Excelet

The Behavior of Weak Acids

Objectives:
1. Review pH for strong acids

2. Examine how the acid dissociation constant and concentration

influence the amount of dissociation.

3. Explore the effect of common ions on the equilibrium.

4. Explore the effect of salt (uncommon ions) on the equilibrium.

5. Examine how temperature can influence the equilibrium.

Click on the tabs to navigate

The pH of strong acids
HNO3 H+ + NO3- Dissociation is 100%.
Enter an initial concentration: 5.00E-01 M 5.00E-01 M 5.00E-01 M What do you notice about
the (acid)o and (H+)? answer
pH = 0.30

at 25oC:
pH = 7.00 70 (H+) = 1.00E-07 (OH-) = 1.00E-07 pOH = 7.00

OH- 7
H+ 7

H+ OH-

NEUTRAL

Sinex 2007
The Dissociation of a Weak Acid
HA H+ + A-
select a weak acid and select the initial
its dissociation constant Ka = 1.80E-05 (HA)o = 1.00E-01 concentration of acid
chlorous 1.00
nitrous5 0.100
formic
Percentage of each chemical species
0.0100
benzoic 100 2 0.00100
acetic 0.000100
hypochlorous 90 % 1 1.00 0.0000100
hydrocyanic
HA 98.67 2 0.100
80
H+ 1.33 3 0.0100 Questions to address:
70
A -
1.33 4 0.00100 1. How does %dissociation vary
equilibrium concentrations 60 5 0.000100 with the Ka or the strength of
(HA) = 9.87E-02 M 50 6 ### the weak acid?
(H ) = 1.33E-03 M
+
40
(A-) = 1.33E-03 M 2. How does %dissociation vary
30
with the concentration of
%dissociation = 1.333 20 the weak acid?
10
We can investigate the 0 3. How does the pH vary as the
influence of the Ka and acid gets weaker (smaller Ka)?
HA H+ A-
concentration of a weak
acid on the amount of acetic acid 4. How would a strong acid
dissociation. pH = 2.88 behave as its concentration
was decreased?

Sinex 2007
Effect of adding common ions
What happens to the
For 1.00 L 0.10 M nitrous acid - HNO2 Ka = 4.60E-04 dissociation of the weak acid
when we add a common ion?
HNO2 H+ + NO2-
Pick a common ion
acid only add common
weak ion
acid only with common weak acid with common ion added
ion added 1
add HCl (strong acid)
100 2)
(HNO 0.093444 0.093444 HNO2 93.44377 93.44377
add sodium nitrite
90)
(H +
0.006556 0.006556 H +
6.556229 6.556229
(NO
802-) 0.006556 0.006556 NO2- 6.556229 6.556229 (HCl)
0 0
70
6.556229
60
50 %dissociation = 6.56
40
30 The percent dissociation
for 0.10 M HNO2 is 6.56%.
20
10 How do you calculate the
0 percent dissociation when a
HNO2 H+ NO2-
common ion is present?
answer
When you add the common ion, which way does the reaction shift? answer
When you decrease the common ion, which way does it shift? answer

Sinex 2007
What if we add salt or ions that are uncommon?
Consider formic acid:
HCOOH H+ + HCOO- What happens to the
dissociation of the weak acid
(NaCl) when we add a salt (NaCl)
Ka = 1.80E-04 S= 0.00 0 that is not a common ion?

For a 0.10M HCOOH pure waterwith NaCl added

(HCOOH) = 9.58E-02 HCOOH pure water
95.8464 9.58E+01with NaCl added 3.745 Increase the ionic
100
(H+) = 4.15E-03 90 H+ 4.153595 4.15E+00 1.80E-04 strength, S, and
(HCOO ) = 4.15E-03
-
HCOO -
4.153595 4.15E+00 observe the Ka
80
and %dissociation.
70
Based on Enke (2001)
%dissociation = 4.15 60 Art and Science of What happens?
50 Chemical Analysis
The percent dissoication 40 pKa = pKa - N*0.5091*S^0.5
o

in pure water is 4.15% N = 2 for formic acid

30
20
10
0
HCOOH H+ HCOO-

Ka (pure water) = 1.8 x 10-4

Sinex 2007
The effect of temperature
HA H+ + A- Is the dissociation reaction
Temperature (K) endothermic or exothermic?
select an acid 312
acetic 1 - +
hydrocyanic
phenol Ka (25oC) = 1.80E-05 Ka = 1.79E-05
pKa (25 C) =
o
4.745 pKa = 4.747

For a 0.010 M solution

Temperature (oC) Comparison Is the dissociation
25 39 As the temperature endothermic or
(HA) = 9.58E-03 9.59E-03 weak acid increases, Ka exothermic?
(H ) = 4.15E-04 4.14E-04
+
acetic
(A-) = 4.15E-04 4.14E-04 hydrocyanic
phenol
%dissociation = 4.154 4.144
type increases type endothermic
If the percent dissociation increases or decreases or exothermic
how is the Ka changing? answer in the yellow boxes in the yellow boxes

Correct answers will be acknowledged!

Sinex 2007
 acid Ka formulas enthalpy of ionization, kJ/
1 chlorous 1.00E-02 HClO2 DHo
2 nitrous 4.60E-04 HNO2 1 acetic -0.25
3 formic 1.80E-04 HCOOH 2 hydrocyanic 43.5
4 benzoic 6.50E-05 C6H5COOH 3 phenol 23.6
5 acetic 1.80E-05 CH3COOH
6 hypochlorous 3.00E-08 HOCl using van't Hoff's equatio
7 hydrocyanic 4.90E-10 HCN for different temperatur

Ka Source: Wired Chemist DHo Source:

http://wulfenite.fandm.edu/Data%20/Table_19a.html Tinoco, Sauer, and Wang (
Physical Chemistry: Princ
All calculations are based on solving the quadratic equation; in Biological Sciences
hence, they are good for dissociations > 5%.
enthalpy of ionization, kJ/mole
Ka
1.80E-05
4.90E-10
1.30E-10

using van't Hoff's equation to adjust Ka

for different temperatures

DHo Source:
Tinoco, Sauer, and Wang (1995)
Physical Chemistry: Principles and Application
in Biological Sciences

Sinex 2007