General Chemistry II

Chapter 15 Lecture Notes

Acids and Bases

Brønsted Acids and Bases

Arrhenius (classical) acids are proton donors. Arrhenius bases are hydroxide ion donors

Brønsted acids are defined as proton donors but in a more general definition, Brønsted bases are proton
acceptors.
This leads to the concept of Acid-base conjugate pairs.
The removal of a proton from any species (a Brønsted acid) produces its conjugate base (a proton
acceptor).
The addition of a proton to any acceptor species (a Brønsted base) produces its conjugate acid (a proton
donor).
All acid-base reactions now become the reaction of an acid-base pair to produce another acid-base pair
(the conjugate base and the conjugate acid of the first pair).

The dissociation of an acid in water produces a hydronium ion (the conjugate acid of water), not a bare
proton.

HA(aq) + H2O(l) ↔ H3O+1(aq) + A-1(aq)

(Hydrogen ion does not have a free existence in water and can only exist as the hydronium ion,
H3O+1(aq). It is often still represented as just H+1.)

Many substances which do not contain hydroxide ion can now be classed as bases, such as fluoride ion,
cyanide ion, phosphate ion, bicarbonate ion, ammonia, etc. All are proton acceptors to some degree and
all produce some hydroxide ion in aqueous solution.

Ammonia is the classic example of a base that does not have hydroxide in its molecular formula.

NH3(aq) + H2O(l) ↔ NH4+1(aq) + OH-1(aq)

Exs: Identify conjugate acids of bases and conjugate bases from acid formulas.

Acid-Base Properties of Water

Water can donate a proton to a stronger base and become hydroxide ion or can accept a proton from a
stronger acid and become the hydronium ion.
Exs: ammonia, carbonate ion (washing soda), phosphate ion (TSP), HCl, HOAc

Water also autoionizes to a very small (but very important) extent to produce low concentrations of
hydronium ion and hydroxide ion. This is also a Brønsted acid-base reaction.

H2O(l) + H2O(l) ↔ H3O+1(aq) + OH-1(aq)

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The Ion Product of Water

The autoionization of pure water produces equal concentrations of hydronium ion and hydroxide ion
~(10-7M at 24 ºC). Autoionization occurs at any temperature and with any concentration of added acid or
base.
Kc = [H+1] · [OH-1]/[H2O]

Since [H2O] is a constant in most aqueous systems, equal to 55.55M, it is incorporated into the K term
and the equilibrium expression now becomes the ion product constant expression:

Kw = [H+1] · [OH-1] = 10-14 at 25ºC

(The values of Kw and Kc differ by a factor of 55.55M but [H+1] and [OH-1] would be the same whichever
version of the equation is used, because Kc = 1.80 x 10-16 )
[H+1] and [OH-1] can be varied independently by the addition of acids or bases, but their product must
always equal 10-14. This enables the calculation of any [H+1] or [OH-1] given the [OH-1] or [H+1].
(Note that when [H+1] = [OH-1], they both equal 10-7M. this is defined as a neutral solution.)

Exs: [H+1] = 6 x 10-5M, [OH-1] = 2 x 10-10 M.

[OH-1] = 2.5 x 10-9 M, [H+1] = 4.0 x 10-6M

The pH Concept

A more concise way to express the acidity or basicity of any aqueous solution.
Important to know [H+1] of any aqueous system, organic, inorganic or biochemical.

Acidic solutions are defined as [H+1] > [OH-1] or [H+1] > 10-7M
Basic solutions are defined as [H+1] < [OH-1] or [OH-1] > 10-7M
Neutral solutions are defined as [H+1] = [OH-1] = 10-7M .

pH is a concise term, devised by Arrhenius, to express [H+1] without units or exponents.

pH = -log[H+1]

Why log? Why negative log? Wide range of [H+1] values possible
pH easy to calculate from simple exponential [H+1] values as 10-1M, 10-12M, 10-7M, 100M, 10-5M, etc.
resulting range of possible pH values.
Use a calculator for terms with significant parts other than one.
(Dissection of negative log terms.)
How are sig. figs. handled in common log problems?
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+1 -5
Exs: [H ] = 6 x 10 M. pH = 4.2
[H+1] = 3.7 x 10-11 M. pH = 10.43
pH = 9.7. [H+1] = 2 x 10-10M
pH = 2.90. [H+1] = 1.3 x 10-3M

Alternative, but rarely used, pOH = -log[OH-1]

Since = [H+1] · [OH-1] = 10-14, then pH + pOH = 14

Exs: pOH = 12.60. pH = 1.40, [H+1] = 4.0 x 10-2M, [OH-1] = 2.5 x 10-13M

Exs of Specific Solutions:

What are the [H+1], pH, pOH and [OH-1] of a 0.0023 M HCl solution?
[H+1] = 0.0023M, pH = 2.64, pOH = 11.36, [OH-1] = 4.3 x 10-12.

What are the [H+1], pH, pOH and [OH-1] of a 0.00065 M Ba(OH)2 solution?
[OH-1] = 1.3 x 10-3M, pOH = 2.89, pH = 11.11, [H+1] = 7.8 x 10-12M

Acid and Base Strengths

Define acid and base strength.

Most acids are weak.
Memorize the short list of strong acid formulas, names and anions (conjugate bases).
All other acids are weak!
All strong acids are strong electrolytes.
Their conjugate bases have negligible base strength. Why?
Memorize the short list of strong acid formulas, names and anions (conjugate bases).

All weak acids are weak electrolytes.

Their conjugate bases are fairly strong proton acceptors. Why?
Some examples of well-known weak acids:

Memorize the short list of strong base formulas and names.

All other bases are weak, including all other metal hydroxides, ammonia.

Hydronium ion is the strongest acid that can exist in water. Why?
Any acid such as HCl immediately dissociates and donates its proton to water to form hydronium ion.

Hydroxide ion is the strongest base that can exist in water.

Ex: dissociation of perchloric acid. (Also nitric, HCl, etc.)

Stronger bases such as oxide ion or amide ion react with water to form hydroxide ion.
Ex: Potassium oxide or sodium amide.
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Weak Acids and Acid Ionization Constants

All weak acids have an associated acid dissociation constant, Ka.

(Ka values for strong acids are "large" and have no useful meaning.)

Kc applies to the "true" reaction HA(aq) + H2O(l) ↔ H3O+1(aq) + A-1(aq)

Ka applies to the simplified equation HA(aq) ↔ H+1(aq) + A-1(aq) where [H2O(l)] is 55.55M and
incorporated into Kc.

Ka = [HA]/[H+1] · [A-1]

Ka is an index of acid strength and can be calculated easily because [HA], [H+1] and [A-1] are usually
measurable. It is sometimes more work to calculate equilibrium [HA], [H+1] and [A-1] values form a
given Ka. Some equations are easily solved. Some require the quadratic formula or the method of
successive approximations.

Ex: What is the expected pH of a 0.300M HNO2 solution given Ka = 4.5 x 10-4?
Assume [H+1] = [NO2-1] = X [HNO2] 0.300M - X
Is X small enough to ignore in relation to the initial [HNO2]? Do a trail calculation

Set 4.5 x 10-4 = X2/(0.300).

X2 = 1.35 x 10-4. X = 1.2 x 10-2, too large to ignore in relation to 0.300M.
To get a better value for the new equilibrium [HNO2] value, try the method of successive approximation.
Set X2 = 4.5 x 10-4 (0.300 - 0.012). Now X = 1.14 x 10-2 ≈ 1.1 x 10-2. [H+1] = [NO2-1] = 1.1 x 10-2M
and [HNO2] = 0.289M. Substituting the new [H+1], [NO2-1] and [HNO2] values back into the Ka
equation gives Ka = 4.5 x 10-4, the correct original value.
Only one approximation step was needed to get the correct answer.

Try the same problem using the quadratic formula.

4.5 x 10-4 = X2/(0.300 - X) gives the quadratic equation X2 + 4.5 x 10-4X - 1.35 x 10-4 = 0
Plugging into the quadratic formula gives X = 1.1 x 10-2.
The equilibrium concentration values are the same as with the approximation method.

Weak Bases and Base Ionization Constants

In general, B(aq) + H2O(l) ↔ BH+1(aq) + OH-1(aq)

K = [BH+1] · [OH-1] / [B] · [H2O]

Kb = K[H2O] = [BH+1] · [OH-1] / [B]

Typical Kb values range from 0.1 to 10-10.

Ex: Calculate pH, pOH, [OH-1], [H+1], [BH+1] and [B] for a 0.200 M ethylamine solution.
Kb of ethylamine = 5.6 x 10-4.

Kb = [BH+1] · [OH-1] / [B] [BH+1] = [OH-1] = x

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Try the assumption that [B] = 0.200 - x ≈ 0.200

Kb = 5.6 x 10-4 = [BH+1] · [OH-1] / [B] = X2/(0.200 - X)

X2 = 5.6 x 10-4/(0.200) = 1.12 x 10-4
X = 1.06 x 10-2 (Temporarily carry three significant figures to avoid rounding errors.)

[BH+1] = [OH-1] = 1.06 x 10-2 M ≈ 1.1 x 10-2 M

pOH = 1.97 pH = 12.03 [H+1] = 9.4 x 10-13 M
[B] = 0.200 - x = 0.200 - 1.06 x 10-2 = 0.189 M. Cannot ignore change in [B].

To get a better answer, either start by using the quadratic equation, or use [B] = 0.189 M instead of 0.200
M when solving the equation to get X = 1.03 x 10-2 M, a better value. Then pOH changes to 1.99, etc.

Ka Values of Weak Acids and Kb Values of Their Conjugate Bases

A simple relationship:

For a weak acid, HA(aq) ↔ H+1(aq) + A-1(aq)

Ka = [H+1] · [A-1]/[HA]

For the conjugate base of that acid, A-1(aq) + H2O(l) ↔ HA(aq) + OH-1(aq)

Kb = [HA] · [OH-1] / [A-1]

Multiplying Ka and Kb gives [H+1] · [OH-1], the ion product of water,

It is now possible to calculate any Ka from the Kb of its conjugate base and vise-versa.

Diprotic and Polyprotic Acids

Common examples are: sulfuric acid, oxalic acid, phosphoric acid, carbonic acid, and sulfurous acid.
Why is the second Ka always smaller than the first?
Usually the contribution that the second ionization step makes to [H+1] can be ignored.

Molecular Structure and Acid Strengths

Define “Acid Strength” again

HA ↔ H+1 + A-1

The strength of an acid depends on the strength of the bond and the polarity (the difference in
electronegativity of the anion atom and the hydrogen) of the bond.
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The more electronegative the anion atom(s), the more polar the H-X bond and the easier it is for the H to
leave as a proton.

The hydrohalic acid series is an exception to this rule. HF is a weak acid while HCl. HBr and HI are all
strong. (HI is the strongest, but this does not make any difference in aqueous solution because they all
form hydronium ion.) HF is a weak acid because of the small size of the fluoride ion, which makes the
H-F bond very short and therefore strong.

Oxyacids are easier to understand. Consider the structure Z—O—H. The more electronegative Z is or
the higher its oxidation state is, the more polar the H—H bond will be and the easier it is for H to leave
without its electrons.

Compare HNO2 and HNO3; H2SO4 and H2SO3.

Compare H2SO4 and H2SeO4.

Acid-base Properties of Salts

Salts are ionic compounds that result for the reaction of an acid or a base. (Excluded ions are H+1, OH-1
and O-2. If a salt is soluble in water, it dissociates completely into its constituent cations and anions.
Salts, however, do not generally produce neutral solutions. Some cations and some anions undergo
hydrolysis in water to produce excess H+1 or OH-1 in the solution.

A Negative Example: Salts That Do Not Undergo Hydrolysis

KCl is soluble salt and dissociates into K+1 and Cl-1 ions ion solution. A solution of KCl in water is
neutral. Neither constituent ion produces an acidic or basic solution.

Remember that potassium ion is the cation of a strong base; it cannot covalently hold onto hydroxide ion.

K+1(aq) + H2O(l) ≠ KOH(aq) + H+1(aq)

Therefore we say potassium ion does not hydrolyze. It does not react with water to produce hydrogen ion.

Chloride ion also does not hydrolyze because it is the anion of a strong acid, and as such, it does not have
the ability to bond tightly to a proton or take one away from water..

Cl-1(aq) + H2O(l) ≠ HCl(aq) + OH-1(aq)

Chloride does not react with water to produce hydroxide ion in solution.

Salts That Produce Basic Solutions:

The majority of anions hydrolyze in aqueous solution to produce hydroxide. This is because the majority
of anions (F-1, SO3-2, CH3COO-1, CO3-2, etc.) are derived from weak bases. (Remember, most acids are
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weak.) These anions by definition form strong bonds with hydrogen ion (as in HF, H2SO3, CH3COOH,
HCO3-1, etc.) and are able to abstract a proton away from water, producing a small but significant amount
of hydroxide ion, making the solution basic.

F-1(aq) + H2O(l) ↔ HF(aq) + OH-1(aq)

The Kb of this reaction is given as Kb = [HF] · [OH-1]/[F-1]

Calculate the parameters of the equation as usual.

Ex: What is the pH of a 0.300 M NaHCO3 solution. (Remember, Na+1 is merely a spectator ion.)

Kb = 2.4 x 10-8 = [H2CO3] · [OH-1]/[ HCO3-1] = X2/(0.300 - X) Can we ignore X?

X2 = 2.4 x 10-8 x (0.300) = 7.2 x 10-9 X = 8.5 x 10-5 [OH-1] = 8.5 x 10-5 M
(The value of X can be ignored relative to 0.300M)
pOH = 4.07 pH = 9.93

Salts that Produce Acidic Solutions

The most obvious example is the ammonium ion.

NH4+1(aq) + H2O(aq) ↔ H3O+1(aq) + NH3(aq)

Ammonium in is itself the product of the neutral molecule ammonia and a proton so it will have the
ability to donate protons in aqueous solution.
Therefore the salts ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium iodide, etc.
will give acidic aqueous solutions.

Metal cations hydrolyze in a more interesting manner. For instance, aluminum ion hydrolyzes
extensively in water to give acidic solutions. How can this be when Al+3 contains no protons?

All metal cations are hydrated. They exist as the hexaquo species M(H2O)6+n. When the cation is small
and n is larger than 1, the H-O bonds in water are highly polarized and the complex easily donates a
proton to H2O, making the solution acidic. Theoretically, any cation will generate protons in solution but
some, such as Na+1 and K+1 do so at almost undetectable levels.

Ex: What is the pH of 0.045 M Al(NO3)3?

Al(H2O)6+3(aq) + H2O(aq) ↔ Al(H2O)5(OH)+2(aq) + H3O+1(aq) Ka = 1.3 x 10-5

Ka = 1.3 x 10-5 = [Al(H2O)5(OH)+2] · [H+1]/ [Al(H2O)6+3]

1.3 x 10-5 = X2/(0.045 - X) X2 = 5.85 x 10-7 X = 7.6 x 10-4

+1 -4 +3
[H ] = = 7.6 x 10 M [Al(H2O)6 ] ≈ 0.044 M pH = 3.12
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Salts in Which both the Cation and Anion Hydrolyze

The math is complicated so we will only do qualitative examples.

If Ka = Kb, the rate of hydrogen ion and hydroxide ion formation are the same and the solution is neutral.
The classic example is ammonium acetate where Kb of acetate ion = Ka of ammonium ion = 5.6 x 10-10.

NH4+1(aq) + H2O(l) ↔ NH3(aq) + H3O+1(aq)

C2H3O2-1(aq) + H2O(l) ↔ C2H3O2H(aq) + OH-1(aq)

Hydrogen ion and hydroxide ion are produced in equal amounts so the solution remains neutral.

If Ka > Kb, the solution is acidic.

If Ka < Kb, the solution is basic.
Ex: The three ammonium phosphate salts. (NH4)3PO4 (NH4)2HPO4 (NH4) H2PO4
(Uses as fertilizer or fire extinguishants)

One can qualitatively rank the relative acidity of the salts without even looking at the relative acid and
base constants.
Knowing the values gives a more confident prediction of their relative acidity or basicity.

Ka of NH4+1 = 5.6 x 10-10

Kb of H2PO4-1 = 1.3 x 10-12
Kb of HPO4-2 = 1.7 x 10-7
Kb of PO4-3 = 2.1 x 10-2

The example of bicarbonate ion is interesting in that bicarbonate can act as an acid or a base.
(Reaction as a stomach acid neutralizer.)
Bicarbonate is a stronger base than it is an acid.

HCO3-1 Ka = 4.8 x 10-11 Kb = 2.4 x 10-8

Acid-Base Properties of Oxides and Hydroxides

General rule: Oxides of metals are basic, oxides of nonmetals are acidic. Metalloids and elements near
them may have little acid-base character or may be amphoteric, capable of acting as an acid or a base.

Compare the acid-base character and the acid-base strength of the oxides of the third period elements Na,
Mg, Al, Si, P, S and Cl. All the oxides react with water to form a potential acid or base.

The left-to-right base-to-acid trend can be explained by the electronegativity of the element and its effect
on the polarity of the M-O-H bonds in the acid or base derived from each oxide.
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Lewis Acids and Bases

A further extension of acid-base theory.

In the Lewis theory, a Lewis acid is any species that can accept an electron pair.
(Note that a proton fits this definition, so all Arrhenius and Brønsted acids fall under the Lewis category.
A Lewis base is any species that can donate an electron pair. This definition includes hydroxide ion and
all the Brønsted bases we have so far studied.

BF3 (neither an Arrhenius nor a Brønsted base) and NH3 (a Brønsted base but not an Arrhenius base) will
react to form an adduct.

Also the reaction of Cu+2 ion and water to form the hexaquo species, the reaction of Cu+2 with ammonia,
the reaction of a proton with water, the reaction of fluoride ion with a proton, etc.