CHEM 102/105 Dr. M.

Gedik
Problem Set #4: Acid-Base Equilibria and Buffers

Use data given on the chemistry data sheet (or textbook).

1. Identify the conjugate bases of the following acids and calculate their Kb and write the reaction
corresponding to the Kb: benzoic acid, hydrazinium ion and nitrous acid.

The conjugate base is obtained by ²subtracting² H+ from the acid formula. Watch out for the resulting
charge based on the initial acid charge.
Benzoic acid = C6H5COOH
Kw 10–14
Conjugate base = benzoate ion = C6H5COO– Kb = K = 6.31 x 10–5 = 1.58 x 10–10
a

The corresponding reaction for Kb is the base reacting with water to yield the conjugate acid and the
hydroxide ion.
®
C6H5COO– + H2O ¬ C6H5COOH + OH–

10–14
Hydrazinium ion = N2H5+ conjugate base = hydrazine = N2H4 Kb = 3.30 x 10–9 = 3.03 x 10–6

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N2H4 + H2O ¬ N2H5+ + OH–

10–14
Nitrous acid = HNO2 conjugate base = nitrite ion = NO2– Kb = 7.22 x 10–4 = 1.39 x 10–11

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NO2– + H2O ¬ HNO2 + OH–

Note: while the Kb is calculated as Kw/Ka, the Kb reaction is not the reverse of the Ka reaction.
For example, the Ka reaction for benzoic acid is:
®
C6H5COOH + H2O ¬ H3O+ + C6H5COO– not the reverse of Kb !

2. Suppose you mix 25 mL of 0.052 M sodium hypochlorite with 25 mL of 0.052 M pyridinium chloride
(C5H5NHCl). Write the reaction that could occur between the ions that are formed when the two salts
dissolve in the solution. Identify the conjugate pairs and state whether you would expect to find the
reactants or the products in greater concentration at equilibrium. Give your reasoning briefly but
clearly. No calculations are necessary for this question.
 NaOCl ® Na+ + OCl–
Neutral Weak base

C5H5NHCl ® C5H5NH+ + Cl–

Weak acid Neutral

®
Possible rxn C5H5NH+ + OCl– ¬ HOCl + C5H5N
Acid base conjugate acid conjugate base
Find Ka from Chemistry Data Sheet (CDS)
Ka (HOCl) = 2.95 x 10–8 Ka (C5H5NH+) = 6.60 x 10–6
C5H5NH+ is stronger acid than HOCl
Ka (C5H5NH+) > Ka (HOCl) then K>1

Since HOCl is the weaker acid, the equilibrium is lying to the right.
Another way to think about this is from a concept you (hopefully) learned in High School Chemistry:
The equilibrium will always favour the side with the weaker acid/base pair.
Initially, the initial concentrations before equilibrium are the same Q = 1
Q<K Þ products would have larger concentrations at equilibrium

3. Arrange the following 0.10 M solutions in order of most acidic to most basic: Ca(NO3)2, NaNO2,
HNO3, NH4NO3, Ca(OH)2.

HNO3 = strong acid Ca(OH)2 = strong base

Cation Anion Overall effect

Ca(NO3)2 neutral neutral neutral

NaNO2 neutral basic basic

NH4NO3 acidic neutral acidic

most acidic HNO3 > NH4NO3 > Ca(NO3)2 > NaNO2 > Ca(OH)2 most basic

4. Calculate the pH of a 1.00 M solution of dichloroacetic acid at 25⁰C.

HINT: This is an intermediate K problem. Look up the Ka of dichloroacetic acid: Ka = 4.50 x 10-2
®
HA (aq) + H2O(l) ¬ A- (aq) + H3O+ (aq) * you can always use this generic expression
instead of writing out the formulas of the conjugate species.
 ®
CHCl2COOH (aq) + H2O(l) ¬ CHCl2COO- (aq) + H3O+ (aq)

I 1.00 0 0
C -x +x +x
E 1.00 - x x x

Substitute into the expression for Ka to solve for x. Must solve exactly because it is an intermediate K
problem
x2
Ka = 4.50 x 10–2 = 1.00 – x

x2
1.00 – x à (0.0450)(1.00 - x) = x2

0.0450 – 0.0450x = x2
x2 + 0.0450x – 0.0450
a b c

Use the quadratic formula to solve for x:

- b + b 2 - 4ac
x=
2a

-0.0450±$(0.0450)2 - 4(1)(-0.0450)
x="H3 O+ #=
2(1)
= 0.191 and - 0.236
Concentration cannot be negative thus x = [H3O+] = 0.191 M

pH = - log[H3O+] = - log (0.191) = 0.719

5. Calculate the pH of a 0.25 M solution of sodium benzoate at 25⁰C

®
C6H5COO- + H2O ¬ C6H5COOH + OH-

I 0.25 M 0.00 M 0.00 M

C -x +x +x
E 0.25 -x x x
Kw 10–14
Kb (C6H5COO-) = K = 6.31 x 10–5 = 1.58 x 10–10
a
 x2
1.58 x 10–10 = 0.25 - x

x2
Make small x approximation: 1.58 x 10–10 » 0.25

x = [OH-] = 6.3 x 10–6 M

6.3 x 10–6 –3
Check approx. % dissociation = 0.25 100% = 2.5 x 10 % valid

pOH = – log (6.3 x 10–6 ) = 5.20

pH = 14.00 – pH = 14.00 - 5.20 = 8.80

BUFFERS

6. Chapter 17 – problem 31. A buffer is prepared by mixing 204 mL of 0.452M HCl and 0.500 L of
0.400 M sodium acetate.

a. What is the pH?

b. How many grams of KOH must be added to 0.500 L of the buffer to change the pH by 0.15 units?

a. A strong acid is mixed with a weak base to form a buffer solution containing the weak base (acetate)
and its conjugate weak acid (acetic acid).

Find the number of moles of HCl and sodium acetate

nHCl = nH3O+ = (0.204 L)(0.452 mol/L) = 0.0922 mol

*HCl (strong acid): dissociates completely into H3O+

nacetate = (0.500 L)(0.400 mol/L) = 0.200 mol

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CH3COO– + H3O+ ¬ CH3COOH + H2O

I (mol) 0.200 0.0922 0

C(mol) – 0.0922 – 0.0922 + 0.0922
Comp (mol) 0.1078 0 0.0922

n H3O+ = nacetic acid because all the strong acid. HCl has been consumed (converted to acetic acid).
HCl (H3O+) is the limiting reagent.

0.0922 mol
[CH3COOH] = (0.204+0.500) L = 0.131 M
 *Note that the amount of acetic acid formed is equal to the amount of acetate that reacted.

0.1078 mol
[CH3COO–] = (0.204+0.500) L = 0.153 M

Using the Henderson–Hasselbalch equation: (you can use moles instead of concentration as well)

[CH3COO–] 0.153
pH = pKa + log [CH COOH] = – log (1.76 x 10–5) + log 0.131 = 4.82
3

b. For this part of the question, use concentrations in the H-H equation (change in volume needs to be
considered).

The addition of a base (KOH) will increase the pH by 0.15 so that pH = 4.82 + 0.15 = 4.97

The relevant reaction for the neutralization of the added base:

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CH3COOH + OH– ¬ CH3COO– + H2O

I (M) 0.131 x 0.153

C -x -x +x
Comp 0.131 -x 0 0.153 + x

0.153 + x
Using H-H: 4.97 = – log (1.76 x 10–5) + log 0.131 – x

0.153 + x
0.22 = log 0.131 – x *carrying at least 3 sig figs in this calculation

0.153 + x
1.65 = 0.131 – x x = 0.024 M

0.024 mol 56.11 g KOH

1L 0.500 L 1 mol KOH = 0.67 g KOH

7. Chapter 17 – problem 138. A 500 mL solution consists of 0.050 mol of solid NaOH and 0.13 mol of
hypochlorous acid HClO dissolved in water.

a. Aside from water, what is the concentration of each species that is present?

NaOH will dissociate completely into Na+ (0.05 mol, spectator ion) and OH– (0.050 mol).

Then, all of the OH– (strong base) will react with the weak acid HClO to form the weak conjugate
base, ClO–
 ®
HClO + OH- ¬ ClO– + H2O

I (mol) 0.13 0.050 -

C (mol) – 0.050 – 0.050 + 0.050
Comp (mol) 0.080 0 0.050
0.080mol 0.050mol
Conc. 0.500L = 0.16 M 0 0.500L = 0.10 M

[HClO] = 0.16 M [ClO–] = 0.10 M

[ClO–] 0.10
Use H-H: pH = pKa + log [HClO] = – log (2.95 x 10–8) + log 0.16 = 7.33

[H3O+] = 10-pH = 10-7.33 = 4.7 x 10–8 M

b. What is the pH of the solution? See above

c. What is the pH after adding 0.0050 mol of HCl to the flask?

Adding a strong acid HCl to a buffer solution (appreciable amounts of HClO and ClO–)

0.005 mol
[HCl] = 0.5 L = 0.01 M

[ClO–] 0.050 – 0.0050

pH = pKa + log [HClO] = – log (2.95 x 10–8) + log 0.080 + 0.0050 = 7.25

8. 500.0 mL of 0.150 M NaOH is added to 585 mL of 0.200 M of a weak acid (Ka = 6.16´10-5). Calculate
the pH of the resulting buffer.
When a strong base is added to a buffer solution, it reacts with the weak acid to produce the conjugate
(weak) base.
nOH- = (0.500 L)(0.150 mol/L) = 0.0750 mol

nHA = (0.585 L)(0.200 mol/L) = 0.117 mol

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HA (aq) + OH– (aq) ¬ A– (aq) + H2O (l)

I (mol) 0.117 0.0750 (LR) 0

C (mol) – 0.0750 – 0.0750 + 0.0750

Comp (mol) 0.0420 0 0.0750

[A–] 0.0750
Use H-H: pH = pKa + log [HA] = – log (6.16´10–5) + log 0.042 = 4.46
9. Calculate the pH after 0.15 mol solid NaOH is added to 1.00 L solution containing 0.050 M propanoic
acid (HC3H5O2, Ka = 1.33 x 10–5) and 0.080 M sodium propanoate.

When a strong base is added to a buffer solution (propanoic acid and the conjugate base propanoate
ion), it reacts with the weak acid to produce the weak base.

However, in the present case, the amount of strong base is greater than the initial amount of acid. So
the addition of excess OH– means the solution is no longer capable of resisting pH change.

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HC3H5O2 + OH– ¬ H2O + C3H5O2–

I (mol) 0.050 (LR) 0.15 0.08

C (mol} – 0.050 – 0.050 + 0.05

Comp (mol) 0 0.10 0.13

1 L solution, hence moles = concentration:

[OH–] = 0.10 M pOH = 1.0 pH = 14.00 –pOH = 13.0

10. Two solutions are mixed: 100.0 mL of HCl with pH 2.50 and 100.0 mL of NaOH with pH 11.00.
What is the pH of the resulting solution?

Strong acid and strong base, but in different amounts. Find which one is in excess (either H+ or OH–)

From the HCl solution

[H+] = 10–2.50 = 0.00316 M nH+ = 0.100 L 0.00316 M = 0.000316 mol

From the NaOH solution (2 SF, carrying an extra digit)

pOH = 14.00 – pH = 14.00 –11.00 = 3.00

[OH–] = 10–3.00 = 0.0010 M nOH– = 0.100 L 0.0010 M = 0.00010 mol

Combined solution

Excess H+ is 0.000316 mol – 0.00010 mol = 0.000216 mol H+

0.000216 mol
[H+] = 0.200 L = 0.00108 M

pH = – log (0.00108) = 2.97