pH of Acids and bases
Calculation of pH for strong acids
• Strong acids ionize completely in aqueous solution:
HCl(aq) + H2O H3O+(aq) + Cl-(aq)
HClO4(aq) + H2O H3O+(aq) + ClO4-(aq)
• In solutions of strong monoprotic acids HA, such as HCl and
HClO4, [H3O+] equals the original concentration of acid
[HA]0
[H3O+] = [HA]0
• The most common strong acids include six monoprotic
acids (HCl, HBr, HI,HNO3, HClO3, and HClO4),
Calculating the pH of a Strong Base
Like strong acids, strong bases also ionize
completely in aqueous solution.
Examples: NaOH(aq) Na+(aq) + OH-(aq);
Ba(OH)2(aq) Ba2+(aq) + 2 OH-(aq);
• The concentration of OH- in solution will be
equal to the concentration of the strong base.
GIVE IT SOME THOUGHT
Which solution has the higher pH, a 0.001 M
solution of NaOH or a 0.001 M solution of Ba(OH)2?
Calculating pH of strong bases.
• In a base solution such as 0.050 M NaOH,
[OH-] = [NaOH]0 = 0.050 M;
pOH = -log(0.050 M) = 1.30; pH = 14.00 - 1.30 = 12.70
• In a base solution such as 0.050 M Ba(OH) 2,
[OH-] = 2 x [Ba(OH)2]0 = 0.10 M;
pOH = -log(0.10) = 1.00; pH = 14.00 - 1.00 = 13.00
• An aqueous solution of a strong base has pH 12.24 at 25°C.
Calculate the concentration of base in the solution (a) if the base
is NaOH and (b) if the base is Ba(OH)2.
•Answer: pH = 12.24 means that pOH = 14 – 12.24 = 1.76
Therefore [OH–] = 10–1.76 = 0.0174 With NaOH, we must have [NaOH]
= 0.017 M With Ba(OH)2, we have [Ba(OH)2] = (0.017 / 2) = 8.7 x
10–3 M
Calculating pH of week acids using Ka
• In weak acid solutions, [H3O+] < [HA]0;
• [H3O+] and pH can be calculated from the initial concentration of the acid
and its Ka value.
Example: in 0.30 M acetic acid, CH3COOH, with Ka = 1.8 x 10-5, [H3O+]
the pH calculate the pH
Sol. Initial change equilibrium table is used as follows:
Ka << [HA]0 ( 1.8x 10-5) << 0.3) Therefore, x << 0.3 and hence 0.30 - x≈ 0.3
[OH-] and pH of a Weak Base
• In a weak base, [OH-] < [Base]0;
• [OH-] and pH can be calculated from the initial concentration of
the base and its Kb value.
• For example, in 0.100 M ammonia, NH3, with Kb = 1.8 x 10-5,
[OH-] and pH can be calculated using the following “ICE” table.
ICE Table for the Ionization of Ammonia
• Ionization: NH3 + H2O NH4+ + OH-
•
• Initial [M] 0.100 0.00 0.00
• Change [M] -x +x +x
• Equilm. [M] (0.100 – x) x x
•
Calculate [OH-] from initial concentration and Kb by
approximation method.
• Solving for x in the expression for Kb:
[NH 4 ][ OH - ] x2
Kb 1.8 x 10 5
[NH 3 ] (0.100 x )
K b [B] 0 (1.8 x 10-5 0.100) x 0.100, and
x2 x2
(0.100 - x ) ~ 0.100, which makes ~ 1.8 x 10-5 ;
(0.100 - x ) 0.100
x 2 (0.100)(1.8 x 10-5 ) 1.8 x 10-6 , which yields x 1.34 x 10-3 ;
[OH - ] 1.34 x 10-3 M pOH 2.873, and pH 11.127
Exercises
1) Calculate the pH of a 0.20 M solution of HCN. Ka = 4.9 x
10-10 ( answer pH = 5)
2) Ethylamine, C2H5NH, has Kb = 5.6 x 10-4. Calculate the concentration of
H3O+ in 0.10 M ethylamine solution and the pH of the solution?
(Answer: [H3O+] = 1.3 x 10-12 M; pH = 11.87)
Relationship between Ka and kb for
conjugate acid-basepair
14
K w K a K b 1 10
Kw Kw
Ka Kb
Kb Ka
• Calculate (a) Kb for the fluoride ion,(b) Ka for the
ammonium ion.
• (Ka for HF= 6.8x10-4 , Kb for NH3= 1.8x10-5)
• SOLUTION:
• We are asked to determine dissociation constants for , the
conjugate base of HF, and ,the conjugate acid of NH3.
Buffered solutions
• Buffer solutions consist of a weak acid and its conjugate base
(acidic buffer such as CH3COOH/CH3COO-, or a weak base and
its conjugate acid (alkaline buffer such as NH 4 + /NH3 ). They
have the property of resisting pH change even when strong
acid or strong base is introduced into solution.
• Human blood, for example, is a complex buffered solution
contains H2CO3/HCO3-that maintains the blood pH at about
7.4.
• Buffered solutions find many important applications in the
laboratory and in medicine
Henderson–Hasselbalch Equation
• HA(aq) ⇌ H+(aq) + A-(aq);
[ H ][ A ]
• Ka =
[ HA ]
pH of Buffer Solution: example #1
• What is the pH of a buffer solution that is 0.45 M acetic acid
(HC2H3O2) and 0.85 M sodium acetate (NaC2H3O2)? The Ka for
acetic acid is 1.8 × 10–5.
• Solution:
• pH = pKa + log([C2H3O2-]/[HC2H3O2]
• pH = -log(1.8 × 10–5) + log(0.85/0.45)
• pH = 4.74 + 0.28 = 5.02
Making Buffer Solution: example #2
A phosphate buffer with pH = 7.40 is prepared using KH2PO4
and K2HPO4.
(a) What is the molar ratio of [HPO42-] to [H2PO4-] in the
buffered solution?
(b) If [H2PO4-] = 0.20 M, what is [HPO42-]?
(c) How many grams of KH2PO4 and K2HPO4, respectively,
are needed to make 500. mL of this solution? (H2PO4- has Ka
= 6.2 x 10-8)
Solutions to Buffer example #245
(a) Use Henderson-Hasselbalch equation:
• pH = pKa + log([HPO42-]/[H2PO4-])
• 7.40 = 7.21 + log([HPO42-]/[H2PO4-])
• log([HPO42-]/[H2PO4-]) = 7.40 – 7.21 = 0.19
• [HPO42-]/[H2PO4-] = 100.19 = 1.55
(b) If [H2PO4-] = 0.20 M,
• [HPO42-] = 1.55 x 0.20 M = 0.31 M
Solutions to Buffer example #2
(c) Moles of KH2PO4 needed =
500. mL x (1 L/1000 mL) x 0.20 mol/L = 0.10 mole
• Moles of K2HPO4 needed =
500. mL x (1 L/1000 mL) x 0.31 mol/L = 0.155 mole
• Grams of KH2PO4 needed =
0.10 mol x (136.086 g/mol) = 14 g
• Grams of K2HPO4 needed =
0.155 mol x (174.178 g/mol) = 27 g
Ka for benzoic= 6.3x10-5
