CHEM 123 Recitation Activity #8

A. pH of Polyprotic Acids

For polyprotic acids (more than one acidic hydrogen), the pH is usually determined based on the first
dissociation. Subsequent dissociations still occur, however, one must remember that there is already
hydronium ion present for those subsequent dissociations.

Example: What is the pH of a 0.25M carbonic acid, H2CO3, solution? Ka1 = 4.3 x 10-7, Ka2 = 5.6 x 10-11

Plan: We will perform a standard weak acid dissociation.

Solution:
H2CO3 (aq) + H2O(l) ⇌ HCO3-(aq) + H3O+(aq)
I 0.25 0 0
C –x +x +x
E 0.25-x x x
Ka = 4.3 x 10 = (x)(x)/(0.25-x) x = [H3O ] = 3.3x10-4 pH = 3.48
-7 +

1. What is the pH of a 1.5 x 10-2 M H2SO4 solution? Ka1 = large Ka2 = 1.2 x 10-2

[H3O+] = 1.5x10-2
pH = -log(1.5x10-2) = 1.82
2. What is the pH of a 0.15M H3PO4 solution? Ka1 = 7.5 x 10-3, 6.2 x 10-8, 4.2 x 10-13

Weak acid: Ka = [H2PO4-][H3O+]/[H3PO4]

Ka = 7.5x10-3 = (x)(x)/0.15-x)
From quadratic or successive approximations…
x = 0.030
[H3O+] = 0.030
pH = 1.52
3. Challenge: What is the concentration of HPO42- and PO43- in the 0.15M H3PO4 solution?

First Dissociation Produced 0.030 [H3O+] and 0.030 [H2PO4-]

Second dissociation:
H2PO4-(aq) + H2O(l) ⇌ HPO42-(aq) + H3O+(aq)
I 0.030 0 0.030
C -x +x +x
E 0.030 – x x 0.030+x
Ka = 6.2x10-8 = (x)(0.030+x)/(0.030-x) x = 6.2x10-8

Third dissociation:
HPO42-(aq) + H2O(l) ⇌ PO43-(aq) + H3O+(aq)
I 6.2x10-8 0 0.030
C -x +x +x
E 6.2x10-8 – x x 0.030+x
Ka = 4.2x10-13 = (x)(0.030+x)/(6.2x10-8-x) x = 8.7x10-19
B. Conjugates of Polyprotic Acids
Polyprotic acids have more than one conjugate. All but the last conjugate can act as an acid or a base
and will have both a Ka and a Kb. Whichever is larger will determine if it acts as an acid or a base in
water. The final conjugate after removing all acidic hydrogens is a base. The Kbs for each conjugate are
related to the previous Ka.

Example: What is the Ka and Kb for the HPO42- ion? (H3PO4 Ka1 = 7.5 x 10-3, Ka2 = 6.2 x 10-8,
Ka3 = 4.2 x 10-13?

Plan: Each Ka is given, so we already have the Ka for HPO42-. The Kb will be determined from the
previous Ka since the previous one is the conjugate acid of HPO42-.

Solution:

Ka = Ka3 = 4.2 x 10-13

Kb = Kw / Ka2 = 1x10-14 / 6.2 x 10-8 = 1.6 x 10-7

Since Kb > Ka a solution containing HPO42- will be basic (as long as no acidic cations are present).

4. What are the Ka and Kb for HCO3-? (H2CO3 Ka1 = 4.3 x 10-7, Ka2 = 5.6 x 10-11)

Ka = 5.6x10-11 Kb = 1.0x10-14/4.3x10-7 = 2.3x10-8

5. Is a solution of NaH2C6H5O7 acidic or basic? (H3C6H5O7 Ka1 = 7.4 x 10-4, Ka2 = 1.7 x 10-5, Ka3 = 4.0 x 10-7?
Show your work to justify your answer.

Ka = 1.7x10-5
Kb = 1.0x10-14/7.4x10-4 = 1.4x10-11
Since Ka is bigger than Kb it is Acidic

6. Is the pH solution of an ammonium sulfate (NH4)2SO4 solution greater than or less than 7?

NH3 Kb = 1.8 x 10-5 H2SO4 Ka1 = large, Ka2 = 1.2 x 10-2

NH4+ Ka = 1.0x10-14 / 1.8x10-5 = 5.6x10-10

SO42- Kb = 1.0x10-14 / 1.2 x 10-2 = 8.3x10-13

The acid is a stronger acid than the base is a base so the pH is less than 7

7. Is the pH of a solution of trimethylammoniumbisulfite ((CH3)3NHHSO3) greater than or less than 7?

(CH3)3N Kb= 6.4 x 10-5 H2SO3 Ka1 = 1.7 x 10-2, Ka2 = 6.4 x 10-8

(CH3)3NH+ Ka = 1.0x10-14 / 6.4x10-5 = 1.6x10-10

HSO3- = Kb = 1.0x10-14 / 1.7x10-2 = 5.9x10-13

The acid is a stronger acid than the base is a base so the solution is acidic. Additionally, HSO3- has a
larger Ka than Kb so it is not a base anyway and will behave as an acid in the solution.
C. Salts: Conjugate Acids and Bases

For a weak acid-base conjugate pair, Ka times Kb equals Kw (Ka · Kb = Kw). This demonstrates that the
stronger an acid is (larger Ka) the weaker base its conjugate base will be (smaller Kb). It also allows one
to handle salt solutions which will often contain a conjugate acid or base.

Example: The salt ammonium sulfide NH4F contains the ammonium ion (NH4+) and the fluoride ion (F-).
Are each of these ions acids or bases, what are their Kas or Kbs, and will a solution of the salt be acidic or
basic? Given info: NH3 is a base with a Kb = 1.8 x 10-5 and HF is an acid with a Ka = 6.8 x 10-4

Plan: For each ion, we will use the information known about its conjugate to determine its acidity or
basicity and the K values. To determine if the ions as a pair give an acidic or basic solution, the one with
the larger K value will determine this.

Solution:

Evaluate NH4+ first: NH3 is a base, so NH4+ is its conjugate acid. We are given the Kb of NH3 and will use it
to determine the Ka of its conjugate acid, NH4+.

Ka · Kb = Kw Ka · (1.8 x 10-5) = (1.0 x 10-14) Ka = 5.6 x 10-10

Evaluate F-: HF is an acid, so F- is its conjugate base. We are given the Ka of HF and will use it to
determine the Kb of its conjugate base, F-.

Ka · Kb = Kw (6.8 x 10-4) · Kb = (1.0 x 10-14) Kb = 1.5 x 10-11

The Ka of NH4+ is larger than the Kb of F- so the solution will be acidic.

Reminder: Conjugates of strong acids (Cl-, Br-, I-, NO3-, ClO3-, ClO4-) are non-bases. Group 1 metal ions
are non-acids.

8. For each of the ions, identify it as an acid or a base and determine its Ka or Kb. If it is neither an acid or
a base say it is neutral.

a) NH4+
Acid Ka = 1x10-14/1.8x10-5 = 5.6x10-10 Substance Ka or Kb
b) F- HNO2 Ka = 7.1 x 10-4
Base Kb = 1.4x10-11 C6H5NH2 Kb = 4.0 x 10-10
c) Cl- HC2H3O2 Ka = 1.8 x 10-5
Non acid or base CH3NH2 Kb = 4.4 X 10-4
d) NO2- HF Ka = 7.2 x 10-4
Base, Kb = 1.4x10-11 HClO Ka = 3.0 x 10-8
e) Na+ HIO3 Ka = 1.6 x 10-1
Non acid or base NH3 Kb = 1.8 x 10-5
f) ClO-
Base Kb = 3.3 x 10-7
g) Zn2+(Just identify this as an acid or base. Do not worry about Ka or Kb)
Acid
9. For each of the following, split each ionic compound into its ions. For each ion, determine if it is an
acid or a base and determine its Ka or Kb.

a) NaC2H3O2 Substance Ka or Kb
Na+ is neutral HNO2 Ka = 7.1 x 10-4
C2H3O2- is a Base Kb = 5.6x10-10 C6H5NH2 Kb = 4.0 x 10-10
b) NH4Cl HC2H3O2 Ka = 1.8 x 10-5
NH4+ is an Acid Ka = 5.6x10-10 CH3NH2 Kb = 4.4 X 10-4
HF Ka = 7.2 x 10-4
Cl- is neutral
HClO Ka = 3.0 x 10-8
c) CH3NH3NO3
HIO3 Ka = 1.6 x 10-1
CH3NH3+ is an Acid Ka = 2.3x10-11 NH3 Kb = 1.8 x 10-5
NO3- is neutral
d) KNO2
K+ is neutral
NO2- is a Base Kb = 1.4x10-11
e) NaBr
Both Na+ and Br- are Neutral

D. pH of Salt Solutions

Once you are able to determine if a salt solution contains an acidic or basic ion, determining the pH of
these solutions follows the normal weak acid or weak base dissociation calculations.

Example: What is the pH of a 0.50 M NH4Cl solution?

Plan: For ionic compounds, we split the compound into its ions and evaluate each ion.

Solution:

NH4Cl(s) → NH4+(aq) + Cl-(aq)

Cl- is the conjugate of a strong acid so it is a non-base

NH4+ is the conjugate acid of a weak base NH3. Thus we have 0.50M of the weak acid NH4+.

For NH3 Kb = 1.8 x 10-5, therefore Ka of NH4+ = 1x10-14/1.8 x 10-5 = 5.6 x 10-10.

NH4+(aq) + H2O(l) ⇌ NH3(aq) + H3O+(aq)

Ka = [NH3][H3O+]/[NH4+] = (x)(x)/(0.50-x) = 5.6 x 10-10 x = [H3O+] = 1.7 x 10-5 pH = -log(1.7x10-5) = 4.78

10. What is the pH of a solution that is 0.50 M in NaNO2? (See table on previous page for Ka or Kb values)

NO2-(aq) + H2O (l) HNO2 (aq) + OH-(aq)

NO2- (aq) + H2O (l) ⇌ HNO2 (aq) + OH- (aq)

Initial 0.50 --- 0 0
Change -x --- +x +x
Equilibrium 0.50 - x --- x x

Ka* Kb = 1 x 10-14

Kb = 1x10-14/7.1 x 10-4 = 1.4 x 10-11

1.4 x 10-11 = (x)(x)/(0.50 – x)

0.50/1.4x10-11 is much greater than 1000, so x is negligible

1.4 x 10-11 = (x)(x)/(0.50)

x = [OH-] = 2.6 x 10-6 M

pOH = 5.58

pH = 8.42

11 What is the pH of a solution that is 0.50 M in CH3NH3Cl?

CH3NH3+(aq) + H2O (l) CH3NH2 (aq) + H3O+ (aq)

CH3NH3+ (aq) + H2O (l) ⇌ CH3NH2 (aq) + H3O+ (aq)

Initial 0.50 --- 0 0
Change -x --- +x +x
Equilibrium 0.50-x --- x x

Ka = 1x10-14/4.4 x 10-4 = 2.3 x 10-11

2.3 x 10-11 = (x)(x)/(0.50 – x)

0.50/2.3x10-11 is much greater than 1000, so x is negligible

2.3 x 10-11 = (x)(x)/(0.50)

x = [H3O+] = 3.4 x 10-6 M

pH = 5.47