a weak ionization.
• HSO4- is a weak acid.

Weak Bases
• Weak bases remove protons from substances.
• There is an equilibrium between the base and the resulting ions:
weak base + H2O(l)  conjugate acid + OH–(aq)
• Example:
NH3(aq) + H2O(l)  NH4+(aq) + OH–(aq)
• The base-dissociation constant, Kb, is defined as
[NH +4 ][OH − ]
Kb =
[NH3 ]
• The larger Kb, the stronger the base.
Types of Weak Bases
• Weak bases generally fall into one of two categories.
• Neutral substances with a lone pair of electrons that can accept protons
• Most neutral weak bases contain nitrogen.
• Amines are related to ammonia and have one or more N–H bonds replaced with N–C bonds
(e.g., CH3NH2 is methylamine).
• Anions of weak acids
• Example: ClO– is the conjugate base of HClO (weak acid):
ClO–(aq) + H2O(l)  HClO(aq) + OH–(aq) Kb = 3.33  10–7

Relationship between Ka and Kb

• We can quantify the relationship between the strength of an acid and the strength of its conjugate
base.
• Consider the following equilibria:
NH4+(aq)  NH3(aq) + H+(aq)
NH3(aq) + H2O(l)  NH4+(aq) + OH–(aq)
• We can write equilibrium expressions for these reactions:
[NH3 ][H + ] [NH +4 ][OH − ]
Ka = Kb =
[NH +4 ] [NH3 ]
• We add these equations together:
NH4+(aq)  NH3(aq) + H+(aq)
NH3(aq) + H2O(l)  NH4+(aq) + OH–(aq)
• The net reaction is the autoionization of water:
H2O(l)  H+(aq) + OH–(aq)
• Recall that
Kw = [H+][OH–]
• We can use this information to write an expression that relates the values of Ka, Kb, and Kw for a
conjugate acid-base pair.
 [NH3 ][H + ]  [NH +4 ][OH − ]  + −
Ka K b =  +   = [H ][OH ] = K w
 [NH 4 ]  [NH 3 ] 
 • The product of the acid-dissociation constant for an acid (Ka) and the base-dissociation constant
for its conjugate base (Kb) equals the ion-product constant for water (Kw):
Ka  Kb = Kw
• Alternatively, we can express this as
pKa + pKb = pKw = 14.00 (at 25 °C)
• Thus, the larger Ka (and the smaller pKa), the smaller Kb (and the larger pKb).
• The stronger the acid, the weaker its conjugate base, and vice versa.

Acid-Base Properties of Salt Solutions

• Nearly all salts are strong electrolytes.
• Therefore, salts in solution exist entirely as ions.
• Acid-base properties of salts are a consequence of the reactions of their ions in solution.
• Many salt ions can react with water to form OH – or H+.
• This process is called hydrolysis.
An Anion’s Ability to React with Water
• Consider an anion, X–, as the conjugate base of an acid.
• Anions from weak acids are basic.
• They will cause an increase in pH.
• Anions from strong acids are neutral.
• They do not cause a change in pH.
• Anions with ionizable protons (such as HSO3– ) are amphiprotic.
• How they behave in water is determined by the relative magnitudes of Ka and Kb for the ion.
• If Ka > Kb, the anion tends to decrease the pH.
• If Kb > Ka, the anion tends to increase the pH.
A Cation’s Ability to React with Water
• Polyatomic cations that have one or more ionizable protons are conjugate acids of weak bases.
• They tend to decrease pH.
• Many metal ions can cause a decrease in pH.
• Group 1A and heavy Group 2A metal cations are cations of strong bases and do not alter pH.
• Metals with small, highly charged cations (such as Fe3+ and Al3+) have Ka values comparable to
values for familiar weak acids such as acetic acid.
• The metal ions attract unshared electron pairs of water molecules and become hydrated.
• The larger the charge on the metal ion, the stronger the interaction between the ion and
the oxygen of its hydrating water molecules.
• This weakens the O–H bonds in the water molecules and facilitates proton transfer from
hydration water molecules to solvent water molecules.

Combined Effect of Cation and Anion in Solution

• The pH of a solution may be qualitatively predicted using the following guidelines:
• Salts derived from a strong acid and a strong base are neutral.
• Examples are NaCl and Ba(NO3)2.
• Salts derived from a strong base and a weak acid are basic.
• Examples are NaClO and Ba(C2H3O2)2.
• Salts derived from a weak base (or a small cation with a charge of 2+ or greater) and a strong acid
are acidic.
• Examples are NH4NO3 and AlCl3.
• Salts derived from a weak acid and a weak base can be either acidic or basic.
• Equilibrium rules apply!
 • We need to compare Ka and Kb for hydrolysis of the anion and the cation.
• For example, consider NH4CN.
• Both ions undergo significant hydrolysis.
• Is the salt solution acidic or basic?
• • The Ka of NH4+ is smaller than the Kb of CN–, so the solution should be basic.

Acid-Base Behavior and Chemical Structure

Factors That Affect Acid Strength
• Consider H–A.
• Three factors influence acid strength:
• O–H bond polarity: As bond polarity increases, more electron density is drawn from the
H, and acid strength increases.
 
• The H–A bond must be polar with H + and A –.
• In ionic hydrides such as NaH, the bond polarity is reversed.
 
• The H–A bond is polar with H – and A +.
• In this case, the substance is a base.
• O–H bond strength: As the bond strength decreases, acid strength increases.
• The H–A bond must be weak enough to be broken.
• Conjugate base stability (A–): The greater the stability of the conjugate base, the stronger
the acid.
Binary Acids
• The H–X bond strength is important in determining relative acid strength in any group in the periodic
table.
• The H–X bond strength tends to decrease as the element X increases in size.
• Acid strength increases down a group; base strength decreases down a group.
• H–X bond polarity is important in determining relative acid strength in any period of the periodic table.
• Acid strength increases and base strength decreases from left to right across a period as the
electronegativity of X increases.
• For example, consider the molecules HF and CH 4.
• HF is a weak acid because the bond energy is high.
• The electronegativity difference between C and H is so small that the polarity of C–H bond is
negligible, and CH4 is neither an acid nor a base.
Oxyacids
• Many acids contain one or more O–H bonds.
• Acids that contain OH groups (and often additional oxygen atoms) bound to the central atom are
called oxyacids.
• All oxyacids have the general structure Y–O–H.
• The strength of the acid depends on Y and the atoms attached to Y.
• As the electronegativity of Y increases, so does the acidity of the substance.
• The bond polarity increases, and so does the stability of the conjugate base (usually an anion).
• We can summarize how acid structure relates to the electronegativity of Y and the number of groups
attached to Y.
• For oxyacids with the same number of OH groups and the same number of oxygen atoms:
• Acid strength increases with increasing electronegativity of the central atom, Y.
• Example: HClO > HBrO > HIO
• For oxyacids with the same central atom, Y:
• Acid strength increases as the number of oxygen atoms attached to Y increases.
• Example: HClO4 > HClO3 > HClO2 > HClO
Carboxylic Acids
• There is a large class of acids that contain a –COOH group (a carboxyl group).
• Acids that contain this group are called carboxylic acids.
• Examples include acetic acid, benzoic acid, and formic acid.
• Why are these molecules acidic?
• The additional oxygen atom on the carboxyl group increases the polarity of the O–H bond and
stabilizes the conjugate base.
• The conjugate base (carboxylate anion) exhibits resonance.
• This gives it the ability to delocalize the negative charge over the carboxylate group, further
increasing the stability of the conjugate base.
• The acid strength also increases as the number of electronegative groups in the acid increases.
• For example, acetic acid is much weaker than trichloroacetic acid.

Lewis Acids and Bases

• A Brønsted-Lowry acid is a proton donor.
• Focusing on electrons, a Brønsted-Lowry acid can be considered an electron pair acceptor.
• Lewis proposed a new definition of acids and bases that emphasizes the shared electron pair.
• A Lewis acid is an electron pair acceptor.
• A Lewis base is an electron pair donor.
• Note that Lewis acids and bases do not need to contain protons.
• Therefore, the Lewis definition is the most general definition of acids and bases.
• What types of compounds can act as Lewis acids?
• Lewis acids generally have an incomplete octet (e.g., BF3).
• Transition-metal ions are generally Lewis acids.
• Lewis acids must have a vacant orbital (into which the electron pairs can be donated).
• Compounds with multiple bonds can act as Lewis acids.
• For example, consider the following reaction:
H2O(l) + CO2(g) → H2CO3(aq)
• Water acts as the electron pair donor and carbon dioxide as the electron pair acceptor in this
reaction.
• Overall, the water (a Lewis base) has donated a pair of electrons to the CO 2 (a Lewis acid).
• The Lewis concept may be used to explain the acidic properties of many metal ions.
• Metal ions are positively charged and attract water molecules (via the lone pairs on the oxygen atom
of water).
• This interaction is called hydration.
• Hydrated metal ions act as acids.
• For example,
Fe(H2O)63+(aq)  Fe(H2O)5(OH)2+(aq) + H+(aq) Ka = 2  10–3.
• In general:
• The higher the charge, the stronger the M–OH2 interaction.
• The smaller the metal ion, the more acidic the ion.
• Thus, the pH increases as the size of the ion increases (e.g., Ca2+ vs. Zn2+) and as the charge
increases (e.g., Na+ vs. Ca2+ and Zn2+ vs. Al3+).