Ex. 2: Calculate the pH of a 0.15M ammonium nitrate solution given the Kb for ammonia is 1.810-5 at 25C.

ACIDIC, BASIC, AND NEUTRAL SALTS A salt is simply an ionic compound. When soluble salts dissolve in water, they form ions. Salts that produce Weakly Acidic Solutions react with water to produce H+ ions 1. When the cation is the conjugate acid of a weak base: NH4+ 2. When the cation is a highly charged (+2, +3) metal ion: Al3+, Zn2+, Mg2+, etc. These form hydrated metal ionse.g. Al(H2O)63+that can donate a proton, H+. exceptions are the cations of strong bases (Li+, Na+, K+, Ca2+, Sr2+, Ba2+) which do not react with water Salts that produce Weakly Basic Solutions react with water to produce OH ions When the anion is the conjugate base of a weak acid essentially every anion except those derived from strong acids (e.g. Cl, Br, I, NO3, ClO3, ClO4) Note: Sulfate ion (SO42) reacts with water to form HSO42 and OH. Salts that produce Neutral Solutions does not react with water to produce H+ or OH ions When the cation is the cation of a strong base (Li+, Na+, K+, Ca2+, Sr2+, Ba2+) and the anion is the conjugate base of a strong acid (Cl, Br, I, NO3, ClO3, ClO4).
CHEM 162: Zumdahl Chapter 14 page 25

Ex. 1:

Predict whether the following each salt will result in an acidic, basic, or neutral solution. Explain why for each. Salt a. NaCl b. Al(NO3)3 c. KC2H3O2 d. NH4Br d. Sr(NO2)2 acidic, basic, or neutral? Explanation

Ex. 2: Ammonium fluoride is soluble. Will it result in an acidic, basic, or neutral solution?

Compare the cations Ka with the anions Kb. For NH4F, K 1.0 10 -14 = 5.6 10 -10 consider NH4+s K a = w = Kb 1.8 10 - 5 and Fs K b =

K w 1.0 10 -14 = = 1.4 10 -11 Ka 7.2 10 - 4

Table of Ka and Kb values at 25C

HClO2 HCOOH HF HNO2 HC2H3O2 (or CH3COOH) HClO HCN
CHEM 162: Zumdahl Chapter 14

Value of Ka 0.012 1.810-4 7.210-4 4.510-4 1.810-5 3.510-8 4.910-10

Value of Ka [Fe(H2O)6] [Al(H2O)6]3+ [Zn(H2O)6]2+ [Ni(H2O)6]2+ NH3

3+

6.310-3 1.410-5 2.510-10 2.510-11 Value of Kb 1.810-5

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Combining an Acidic Cation and a Basic Anion If Ka > Kb, then [H+] > [OH] in solution The salt and resulting solution are acidic. If Ka > Kb, then [H+] < [OH] in solution The salt and resulting solution are basic. If Ka = Kb, then [H+] = [OH] in solution The salt and resulting solution are neutral.

Example:

Use the Table of Ka and Kb values to classify each of the following salts as acidic, basic, or neutral. a. NH4F where NH4+s Ka=5.610-10 and Fs Kb=1.410-11

b. ammonium cyanide

c. zinc nitrite

d. aluminum acetate

CHEM 162: Zumdahl Chapter 14

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14.7 Polyprotic Acids Some acids are polyprotici.e. they have more than one ionizable H atom. e.g., H2SO4 and H2CO3 are both diprotic, and H3PO4 is triprotic. Polyprotic acids always dissociate in a stepwise manneri.e., one proton at a time. e.g., sulfurous acid, H2SO3(aq), dissociates according to the following steps at 25C, where the successive acid dissociation constants are designated Ka1 and Ka2: H2SO3(aq) H+(aq) + HSO3(aq) Ka1 = Ka2 =
[H + ][HSO 3 - ] -2 = 1.510 [H2 SO 3 ]

HSO3 (aq)

H (aq) + SO3 (aq)

[H+ ][SO 3 2 - ] [HSO 3 ]

-

= 6.310

-8

Experimentally, this can be shown be carrying out a titration. In the titration of a polyprotic acid, the protons are titrated in succession. The anion formed in one step is then ionized in the next step. With each successive step, the ionization constant becomes much smaller, usually by several orders of magnitude. It is much more difficult to remove a proton from a positively charged ion. Ka1 > Ka2 for all polyprotic acids. Essentially all the of the H+ ions in solution come from the dissociation of the first acid.

Ex. 1: Calculate the pH of a 1.50M sulfurous acid solution. a. First, calculate the [H+] after the dissociation of the first acid, H2SO3.

CHEM 162: Zumdahl Chapter 14

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Ex. 1 (Continued): Calculate the pH of a 1.50M sulfurous acid solution. b. Next, calculate the [H+] resulting from the dissociation of the second acid, HSO3, where the initial concentration of HSO3, [HSO3]0, is equal to the [H+] from part a (since [H+] = [HSO3] = x).

c. How do the hydrogen ion concentrations compare after the first dissociation and the second dissociation?

d. Calculate the [SO32] at equilibrium?

Thus, because the contribution of H+ ions from the second dissociation step is negligible compared to the [H+] after the first dissociation step, [H+] = [HSO3]. Substituting into the Ka2 expression,
CHEM 162: Zumdahl Chapter 14

Ka2 =

[H + ][SO 3 2 - ] [HSO 3 ]
-

= 6.310

-8

[SO32] = Ka2.
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