Chang, 7th Edition, Chapter 15, Worksheet #1

S. B. Piepho, Fall 2002

Acid-Base Calculations The Ion-Product Constant for Water, Kw Water undergoes ionization to a small extent: H20(l) H+(aq) + OH(aq) The equilibrium constant for the reaction is the ion-product constant for water Kw:

K w = [H ][OH ] = 1.0 10

- 14

(1)

This is a key equation in acid-base chemistry. Note that the product of [H+] and [OH] is a constant at a given temperature (Eq(1) value is for 25oC). Thus as the hydrogen ion concentration of a solution increases, the hydroxide ion concentration decreases (and vice versa). The pH scale is widely used to report the molar concentration of hydrogen ion H+(aq) in aqueous solution. The pH of a solution is defined as

pH = - log10[H + ]
Similarly, pOH and pKw are defined as

(2)

pOH = - log10 [OH- ] pK w = - log10 (K w ) = 14.00

If you take the log10 of both sides of Eq(1), multiply the resulting equation by (-1), and use the definitions of pH, pOH and pKw above, the result is the very useful equation pH + pOH = pKw = 14.00 Equations (2) and (3) above may be solved for [H+] and [OH] respectively to give

(3) (4)

(5)

[H + ] = 10 - pH - pOH [OH ] = 10
(Here we use the well known rule that if log10 y = x , then y = 10 x .) In practice, the pH scale is only used when [H+(aq)] is less than 1.0 M. Acidic, basic, and neutral solutions can be distinguished as shown below: Type of Solution pH
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(6) (7)

[H+]

Color of litmus

Chang, 7th Edition, Chapter 15, Worksheet #1 Acidic Neutral Basic < 7.00 = 7.00 > 7.00 > 1.0 10 7 = 1.0 10 7 < 1.0 10 7

S. B. Piepho, Fall 2002 pink in between blue

pH and [H+] Calculations for Strong Acids and Bases By definition, strong acids and bases are 100% ionized in water solution. Ionization of a strong acid gives rise to H+ ions, and ionization of a strong base produces OH ions. The equilibrium constant for a strong acid or strong base is undefined, since the reaction the ionization is complete. There is no equilibrium! In nearly all cases of practical interest the [H+] for a strong acid (or the [OH] for a strong base) is determined completely by the stoichiometry of the reaction. Once the [OH] or pOH is known for a base, the [H+] or the pH of the base may be calculated using Eq(1) and/or Eq(5).

Exercises 1. Complete the following table: Acidic, basic, or neutral?

pH (a) (b) (c) (d)

[H ]
+

pOH

[OH ]

5.4 x 104 7.8 x 10-10 10.75 5.00

Answers: (a) pH = 3.27; pOH = 10.73; [OH] = 1.85 x 1011 = 1.9 x 1011, acidic (since pH < 7). (b) pH = 4.89, [H+] = 1.3 x 105, pOH = 9.11, acidic (since pH < 7). (c) [H+] = 1.8 x 10-11, pOH = 3.25, [OH] = 5.6 x 104, basic (since pH > 7). (d) pH = 9.00, [H+] = 1.0 x 109, [OH] = 1.0 x 105, basic (since pH > 7).

2. Calculate the pH of a 0.0430 M HNO3 solution.

Answer: Since HNO3 is a strong acid, the nitric acid solution will be 100% ionized. Thus [H+] = [NO3] = 0.0430 M. The pH = 1.37 (use Eq(2)). Page 2 of 7

Chang, 7th Edition, Chapter 15, Worksheet #1

S. B. Piepho, Fall 2002

3. Calculate the pH of a 0.020 M Ba(OH)2(aq) solution.

Answer: Since Ba(OH)2 is a strong base it is 100% ionized. Note that ionization gives 2 OH ions for each mole of Ba(OH)2. Thus [OH] = 2 x 0.020 M = 0.040 M. Eq(3) gives pOH = 1.40. Then using Eq(5), pH = 12.60.

pH and [H+] Calculations for Weak Acids and Bases Weak acids and bases are usually less than 5% ionized. The equilibrium constant for a weak acid equilibrium is the acid ionization constant Ka, and for a weak base equilibrium is the base ionization constant Kb. A typical monoprotic weak acid equilibrium can be written in two forms, the second of which emphasizes the Brnsted acid-base nature of the reaction: HA H+(aq) + A(aq) HA + H2O H3O+(aq) + A(aq)

(8)

In Eq(9) the Brnsted acid HA donates a proton H+ to the Brnsted base H2O to form H3O+ and the conjugate base A. The acid ionization constant (using the second form) is

[H 3O + ][A - ] Ka = [HA]

(9)

A typical weak base equilibrium is B + H2O BH+(aq) + OH(aq) (10)

In Eq(10) the Brnsted base B accepts a proton H+ from the Brnsted base H2O to form the conjugate acid BH+ and OH. The base ionization constant is
Kb = [BH + ][OH - ] [B]

(11)

Exercises
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Chang, 7th Edition, Chapter 15, Worksheet #1

S. B. Piepho, Fall 2002

4. Calculate (a) the pH and (b) the percent ionization of a 0.250 M HC2H3O2 solution. Ka(HC2H3O2) = 1.8 x 10-5. (The formula for acetic acid may also be written as CH3COOH.) HINT: Begin by filling out the equilibrium table below. Balanced Equation HC2H3O2 H+ + C2H3O2 Initial Concentration (M) Change (M) Equilibrium Concentration (M)

Answer: Balanced Equation Initial Concentration (M) Change (M) Equilibrium Concentration (M) HC2H3O2 0.250 -x 0.250 - x 0 x x H+ + C2H3O2 0 x x

[H+ ][C2 H3 O2 - ] x2 x2 -5 (a) K a = =1.8 10 = [HC2 H3 O2 ] 0.250 - x 0.250

. This approximation is OK if the %

ionization is < 5%; it is in this case -- see answer to (b) below. Thus x2 = 4.5 x 10-6; x = 2.12 x 10-3 = [H+]. pH = 2.67. (b) % ionization =

2.12 10- 3 x 100% = 0.85% . 100% = 0.250 0.250

5. Calculate the pH of a 0.600 M solution of methylamine CH3NH2. Kb = 4.4 x 104. HINT: Methylamine is a weak base. First write the equation for the reaction following the pattern of Eq(10). Then fill out the equilibrium table below. Balanced Equation Initial Concentration (M) Change (M) Equilibrium Concentration (M) CH3NH2
+
2

CH3NH3+ +

OH

Answer: Since CH3NH2 is a weak base, the balanced equation for the reaction is CH3NH2 + H2O CH3NH3+ + OH. + 2 CH3NH3+ + Balanced Equation CH3NH2 OH Page 4 of 7

Chang, 7th Edition, Chapter 15, Worksheet #1

Initial Concentration (M) Change (M) Equilibrium Concentration (M) 0.600 -x 0.600 - x

S. B. Piepho, Fall 2002

0 x x

0 x x

[BH+ ][OH- ] [CH3 NH3 + ][OH- ] x2 x2 Kb = = = = 4.4 10- 4 . Thus x = 1.62 x 10[B] [CH3NH 2 ] 0.600- x 0.600
= [OH], and pOH = 1.79. It follows from Eq(5) that pH = 12.21. NOTE: The approximation used is OK since the % ionization is 2.7% (i.e., less than 5 %).
2

6. The pH of a 0.10 M solution of a weak base is 9.67. What is the Kb of the base?

Answer: The balanced equation for a weak base B is given in Eq(10). The equilibrium table required is given below. + 2 Balanced Equation B BH+ + OH Initial Concentration (M) 0.10 0 0 Change (M) -x x x Equilibrium Concentration (M) 0.10 - x x x At equilibrium, [OH] = [BH+] = x. Use the pH to calculate the [OH] at equilibrium (which is the value of x). - pOH - 4.33 -5 Here pOH = 14.00 pH = 14.00 9.67 = 4.33. Thus [OH ] = 10 = 10 = 4.68 10 = x .

[BH + ][OH ] 2 2 (4.68 10 5 ) 2 = = = 2.2 10 8 . The approximation is OK [B] 0.10 0.10 0.10

since the % ionization is well under 5%.

Relationship between Ka for a Weak Acid and Kb for its Conjugate Base The relationship between Ka for a weak acid HA and Kb for its conjugate base A is Ka(HA)

K (A ) = K
b

= 1.0 x 10-14

(12)

If we define pKa = - log10(Ka) and pKb = - log10(Kb), the logarithmic form of Eq(12) is pKa(HA) + pKb(A) = pKw = 14.00 (13)

The stronger the acid, the larger the Ka and the smaller the pKa. Likewise the stronger the base, the larger the Kb and the smaller the pKb. Eqs(12) and (3) show that as the Ka increases

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Chang, 7th Edition, Chapter 15, Worksheet #1

S. B. Piepho, Fall 2002

(and the pKa decreases), the Kb decreases (and the pKb increases). These equations give quantitative support to the statement the stronger the acid, the weaker the conjugate base. The justification for Eq(12) follows from the equations below. Recall that if Eq(1) + Eq(2) = Eq(3), then K1 K2 = K3.

Eq(1), Weak Acid: Eq(2), Conjugate Base: Eq(3) = Eq(1) + Eq(2)

HA + H2O H3O+(aq) + A(aq) A(aq) + H2O HA(aq) + OH(aq) ___________________________ 2 H20(l) H3O+(aq) + OH(aq)

K a (HA) =

[H 3O + ][A - ] [HA] [HA][OH - ] K b (A ) = [A- ]

K w = [H 3O ][OH ]

Relationship between Kb for a Weak Base and Ka for its Conjugate Acid Analogous equations to Eqs(12) and (13) above can be written the relationship between Kb for a weak base B and Ka for its conjugate acid HB+: Kb(B)

K (BH ) = K
a +

= 1.0 x 10-14

(14) (15)

pKb(B) + pKa(BH+) = pKw = 14.00 The equations below provide justification for these results: Eq(1), Weak Base: Eq(2), Conjugate Acid: Eq(3) = Eq(1) + Eq(2) B + H2O BH (aq) + OH (aq)
+ + +

[BH + ][OH - ] K b (B) = [B]

+

[H 3 O+ ][B] BH (aq) + H2O H3O (aq) + B(aq) K a (BH ) = + [BH ]

___________________________ 2 H20(l) H3O+(aq) + OH(aq)

K w = [H 3O + ][OH- ]

__________________________________________________________________________ _ Exercise 7. Use the following acidity constants to help answer the questions below: Ka(HC2H3O2) = 1.8 x 10 5 ; Ka(HCN) = 4.9 x 10 10 ; Ka(HCOOH) = 1.7 x 10 - 4 (a) (b) (c) (d) Which of the three acids is the weakest? ________________ Which of the following bases is the strongest: C2H3O2-, CN - , or HCOO- ? __________ What is the pKa of HCN? _____________ What is the Kb for CN- ?____________

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Chang, 7th Edition, Chapter 15, Worksheet #1

S. B. Piepho, Fall 2002

__________________________________________________________________________
Answers: (a) HCN; (b) CN - ; (c) 9.31; (d) 2.04 x 10-5 2.0 x 10-5.

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