Excelet

The Behavior of Weak Acids

Objectives:
1. 2. Review pH for strong acids Examine how the acid dissociation constant and concentration influence the amount of dissociation. 3. 4. 5. Explore the effect of common ions on the equilibrium. Explore the effect of salt (uncommon ions) on the equilibrium. Examine how temperature can influence the equilibrium.

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The pH of strong acids

HNO3 Enter an initial concentration: 5.00E-01 M pH = H+ 5.00E-01 M 0.30 + NO35.00E-01 M Dissociation is 100%. What do you notice about the (acid)o and (H+)? answer

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

OHH+

7 7

H+

OH-

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The Dissociation of a Weak Acid

HA select a weak acid and its dissociation constant 5 100 90 80 70 equilibrium concentrations (HA) = 9.87E-02 M (H ) = 1.33E-03 M (A ) = 1.33E-03 M %dissociation = 1.333
+

H+

Aselect the initial concentration of acid

Ka = 1.80E-05

(HA)o = 1.00E-01

Percentage of each chemical species % 98.67 1.33 1.33 1 2 3

HA H+ A
-

2 1.00 0.100 0.0100 Questions to address: 1. How does %dissociation vary with the Ka or the strength of the weak acid? 2. How does %dissociation vary with the concentration of the weak acid?

60 50 40 30 20 10 0

4 0.00100 5 0.000100 6 #####

We can investigate the influence of the Ka and concentration of a weak acid on the amount of dissociation.

HA

H+
acetic acid
pH = 2.88

A-

3. How does the pH vary as the acid gets weaker (smaller Ka)? 4. How would a strong acid behave as its concentration was decreased?

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Effect of adding common ions

What happens to the For 1.00 L HNO2 0.10 M nitrous acid - HNO2 H+ + NO2Pick a common ion 1 (strong acid) add HCl
add sodium nitrite

Ka = 4.60E-04

dissociation of the weak acid when we add a common ion?

100 (HNO 2)
+ (H90 ) (NO 80 2 )

weak acid ion only acid only add common 0.09344 0.09344

with common ion acid added weak only with common ion added HNO2 93.4438 93.4438

0.00656 0.00656 6.55623

0.00656 0.00656

H+

6.55623 6.55623

6.55623 6.55623

NO2-

70 60 50 40 30 20 10

(HCl) 0

%dissociation =

6.56

The percent dissociation for 0.10 M HNO2 is 6.56%. How do you calculate the percent dissociation when a common ion is present? answer answer answer

HNO2

H+

NO2-

When you add the common ion, which way does the reaction shift? When you decrease the common ion, which way does it shift?

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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 when we add a salt (NaCl) that is not a common ion?

Ka = 1.80E-04 For a 0.10M HCOOH (HCOOH) = 9.58E-02 (H ) = 4.15E-03 (HCOO ) = 4.15E-03

+

S=

(NaCl) 0.00

HCOOH 100 H+ 90 HCOO 80 70 60 50 40 30 20 10 0

-

pure waterwith NaCl added pure water with NaCl added 95.8464 9.58E+01 3.745 4.1536 4.15E+00 4.1536 4.15E+00 Based on Enke (2001) Art and Science of Chemical Analysis pKa = pKao - N*0.5091*S^0.5 N = 2 for formic acid 1.80E-04

Increase the ionic strength, S, and observe the Ka and %dissociation. What happens?

%dissociation =

4.15

The percent dissoication in pure water is 4.15%

HCOOH

H+

HCOO-

Ka (pure water) = 1.8 x 10-4

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The effect of temperature

HA select an acid 1 Ka (25 C) = 1.80E-05 pKa (25 C) = For a 0.010 M solution Temperature (oC) Comparison 25 39 (HA) = 9.58E-03 9.59E-03 (H+) = 4.15E-04 4.14E-04 (A ) = 4.15E-04 4.14E-04 %dissociation = 4.154 4.144 type increases or decreases in the yellow boxes type endothermic or exothermic in the yellow boxes
o o

H+

ATemperature (K) 312 Ka = 1.79E-05 pKa = 4.747 +

Is the dissociation reaction endothermic or exothermic?

4.745

weak acid acetic hydrocyanic phenol

As the temperature increases, Ka

Is the dissociation endothermic or exothermic?

If the percent dissociation increases how is the Ka changing? answer

Correct answers will be acknowledged!

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acid 1 2 3 4 5 6 7 chlorous nitrous formic benzoic acetic hypochlorous hydrocyanic

Ka 1.00E-02 4.60E-04 1.80E-04 6.50E-05 1.80E-05 3.00E-08 4.90E-10

formulas HClO2 HNO2 HCOOH C6H5COOH CH3COOH HOCl HCN 1 2 3 acetic hydrocyanic phenol

enthalpy of ionization, kJ/ DHo -0.25 43.5 23.6

using van't Hoff's equatio for different temperature

Ka Source: Wired Chemist http://wulfenite.fandm.edu/Data%20/Table_19a.html All calculations are based on solving the quadratic equation; hence, they are good for dissociations > 5%.

DHo Source: Tinoco, Sauer, and Wang ( Physical Chemistry: Princi in Biological Sciences

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

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