Unit 3.

Acids and bases

Class notes

1. Species lists
2. Solving chemical equilibrium problems
3. Ionization functions
Acid rain

https://www.cbc.ca/player/play/1890980289
Examples of acid and bases in natural waters
• Most important base: HCO3-
• Other bases: PO43-, NH3, AsO43-, SO42-, CO32-, etc.

• Most important acid: CO2(aq) or H2CO3

• Other acids: H4SiO4, NH4+, H2SO4, CH3COOH
(acetic), H2C2O4 (oxalic), etc.
Major ions in natural waters

4
Recap: Are the following acids or bases
• H2S

• NH3

• CO32-

• HPO42-
Example: Species lists
What species would be in solution at equilibrium in a 1:100 dilution of
vinegar. Vinegar is 0.7 M acetic acid (CH3COOH) solution.
Example 1: Solving chemical equilibrium problems
Calculate species concentrations and pH at equilibrium in a 1:100 dilution
of vinegar.

Vinegar is 0.7 M acetic acid (CH3COOH) solution

Given:
CH3COOH = CH3COO- + H+ pKa = 4.75
Chemical equilibrium problems
Step 1: Define the chemical system
– Open or closed model

Step 2: Generate a species list

– n unknowns (equilibrium concentrations for n species)
– always include H2O, H+ and OH- (for aqueous systems)
– look for H+ transfer
– look for formation of simple ions
– draw a species diagram
Chemical equilibrium problems
Step 3: Define constraints on species concentrations –
equations to solve
– Create list of n equations
– Equilibrium constraints
• Always include self ionization of water H2O = H+ + OH-
– Mass balance constraints
• Identify elements, oxidation states, fragments (CH3COO) to serve as the base of
mass balances
– Charge balance or proton balance
– Other constraints
• Activity of pure liquid = 1
• Activity of solid (if exists)= 1
• Activity of solid ( if completely dissolved) = 0
Method of approximation
• Reduce number of unknowns by making assumptions

• Apply approximation only to equations where species are added (ie.,

mass balance and charge balance, NOT equilibrium expressions)

• Good first approximation is to guess if the system will be basic or acidic

– Acidic: [H+] >> [OH-] and therefore [OH-]  0
– Basic: [H+] << [OH-] and therefore [H+]  0
Example 2: Solving chemical equilibrium problems

Write a species list for the addition of ammonium chloride (NH4Cl (s)) to
water in a closed system.

Note that NH4Cl is highly soluble and therefore will all dissolve in solution

What equations you would use to find the concentrations of species in this
system?
Example 3: solving chemical equilibrium problems
– conjugate base
What is the pH and species concentrations when 7 mmoles sodium acetate
(CH3COONa) completely dissolves in 1 L of water?
Ionization functions
• Functions of pH and Ka that describe the fractional contribution of each
species to the total concentration

• For a monoprotic acid: HA = H+ + A-

0 =
H 
+

[ HA] =  0 AT ( K a + [ H + ]) Same for all

monoprotic acids
[ A− ] = 1 AT Ka
1 =
( K a + [ H + ])
where, 0 + 1 = 1
 Ionization fractions:  values
Monoprotic [HA]T = 10-3, pKa = 6.7

1.0
0.9
H+
0 =
0.8

( K a + [ H + ]) 0.7
0.6 alpha o

alpha
Ka
1 =
0.5 alpha 1

( K a + [ H + ]) 0.4
0.3
0.2
0.1
0.0
0 2 4 6 8 10 12 14
pH
 Ionization fractions:  values
Monoprotic [HA]T = 10-3, pKa = 3.7

1.0
0.9
0.8
0.7

alpha 0.6 alpha o

0.5 alpha 1
0.4
0.3
0.2
[H+] [OH-]
0.1
[HA] [A- ]
0.0
0 2 4 6 8 10 12 14
2 4 6 8 10 12 14 pH
pH
 Ionization functions and  values
Diprotic acid (H2A)

[ H 2 A] =  0 AT [ HA− ] = 1 AT [ A2− ] =  2 AT

[ H + ]2
0 = + 2
[ H ] + K A1[ H + ] + K A1K A2
+ Same for all diprotic acids
K A1[ H ]
1 = + 2
[ H ] + K A1[ H + ] + K A1K A2

K A1K A2
2 = + 2
[ H ] + K A1[ H + ] + K A1K A2 0 + 1 + 2 = 1
21
Ionization fractions:  values
Diprotic [H2A]T = 10-3.52, pKa1 = 6.35, pKa1 = 10.33

1.0

0.8

0.6 alpha o
alpha 1
alpha

0.4 alpha 2

0.2

0.0
0 2 4 6 8 10 12 14

pH
 Ionization fractions:  values
Diprotic [H2A]T = 10-3.52 Diprotic [H2A]T = 10-3.52
pKa1 = 6.35, pKa1 = 10.33 pKa1 = 4.35, pKa1 = 10.33

1.0

0.8

0.6 alpha o
alpha 1
alpha

0.4 alpha 2

0.2

0.0
0 2 4 6 8 10 12 14

pH
  values of n-protic acids
For species Hn-iAi-:
i
+ n −i
[H ] K ak
i = k =1
n
 + j −i j 
  [ H ]  K ak 
j =0  k =1 


i =0
i =1