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Acid-Base Equilibria
81
John A.
Chapter 17-1
Overview
Solutions of a Weak Acid or Base
82
John A.
Chapter 17-2
Weak acids and weak bases only partially dissociate; their strengths are
experimentally determined in the same way as strong acids and bases by
determining the electrical conductivity.
The reaction of a weak acid (or base) with water is the same as discussed in
previous section.
Consider the reaction:
[H3O ][ A ]
[HA ]
Relative strengths of weak acids can be determined from the value of the
equilibrium constant.
E.g. determine which acid is the strongest and which the weakest.
Acid
HCN
HCOOH
CH3COOH
HF
John A.
Ka
4.9x1010
1.8x104
1.8x105
3.5x104
83
Chapter 17-3
Determining K from pH
Ka determined if pH and CHA known.
Use the equilibrium expression for the acid.
E.g. Determine the equilibrium constant of acetic acid if the pH of a
0.260 M solution was 2.68. Determine [H3O+]; [HA]; and [A].
Strategy
Calculate the [H3O+] from pH; this is x in the table above.
The rest of the quantities are obtained from the bottom row.
84
John A.
Chapter 17-4
John A.
Chapter 17-5
85
pH from Ka and Ca
E.g. Calculate the pH of 0.100M acetic acid. Given pKa = 4.76
Method I:
Substitute into equilibrium equation to get
x2 + 1.75x105x 1.75x106 = 0.
Solve using quadratic equation (see book).
Method 2
Assume x << CHA. Then x = (KaCHA)1/2.
Check (confirm assumption to be correct)
1.75 x10 5
x2
0.100 x
John A.
Chapter 17-6
86
% Ionization
x
CHA
100%
Solution: determine x for each and sub into definition above. Check assumptions.
CHA K a 1/ 2
% Ionization
100%
CHA
Ka
CHA
1/ 2
100%
87
John A.
Chapter 17-7
Polyprotic Acids
Some acids can donate more
Treat Polyprotic
than one proton to the solution.
Thus a diprotic acid has two
acids as if they
protons such as H2S and
were monoprotic
H2SO4, while a common
acids; Use Ka1.
triprotic acid has three acidic
protons that can be donated
(H3PO4).
First proton easily removed;
others much more difficult.
The equilibrium constant for removal of each successive proton is
about 105 times the equilibrium constant for removal of the preceeding
proton.
2
E.g. determine the pH of 0.100 M H2SO3. Then determine [SO 3. ]
88
John A.
Chapter 17-8
Treat bases just like we did the weak acid; except you are calculating
[OH].
The general equation that describes the behavior of a base in solution
is:
[BH ][OH ]
+
Remember that x = [OH ] and not [H3O ].
x2
John A.
Chapter 17-9
R2
R1
H
Amine Structure
810
John A.
Chapter 17-
John A.
Acid Ka
HF
3.5x104
HCOOH
1.8x104
HOCl 3.5x108 811
HCN 4.9x1010
Chapter 17-
Salts of WA and WB
Salt: an ionic substance formed as a result of an acidbase
neutralization reaction.
Salt of an acid(base) obtained by its neutralization with acid if it is a
base and base if it is an acid.
John A.
812
Chapter 17-
813
Chapter 17-
John A.
814
Chapter 17-
Salt of WA + WB
Determine Ka and Kb of acidic and basic portions of
salt.
Largest K dominates to make solution either acidic
or basic.
E.g. determine if 0.100 M NH4CN is acidic or basic.
E.g. 2 predict if 0.100 M C6H5NH3F is acidic or basic.
815
John A.
Chapter 17-
CommonIon Effect: the change in the equilibrium that results from the
addition of an ion that is involved in the equilibrium.
E.g. NaOCl is added to 0.100 M HOCl; NH4Cl is added to NH3.
Setting up the standard equilibrium table can show the effect.
E.g. determine the pH of a solution prepared by mixing 50.0 mL of 0.100 M
HOCl with 50.0 mL of 0.100 M NaOCl (Ka = 3.5x108).
Set up equilibrium table after calculating the concentrations of each in the
final mixture.
Initial concentrations change slightly as a result of a change reaction.
John A.
816
Chapter 17-
Buffers
Let r
[base]
then the equilibrium equation is:
[acid]
K a [H3O ] r
K
[H3O ] a
r
817
John A.
Chapter 17-
Cb Vb
r
Ca Va Cb Vb
John A.
818
Chapter 17-
Henderson-Hasselbalch Equation
pH = pK a + log
= pK a + log
[ A ]
[HA]
n
A
nHA
John A.
Chapter 17-
Neutralization Reactions
Neutralization Reaction: the reaction of an acid with a base to
produce water.
Extent of reaction nearly quantitative (except if both acid and
base are weak.
SASB:
E.g. HNO3 + NaOH NaNO3 + H2O
SA produces: H3O+
SB produces: OH
Overall reaction:
WASB: thought of as two step reaction.
E.g. HOCl + NaOH NaOCl + H2O K = ?
820
John A.
Chapter 17-
WB + SA
SA produces H3O+ ions; use base as is.
E.g. NH3 + HCl NH+ Cl or
4
John A.
821
Chapter 17-
pH Titration Curves
Titration curve: plot of pH of
the solution as a function of
the volume of base (acid)
added to an acid (base).
Sharp rise in curve is
equivalence point.
pH at equivalence point is 7.0
for SA but higher for WA.
Equivalence point can be used to determine the
concentration of the titrant.
E.g. the equivalence point for 15.00 mL of an acid
occurred when 25.00 mL of 0.075 M NaOH was added.
What was the molarity of the acid?
John A.
822
Chapter 17-
SASB Titrations
Base removes some acid and pH increases.
Let nb = moles of base added
na,r = moles of acid remaining
na,r = na nb = CaVa CbVb
Moles of hydronium ion same as moles of acid remaining. n H3O+ =
na,r;
nH O+
[H3O ]
V a + Vb
Ca Va Cb Vb
V a + Vb
John A.
823
Chapter 17-
Titration of SB with SA
[OH ]
OH
V a + VB
C V Ca Va
b b
V a + VB
EP: pH = 7.00
Beyond EP: pH due only to excess acid. Use total volume.
E.g. Determine pH of 10.0 mL of 0.100M NaOH after addition of 5.00,
10.0 and 15.0mL of 0.100M HCl.
John A.
824
Chapter 17-
WA with SB Titration
n
pH pK a log A
nHA
pK a log
Cb Vb
Ca Va Cb Vb
John A.
Chapter 17-
WBSA Titrations
John A.
Chapter 17-