Acid Ba See Quil

Acid Base Equilibria
Chapter 17
Topics of Discussion
Solutions of a weak acid and base

Acid-Ionization Equilibria Polyprotic Acids Base-Ionization Equilibria
Acid-base Properties of Salt Solutions
Solutions of Weak Acid/Base with Another Solute

Common-Ion Effect
Buffers
Acid-Base Titration Curves
6/4/2013 CHEM 106, Acid-Base Equilibria 2
Weak acid
HA + H2O H3O+ + A[H3 0 ][A ] KC [HA][H 2 0] [H3 0 ][A ] [H 2 0]KC K a [HA]
Ka is acid dissociation constant HA H+ + A[H ][A ] Ka [HA]

Some weak acids

N am e Io d ic a c id N itr o u s a c id H y d ro flu o ric a c id F o r m ic a c id A c e tic a c id H y p o c h lo ro u s a c id F o r m u la H IO 3 HNO2 HF HCOOH C H 3C O O H HOCl Ka 0 .1 7 7 .1 x 1 0 - 4 6 .8 x 1 0 - 4 1 .8 x 1 0 - 4 1 .8 x 1 0 - 5 3 .0 x 1 0 - 8 pK a 0 .2 3 3 .1 5 3 .1 7 3 .7 4 4 .7 4 7 .5 2
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CHEM 106, Acid-Base Equilibria
Weak Base
B + H20 BH+ + OH[BH ][OH ] Kb [B]
NH3 + H2O NH4+ + OH [NH4 ][OH ] Kb [NH3 ]
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Some weak bases
N am e M e th y l a m in e H y d ra z in e A m m o n ia H y d ro x ila m in e A n ilin e
F o r m u la C H 3N H 2 N 2H 4 NH3 HONH2 C 6H 5N H 2
Kb 4 .4 x 1 0 - 4 1 .7 x 1 0 - 6 1 .8 x 1 0 - 5 6 .6 x 1 0 - 9 4 .4 x 1 0 - 1 0
pK b 3 .3 6 5 .7 7 4 .7 4 8 .1 8 9 .3 6
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Equilibrium calculations
Ka and Kb from percentage ionization %ionization = (amount ionized)/(amount available)x100 Example In a 0.01 M solution of butyric acid the acid is 4 % ionized at 20 0C. Calculate Ka and pKa for butyric acid at this temperature.
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Solution
HBu + H2O H3O + BuH 2O + H B u In itia l 0 .0 1 C hange - 0 .0 1 x 0 .0 4 E q u i l i b r i u m 0 .0 0 9 9 6 H 3O + + 0 + 0 .0 0 0 4 0 .0 0 0 4 Bu0 + 0 .0 0 0 4 0 .0 0 0 4
Ka = (0.0004)2/(0.00996)
= 1.6x10-5
pKa = 4.8
Equilibrium calculations
Ka and Kb from initial concentrations and pH Example In a 0.1 M solution of formic acid, the pH is 2.38 at 25 0C. Calculate the Ka and pKa for formic acid at this temperature. HCOOH + H2O HCOO- + H3O+
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Solution
[H3O+] = 10-2.38 = 0.0042 M

H 2O + In itia l C hange e q u ilib r iu m HCOOH 0 .1 - 0 .0 0 4 2 0 .0 9 6 H 3O + + 0 + 0 .0 0 4 2 0 .0 0 4 2 HCOO0 + 0 .0 0 4 2 0 .0 0 4 2
[HCOO ][H 3O ] Ka [HCOOH]
Ka = 1.84x10-4
Simplifying assumption
HA H+ + A Accuracy of calculations may be set within 5% [H+]/[HA]initial < 0.05 [H+]2/[HA]initial = Ka [HA]initial > Ka 400 [HA]equilibrium = [HA]initial - x (x is negligible) [HA]equilibrium ~ [HA]initial
Example
What is the pH of 0.010 M solution of dimethyl amine, (CH3)2NH? Kb = 9.6x10-4 (CH3)2NH + H2O (CH3)2NH2+ + OH Is simplification possible? [(CH3)2NH]initial > 400 Kb 0.01 > (400)(9.6x10-4) = 0.384 No simplification. Quadratic solution.
Solution
H 2O + (C H 3)2N H In itia l 0 .0 1 C hange -x E q u ilib riu m 0 .0 1 - x (C H 3)2N H 0 +x x
2 +
OH 0 +x x
x2 K b 9.6 x10 4 0.01 x
x2
+ 9.6x10-4x - 9.6x10-6 = 0 x = 2.65x10-3 pOH = -log(2.65x10-3) = 2.58 pH = 11.42

CHEM 106, Acid-Base Equilibria 13
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Polyprotic Acids
Acids with two or more acidic protons H2SO3(aq) HSO3-(aq) + H+(aq) Ka1= 1.3x10-2 HSO3-(aq) SO32-(aq) + H+(aq) Ka2= 6.3x10-8 For polyprotic acids: Ka1> Ka2> Ka3
Number of protons to be dissociated are larger. First proton separates from singly negative charged ion.
For 0.25 M sulfuroz acid; pH=?, SO32-=?

H2O + Initial Change Equilibrium
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H2SO3 0.25 -x 0.25-x
+ H3O 0 +x x
HSO30 +x x
14
Polyprotic Acids-II
x2 K a1 1.3x10 2 x H 3O 0.051, pH 1.29 0.25 x
xapp= 0.06, quadratic equation is needed to obtain x. SO32-=?

H2O + Initial Change Equilibrium
+ HSO3- H3O + 0.051 0.051 -x +x 0.051-x 0.051+x
SO320 +x x
x(0.051 x) 2 8 -8 Ka2 6.3x10 x SO3 6.3x10 0.051 x

Acid-base Properties of Salt Solutions
Ionization of formic acid HCOOH + H2O H3O+ + HCOO[H 3O ][HCOO ] Ka [HCOOH]
[ HCOOH ][OH ] Kb [ HCOO ]
Hydrolysis of formate ion HCOO- + H2O HCOOH + OH-
[ H 3O ][HCOO ] [ HCOOH ][OH ] K a .Kb x [ H O ][ OH ] KW 3 [ HCOOH ] [ HCOO ]

For any acid-base conjugate pairs

Ka x Kb = KW pKa + pKb = pKW = 14 The value of Ka = 1.8x10-5 for CH3COOH. What is the value of Kb for CH3COO-? Solution
K W 1x1014 10 Kb 5.6x10 K a 1.8x105
Solutions of salts of weak acids and bases
HCOOH + H2O HCOO- + H3O+

Strong acid weak conjugate base HCl H+ + ClVery weak base acid conjugate base
Very strong acid
Very weak acid

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H2O H+ + OHVery strong base

What is the pH of 0.1 M solution of NaOCl? Ka = 3.0x10-8 Solution OCl- + H2O HOCl + OH[HOCl][OH ] 1x10 14 Kb 3.3x10 8 [OCl ] 3x10
7
Example
(x2/0.1) = 3.3x10-7 [HOCl] = [OH-] = x = 1.8x10-4 pOH = -log(1.8x10-4) = 3.74 pH = 14.00 - 3.74 = 10.26
NH3 + H2O NH4 + OH
Ammonia and its conjugate acid ammonium ion + [NH4 ][OH ] Kb 1.8x105 [NH3 ]
NH4+ + H20 NH3 + H3O+

[NH3 ][H3O ] K w 1.0x1014 10 Ka 5.6x10 [NH4 ] K b 1.8x105
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Examples of some weak acids and bases
Metal ions with high charge densities are weak acids [Al(H2O)6]3+ + H2O [Al(H2O)5OH]2+ + H3O+ Metal ions with small charges are nonacids Aquous ions of Gr IA: Li+, Na+, K+, Rb+, or Cs+ (except Be2+) and Gr IIA: Mg2+, Ca2+, Sr2+, and Ba2+ do not affect pH of solution.
Acid-base properties of a salt
If only the cation of salt is acidic, the solution will be acidic. If only the anion of the salt is basic, the solution will be basic. If a salt has a cation that is acidic and an anion that is basic, the pH of the solution is determined by the relative strength of the acid or base.
Example
Predict whether the following salts are acidic, basic or neutral.

NaOCl Na+ + OClOCl- + H2O HOCl + OH NaNO2 (basic) KCl (neutral) NH4Br (acidic)
6/4/2013 CHEM 106, Acid-Base Equilibria
NaOCl NaNO2 KCl NH4Br
(basic)
23
Common-Ion Effect
The common-ion effect is the shift in an ionic equilibrium cause by the addition of a solute that provides an ion that takes part in the equilibrium. What is the degree of ionization of 0.10 M formic acid, HCOOH, solution? Ka= 1.84x10-4
a. When it is together with 0.20 M HCl. b.When it is pure.
H2O + Initial Change equilibrium HCOOH 0.10 -x 0.10-x H3O+ + 0.20 +x 0.20+x HCOO0 +x x
4 Deg . Ion . 9 . 5 x 10 [HCOO ][H 3O ] x(0.20 x) Ka x 9.2 x10 5 Deg.Ion. 4.2 x10 2 P [HCOOH] 0.10 x
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Buffers
Buffer solutions are used to keep the pH constant. Dilution of solution, addition of acid or base to buffer solution affects the pH very little. Buffer consists of a weak Bronsted acid and its conjugate base or vice versa. Examples: NH3 and NH4Cl (NH3 / NH4+) CH3COOH and CH3COONa (CH3COOH / CH3COO-)
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How a buffer work?

Buffer: HA H+ + A If extra acid is added: H+ + A- HA (extra acid is neutralized by conjugate base A-) If extra base is added: OH- + HA H2O + A- (extra base is neutralized by acid HA)
Acetic acid / acetate buffer
What is the pH of a buffered solution made up 0.015 M sodium acetate and 0.10 M acetic acid? Ka = 1.8x10-5
In itia l C hange e q u ilib r iu m H C 2H 3O 2 0 .1 0 -x 0 .1 0 - x H + + C 2H 3O 20 .0 0 .0 1 5 +x +x x 0 .0 1 5 + x
1.8 x10
x (0.015 x ) (0.1 x )
[H+]
pH
= x = 1.2x10-4
= 3.92
27
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Ammonia / ammonium ion buffer
Calculate the pH of a buffer solution prepared by dissolving 0.10 mol NH3 and 0.2 mol NH4Cl in 1 L water. Kb = 1.8x10-5
H2O + NH3 NH4+ + OHInitial 0.1 0.2 0.0 Change -x +x +x equilibrium 0.1-x 0.2+x x
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Henderson-Hasselbalch Equation
HA H+ + A[A ][H ] Ka [HA]
-logKa= log[HA] - log[H+] - log[A-]

[A ] pH pK a log [HA]
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Preparation of a buffer solution with a given pH
How do you prepare an acetate/acetic acid buffer solution with a pH = 5.0? (Ka = 1.8x10-5) Solution pH = pKa + log([A-]/[HA]) 5.0 = -log(1.8x10-5) + log([A-]/[HA]) 10(5.00 - 4.74) = [A-]/[HA] [A-]/[HA] = 1.82
Selecting a weak acid for the preparation of a buffer solution
A buffer solution is effective if 0.1 < [HA] / [A-] < 10 pH = pKa + log([A-]/[HA]) pH = pKa 1
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Example
How a buffer solution with pH = 8.00 be prepared? Solution: pH = pKa + log([A-]/[HA]) Hypochlorous acid, HOCl: Ka = 3.0x10-8 pKa = 7.52 8.00 = 7.52 + log([OCl-]/[HOCl]) [OCl-]/[HOCl] = 3.02
Buffer capacity
The ratio [A-]/[HA] defines the pH of buffer solution. The magnitude of concentrations [A-] and [HA] defines the buffer capacity. It is the ability of a buffer solution to compensate extra added acid or base.
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Example (Buffer capacity)
A 1 L buffer solution is prepared using 1.00 M acetic acid, HA, and 1.00 M NaAc. In an experiment 0.11 mol of hydroxide ion is generated without any volume change. Can the buffer solution handle this without a pH change of 0.1 unit? Ka = 1.8x10-5
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Solution
HA + H2O H3O+ + A-
H 1.8x10
[H ][A ] Ka 1.8x10 [HA]

5
pH 4.74
In itia l E q u ilib riu m
OH- + HA 0 .1 1 1 .0 0 .0 0 .8 9
A - + H 2O 1 .0 1 .1 1
[H ](1.11) 1.8x10 0.89
pH =4.84 (buffer solution just tolerates excess base)

Acid-base titrations
The pH of an unknown acid may be found by titrating it with a standard base solution until the end point is reached. The equivalence point occurs when stoichiometrically equivalent acid and base reacts. Titration curves are drawn, pH vs added reagent, and equivalence point is determined.
Titration of 25 mL of 0.2 M HCl with 0.2 M NaOH

Volume NaOH (mL) 0 10.00 20.00 24.00 24.90 24.99 25.00 25.01 25.10 26.00 50.00
24.99
Total volume (mL) 25.00 35.00 45.00 49.00 49.90 49.99 50.00 50.01 50.10 51.00 75.00
Excess ion (mol/L) 0.2 (H+) 8.571x10-2 2.222x10-2 4.082x10-3 4.000x10-4 4.000x10-5 0 3.999x10-5 (OH-) 3.992x10-4 3.922x10-5 6.666x10-2
pH 0.70 1.07 1.65 2.39 3.40 4.40 7.00 9.60 10.60 11.59 12.82
37
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Titration of 25 mL 0.2 M HCl with 0.2 M NaOH

14 12 10
pH
Titration curve
8 6 4 2 0 0 10 20 30 40 50 mL NaOH added
Equivalence point
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Titration of weak acid by strong base

14 12
CH3COOH + OH- CH3COO- + H2O Before the titration begins

Dissociation of weak acid
10
During the titration but before the equivalence point

Formation of a buffer solution
pH
6 4
At the equivalence point

Hydrolysis of conjugate base
0 15 20 25 30 mL NaOH added
After the equivalence point

Concentration of OH39
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Before the titration begins
What is the pH of 0.2 M CH3COOH? Ka = 1.8x10-5

CH3COOH + H2O CH3COO- + H3O+
Solution:
[H3O ][CH3COO ] x 2 1.8X105 [CH3COOH] 0.2
[H3O+] = 1.9x10-3 M
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pH = 2.72
40
Before the equivalence point...
Adding 10 mL 0.2 M NaOH to 25 mL 0.2 M CH3COOH.

In itia l E q u ilib riu m O H - + C H 3C O O H 2 m m ol 5 m m ol 3m m ol C H 3 C O O -+ H 2 O 0 m m ol 2m m ol
[CH3COOH] = (3 mmol)/(35 mL) = 0.0857 M [CH3COO-] = (2 mmol)/(35 mL) = 0.0571 M

[H ](0.0571) 1.8x10 (0.0857)
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5
[H+] = 2.7x10-5 M pH = 4.57

41
25 mL 0.2 M NaOH is added to 25 mL 0.2 M CH3COOH. What is the pH of solution? Acetic acid is converted to acetate ion completely. CH3COO- + H2O CH3COOH + OH5mmol [CH3COO ] 0.1M 50mL [OH ][CH3COOH] K W 10 5.6x10 [CH3COO ] Ka
[OH-] = 7.5x10-6 M pOH = 5.12 pH = 14.00 - 5.12 = 8.88

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35 mL 0.2 M NaOH is added to 25 mL 0.2 M CH3COOH. What is the pH of solution? OH- neutralizes CH3COOH. Excess OH- defines the pH. [OH-] = (35x0.2-25x0.2 mmol)/(60 mL) = 0.033M pOH = 1.48 pH = 12.5
Titration of 25 mL 0.2 M HA by 0.2 M NaOH

14 12 10
pH
8 6 4 2 0
pH = 8.88 at equivalence pt
10
20 mL NaOH added
30
40
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Titration of a weak base by strong acid

Titration of 25 mL 0.2 M NH3 and 0.2 M HCl
14
NH3 + H2O NH4+ + OH Before the titration begins

Dissociation of weak base
12
10
8
pH
During the titration but before the equivalence point

Formation of a buffer solution

Hydrolysis of conjugate acid
0 15 20 mL HCl 25 30

Concentration of H+
45
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12 10 8
pH
6 4 2 0 0 10 20 mL HCl 30 40
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46

14
Titration of 25 mL 0.2 M HA by 0.2 M NaOH

14

14
12
12
12
10
10
8
10
8
pH
pH
pH
6
6
4
4
2
2
15 20 25 30
0 mL NaOH added
0
15 20 25 30
15
20 mL HCl
25
30
mL NaOH added
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Acid-base indicators
HIn(aq) H+(aq) + In-(aq)

Acid form color1 Base form color2
[H ][In ] K in [HIn]
pH = pKa + log([In-]/[HIn]) pH > pKa + 1 ([In-]/[HIn]= 10, base color) pH < pKa - 1 ([In-]/[HIn]= 0.1, acid color)

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Acid Base Equilibria

Solutions of a weak acid and base

Acid-base Properties of Salt Solutions

Solutions of Weak Acid/Base with Another Solute

Ka is acid dissociation constant HA H+ + A[H ][A ] Ka [HA]

Some weak acids

CHEM 106, Acid-Base Equilibria

NH3 + H2O NH4+ + OH [NH4 ][OH ] Kb [NH3 ]

CHEM 106, Acid-Base Equilibria

Some weak bases

CHEM 106, Acid-Base Equilibria

CHEM 106, Acid-Base Equilibria

HBu + H2O H3O + BuH 2O + H B u In itia l 0 .0 1 C hange - 0 .0 1 x 0 .0 4 E q u i l i b r i u m 0 .0 0 9 9 6 H 3O + + 0 + 0 .0 0 0 4 0 .0 0 0 4 Bu0 + 0 .0 0 0 4 0 .0 0 0 4

CHEM 106, Acid-Base Equilibria

[H3O+] = 10-2.38 = 0.0042 M

[HCOO ][H 3O ] Ka [HCOOH]

x2 K b 9.6 x10 4 0.01 x

+ 9.6x10-4x - 9.6x10-6 = 0 x = 2.65x10-3 pOH = -log(2.65x10-3) = 2.58 pH = 11.42

For 0.25 M sulfuroz acid; pH=?, SO32-=?

H2SO3 0.25 -x 0.25-x

CHEM 106, Acid-Base Equilibria

xapp= 0.06, quadratic equation is needed to obtain x. SO32-=?

x(0.051 x) 2 8 -8 Ka2 6.3x10 x SO3 6.3x10 0.051 x

Acid-base Properties of Salt Solutions

Ionization of formic acid HCOOH + H2O H3O+ + HCOO[H 3O ][HCOO ] Ka [HCOOH]

[ HCOOH ][OH ] Kb [ HCOO ]

Hydrolysis of formate ion HCOO- + H2O HCOOH + OH-

[ H 3O ][HCOO ] [ HCOOH ][OH ] K a .Kb x [ H O ][ OH ] KW 3 [ HCOOH ] [ HCOO ]

For any acid-base conjugate pairs

Solutions of salts of weak acids and bases

HCOOH + H2O HCOO- + H3O+

Very strong acid

Very weak acid

H2O H+ + OHVery strong base

NH3 + H2O NH4 + OH

NH4+ + H20 NH3 + H3O+

CHEM 106, Acid-Base Equilibria

Examples of some weak acids and bases

Acid-base properties of a salt

Predict whether the following salts are acidic, basic or neutral.

6/4/2013 CHEM 106, Acid-Base Equilibria

NaOCl NaNO2 KCl NH4Br

CHEM 106, Acid-Base Equilibria

CHEM 106, Acid-Base Equilibria

How a buffer work?

6/4/2013 CHEM 106, Acid-Base Equilibria 26

Acetic acid / acetate buffer

CHEM 106, Acid-Base Equilibria

Ammonia / ammonium ion buffer

CHEM 106, Acid-Base Equilibria

-logKa= log[HA] - log[H+] - log[A-]

CHEM 106, Acid-Base Equilibria

Preparation of a buffer solution with a given pH

Selecting a weak acid for the preparation of a buffer solution

CHEM 106, Acid-Base Equilibria

CHEM 106, Acid-Base Equilibria

Example (Buffer capacity)

[H ][A ] Ka 1.8x10 [HA]

In itia l E q u ilib riu m

[H ](1.11) 1.8x10 0.89

pH =4.84 (buffer solution just tolerates excess base)

Titration of 25 mL of 0.2 M HCl with 0.2 M NaOH

CHEM 106, Acid-Base Equilibria