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Acids and Bases: Arrhenius Definition
▪ An acid is a substance that dissociates in
water to yield H3O+.
▪ A base is a substance that dissociates in
water to yield OH–.
▪ This explains why all neutralization
reactions between strong acids and bases
and have similar heats of reaction:
H+(aq) + OH–(aq) → H2O(l) H0 = -57 kJ/mol
3
Acids and Bases: Arrhenius Definition
Arrhenius acid is a substance that produces H+ (H3O+) in water.
AH A- + H+
B- + H+ BH
Acid-Base Neutralization
acid + base salt + water
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Hydronium Ion
AH A- + H +
Chemical Reality:
HO- + H+ → H2O
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Conjugate Acid-Base Pairs
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Amphiprotic Species
Amphiprotic or amphoteric- species that can gain or lose a
proton under the appropriate conditions
Acid Base
Base Acid
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Water Acid-Base Reaction
+ -
H O + H O [H O H ] + H O
H H H
Kc = [H+][OH-] = Kw
Kw is called the ion-product constant of water.
At 250C
Kw = [H+][OH-] = 1.0 x 10-14 22
Acidic, Basic, and Neutral Solutions
Kw = [H+][OH-] = 1.0 x 10-14
▪ In a neutral solution
[H + ] = [OH − ] = 1.0 10 −14 = 1.0 10 −7 M
▪ In an acidic solution
[H] 1.0 10 −7 M; [OH − ] 1.0 10 −7 M
▪ In a basic solution
[H + ] 1.0 10 −7 M; [OH − ] 1.0 10 −7 M
[OH-] = 0.0025 M
-14
+ K w 1.0 × 10 -12
[H ] = -
= = 4.0 × 10 M
[OH ] 0.0025
Solution Is At 250C
neutral [H+] = [OH-] [H+] = 1.0 x 10-7 pH = 7
acidic [H+] > [OH-] [H+] > 1.0 x 10-7 pH < 7
basic [H+] < [OH-] [H+] < 1.0 x 10-7 pH > 7
pH [H+]
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pH = -log [H+]
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pOH Scale
▪ In the analogy to the pH scale, we can define a
pOH-scale for the concentration [OH–].
Kw = [H+][OH-] = 1.0 x 10-14
pH + pOH = 14
2) pH = -log [H+]
4) pH + pOH = 14
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CH 4, Review
36
Strong and Weak Bases
• Bases can be either strong electrolytes or weak electrolytes.
• Strong bases completely break up into their ions:
NaOH (aq) → Na+(aq) + OH-(aq)
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Strong and Weak Bases
▪ 6 Strong bases:
▪ MOH, where M = Na, K, Li.
▪ M(OH)2, where M = Ca, Sr, Ba.
▪ Weak bases:
▪ Any H+ acceptor that is not those six.
▪ Other metal hydroxides, Mg(OH)2, Zn(OH)2, Co(OH)2, La(OH)3.
▪ Ammonia (NH3).
▪ Amines, such as CH3NH2, (CH3)2NH, C5H5N.
39
Strong and Weak Bases
Strong Bases are strong electrolytes
[OH-] = 0.040 M
pH = 14.00 – pOH = 12.60
pOH = -log 0.040 = 1.40 42
Relative Strength of Acid-Base Pairs
AH + B- A- + BH
acid base conjugate conjugate
base acid
Acids/Bases Conjugate Bases/acids
Very Strong Very Weak
Strong Weak
Weak Strong
Very Weak Very Strong
_______________________________________
• Strong acids lose protons readily ➔ weak conjugate bases;
[H+][A-]
Ka =
[HA]
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Acids: How Strong? How Weak?
[H+][A-]
Ka =
[HA]
Stronger, Large Ka
Strong or
HNO2(aq) H+(aq) + NO2-(aq)
weak acid?
[HNO2] = 0.036 M
https://www.youtube.com/watch?v=OfJ6ArU81KE 50
Bases: How Strong? How Weak?
B-(aq) + H2O(l) BH(aq) + OH-(aq)
[BH][OH-]
Kb =
[B-]
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Bases: How Strong? How Weak?
[BH][OH-]
Kb =
[B-]
base
Kb
strength
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Bases: How Strong? How Weak?
Base Formula Kb Conj. Acid
Ethylamine C2H5NH2 5.610-4 C2H5NH3+
Base strength Methylamine CH3NH2 4.410-4 CH3NH3+
Ammonia NH3 1.810-5 NH4+
Pyridine 1.710-9 C5H5NH+
Kb = 1.810-5
[NH3]0 = 0.40 M
pH = ?
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Example
What is the pH of a 0.40 M NH3 solution (Kb = 1.810-5)?
Find OH-
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
Kb = 1.810-5
[NH3]0 = 0.40 M
pH + pOH = 14
pH + pOH = 14.00
pH + 2.57 = 14.00
pH = 11.43
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Ka and Kb
HA(aq) H+(aq) + A-(aq) A-(aq) + H2O(l) AH(aq) + OH-(aq)
[H+][A-] [AH][OH-]
Ka = Kb =
[HA] [A-]
KaKb = Kw
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Kw, Ka and Kb Summary
Kw Kw
KaKb = Kw Ka = Kb =
Kb Ka
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65
The Ka for formic acid (HCOOH) is 1.7x10-4. What
is Kb for HCOO-?
Kw = 1.0x10-14
KaKb = Kw
Kw
Kb =
Ka
Kb = 1.0x10-14
1.7x10-4
Kb = 5.9 x10-11
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CH 4, Review
67
Common Ion Effect
The common ion effect is the shift in equilibrium caused by the
addition of a compound having an ion in common with the
dissolved substance. Specific case of Le Chatelier’s
Principle
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Example
(a) Calculate the pH of a 0.20 M CH3COOH solution. (2.72)
(b) What is the pH of a solution containing both 0.20 M CH3COOH
and 0.30 M CH3COONa? The Ka of CH3COOH is 1.8 x 10-5.
(x)(0.30+x) (x)(0.30)
+
[H ][CH 3COO ]- 1.8 × 10-5 =
Ka = [0.2] 0.20-x 0.20
[CH3COOH] If > 400
Ka x = [H+] = 1.2 x 10-5 M
(x)(0.30+x)
1.8 × 10-5 = we can neglect x
0.20-x -log (1.2 x 10-5 ) = 4.92
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Example
(a) Calculate the pH of a 0.20 M CH3COOH solution. (2.72)
(b) What is the pH of a solution containing both 0.20 M CH3COOH
and 0.30 M CH3COONa? The Ka of CH3COOH is 1.8 x 10-5. (4.92)
H+ pH
[A-]
pH = pKa + log
[HA]
[0.30]
pH = -log (1.8 x 10-5) + log = 4.92
[0.20]
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Buffer Solutions
A buffer solution consists of:
1. A weak acid (or weak base) HA (or B-)
and
2. The salt of the weak conjugate base (or weak acid)
A - (or BH)
Both must be present!
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Crumple Zones
Sacrificial portion of the car that protects the passengers.
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Buffer- the chemical equivalent to a crumple zone.
Buffer Solutions
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Buffer Solutions
Adding HCl:
Water
vs.
Buffer w/
1.0 M CH3COOH
1.0 M CH3COONa
In Water
If you add enough HCl, all of the
HCl(aq) H+(aq) + Cl-(aq) CH3COO- will be consumed.
HCl ⎯→ H+ + Cl- Wins!
In Buffer
H+ (aq) + CH3COO- (aq) CH3COOH (aq)
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Crumple Zones
more
H+ or OH- H+ or OH-
H+ OH-
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Buffer Capacity
▪ Buffer capacity is its ability to resist pH changes.
▪ The more concentrated the components of a buffer, the
greater the buffer capacity.
▪ A buffer also has the highest capacity when the component
concentrations are equal:
[A − ]
pH = pK a + log = pK a + log1 = pK a
[HA]
▪ A buffer whose pH is equal to or near the pKa (pH = pKa) of
its acid component has the highest buffer capacity.
▪ The addition of strong acid or base weakens the buffer
capacity.
82
Example
(a) Calculate the pH of a buffer system containing 1.0 M CH3COOH
and 1.0 M CH3COONa. The Ka of CH3COOH is 1.8 x 10-5 (Table
15.3).
(b) What is the pH of the buffer system after the addition of 0.10
mole of gaseous HCl to 1.0 L of the solution? Assume that the
volume of the solution does not change when the HCl is added.
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Example
(a) Calculate the pH of a buffer system containing 1.0 M CH3COOH
and 1.0 M CH3COONa. The Ka of CH3COOH is 1.8 x 10-5 (Table
15.3).
[A-]
pH = pKa + log pKa = -log Ka
[HA]
[1.0]
pH = -log (1.8 x 10-5) + log = 4.74
[1.0]
84
Example
(a) Calculate the pH of a buffer system containing 1.0 M CH3COOH
and 1.0 M CH3COONa. The Ka of CH3COOH is 1.8 x 10-5 (Table
15.3). (4.74)
(b) What is the pH of the buffer system after the addition of 0.10
mole of gaseous HCl to 1.0 L of the solution?
0.10 M
0.10 M
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Relevant Equations Summary
1) Kw = [H+][OH-] = 1.0 x 10-14 B-(aq) + H2O(l) BH(aq) + OH-(aq)
Henderson-Hasselbalch equation
HA (aq) H+ (aq) + A- (aq)
NaA (s) Na+ (aq) + A- (aq)
[A-]
pH = pKa + log [HA]