Chapter 2:

Chemical Equilibrium,
Acid-Base Chemistry and
the Carbonate System

Page 102
Chemical Equilibrium
Equilibrium: forward and reverse reactions
occur at same rate
A general equilibrium reaction is written as:

where k is the equilibrium constant

k is dependent on system temperature and

pressure

Winter 2015 CIV ENG 3L03 Page 103

Solubility Product
All compounds are soluble in water to some
degree
If you place a solid in water, at some point in
time no more of the compound will dissolve
The equilibrium constant that involves a
precipitate and aqueous concentration of its
constituent ions

Winter 2015 CIV ENG 3L03 Page 104

Case Study
Flow capacity of reinforced concrete
pipes conveying water from Hetchy
reservoir to San Francisco decreased
over time
Serious pitting (increasing /D)
alkalinity and hardness too low CaCO3
leached from pipe to water to satisfy
equilibrium i.e. .

Solution: add lime (Ca(OH2)) Page 105

Example:
A metal plating plant must precipitate
Zn2+ prior to discharging to a stream.
Regulations state Zn2+ < 30 g/L in
unfiltered samples. Caustic soda (NaOH)
is added to precipitate Zn(OH)2.

Winter 2015 CIV ENG 3L03 Page 106

Solution

Winter 2015 CIV ENG 3L03 Page 107

Ion Product of Water

Recall pH = -log[H+]

Winter 2015 CIV ENG 3L03 Page 108

Equilibrium (contd)

{H2O} = 1 (kw)
{solid} = 1 (ksp )
{gas} = Pgas

Tips:
weak acid: Ka < 1
dilute solution 10-3 M

Page 109
Equilibrium Constants for Acid-
Base Reactions

From: Snoeyink & Jenkins (1980)

Page 110
 Setting up Chemical Equilibrium
Problems
1. Define chemical system

Page 111
Equilibrium Problems (contd)
2. Enumerate chemical species
identify the recipe or starting materials
convention: always include water
identify dissociation products (hydrolysis)
look for formation of simple ions (see table p. 113)
look for H+ transfer
always include H+, OH- and H2O in the species list
no mixing valence states!!
enumerate subsequent hydrolysis products
enumerate other reaction products
when is the list complete?

Page 112
Simple Ions
(dissociation products)
Ion Type Examples
Cations
monoatomic H+ K+ Na+ Ca2+ Mg2+
polyatomic NH4+
Anions
monoatomic Cl- Br- S2-
polyatomic OH- SO42- CO32- HCO3-
NO3-, PO43-
Page 113
Example: dissociation

What are the initial dissociation products

for the dissolution of Fe(NH4)2(SO4)2,
K2Cr2O7 and ClO2 in water?

Page 114
Example: species list

Addition of 1x10-3 moles of ammonium

chloride to 1 L of water in a closed
system.

Page 115
 Equilibrium Problems (contd)

3. Define Constraints on Species

Concentrations
species list mathematical system with
n unknowns
need n equations.based on
equilibrium expressions
mass balances
electroneutrality
constraints based on standard state of mixtures
non-negative concentrations

Page 116
Equilibrium Constraints

Self ionization of water

Equilibria expressions should be
populated solely by the species in the
list
Equilibria expressions MUST be
linearly independent (i.e., cannot
reverse, add or multiply stoichiometric
coefficients by a constant)

Page 117
Example: equilibrium constraints

Develop the equilibrium expressions for

the ammonium chloride example on p.
94.

Page 118
 Mass Balance Constraints
Balance each element in species list
ignore H and O
write different mass balance for each oxidation state
1. Determine system components (any element,
oxidation state or non-dissociating fragment of
starting material about which mass balance is
written)
2. List total concentration of each component (from
starting material or measurement)
3. All species in list must be associated with at least
one mass balance
except those containing only H & O

Page 119
Example:
mass balance constraints

Develop the mass balance expressions

for the ammonium chloride example on
p. 94.

Page 120
Electroneutrality Constraints

Sum of positive charges = sum of

negative charges (eq/L)
Each chemical system has ONE charge
balance equation only
Neutral species do not appear in the
charge balance equation
Do not leave H+ and OH- out of this
constraint!!
Page 121
Example:
electroneutrality constraints
Develop the electroneutrality expression
for the ammonium chloride example on
p. 94.

Page 122
Other Constraints
activity of H2O = 1
salts containing Na+, K+ and NH4+
dissolve completely
compound in which transferable H+ is
replaced by another cation
concentration of solid salt = 0
activity of solids = 1

Page 123
Example: other constraints

Determine the other constraints for the

ammonium chloride example on p. 94.

Page 124
Example:
setting up an equilibrium problem
Set up the chemical system for zinc
acetate in water. (to explore the
speciation of Zn in a zinc acetate
supplement).

Page 125
Graphical Solutions to Chemical
Equilibrium Problems
Graphs provide fast information
beyond equilibrium conditions (< 10
species); aid in visualizing the system
Hand algebraic solutions require many
simplifying assumptions which arent
always easy to see
These days computers facilitate
algebraic solutions; however these
solutions dont improve intuition
through visualization Page 126
A Few Important Concepts
Master Variable
concentrations of controling species
pH (acid-base chemistry)
pe (redox chemistry)
Acid-Base Chemistry
acid & conjugate base
monoprotic, diprotic etc...
pC-pH (instead of log(concentration))

Page 127
Plotting Species Concentrations
Example system: 1:100 dilution of vinegar
(0.7 M acetic acid solution CH3COOH)
acetic acid

Define System:
closed
no solids
7 x 10-3 M CH3COOH

Page 128
Plotting Species Concentrations
(contd)
Generate Species List:
CH3COOH H2O

CH3COO- H+ OH-

Define Constraints:
Equilibrium:

Page 129
Plotting Species Concentrations
(contd)
Define Constraints (contd):
Mass Balance:

Electroneutrality:

Other:

Page 130
pH and pOH pH
0 2 4 6 8 10 12 14
0

6
pC

10

12

14
Plotting Conjugate Base Species

Plot all species as a function of {H+}:

pXi=fi(pH)
Consider Ac- addition first:

Page 132
Ac-: The high pH range pH
0 2 4pKa 6 8 10 12 14
0

pCT2

4
[OH-]
6
pC

10
[H+]
12

14
Ac-: The low pH range pH
0 2 4pKa 6 8 10 12 14
0

pCT2

4
[OH-]
6
pC

10
[H+]
12

14
Ac-: When pKa = pH pH
0 2 4pKa 6 8 10 12 14
0

pCT2

4
[OH-]
6
pC

10
[H+]
12

14
Plotting Acid Species
Plot as a function of {H+}: pXi=fi(pH)
Consider HAc:

Page 136
HAc: The high pH range pH
0 2 4pKa 6 8 10 12 14
0

pCT2

4
[OH-]
[Ac-]
6
pC

10
[H+]
12

14
HAc: The low pH range pH
0 2 4pKa 6 8 10 12 14
0

pCT2

4
[OH-]
[Ac-]
6
pC

10
[H+]
12

14
Equilibrium &
Interpretation
pH
0 2 4pKa 6 8 10 12 14
0

pCT2
system
point 4
[OH-]
[Ac-]
6
pC

10
[H+]
12

14
Example: graphical solution for
chemical equilibrium
Use a pC-pH diagram to find the
equilibrium pH of 1L of pure water to
which 1 x 10-3 moles of ammonia have
been added

Page 140
 pH
0 2 4 6 8 10 12 14
0

6
pC

10

12

14
Example: ambiguous graphical
solution
Use graphical methods to find the
equilibrium pH of a 0.007 M solution of
sodium acetate.

Page 142
 pH
0 2 4 6 8 10 12 14
0

6
pC

10

12

14
Proton Condition
A mass balance on protons
Species added, including H2O, define the
proton reference level (PRL)
PC = proton balance equation (PBE), which
includes all species except those in the PRL
Use either the PC or the EN equation NOT
both (they are not linearly independent)

Page 144
Example: proton condition

Add 10-5 M [H2CO3*] to water; define the

PC.

Page 145
Example: proton condition

Add 10-5 M Na2CO3 to water; define the

PC.

Page 146
When to use the PC?

PC, EN and mass balance equations

not linearly independent
PC will always give an acceptable
solution
PC particularly useful with salt as a
starting material
PC & EN identical when starting
material is not a salt
Page 147
Carbonate System (contd)
Open System
solid carbonate present
no solid carbonate present
Closed System
solid carbonate present
no solid carbonate present
Carbonate system defined by any two
of: CT,CO , pH, Alk
3

most important natural systems

Page 148
When all else fails. pH
0 2 4 6 8 10 12 14
0

6
pC

10

12

14
Chemical Equilibrium - Open
Systems
What happens in open systems?
To examine this, we will add two
additional concepts:
hydration of CO2(aq)
diprotic acids

Page 150
Carbonate System
Most important acid-base system
controls pH of most natural systems
Components
Gas CO2 (g)
Liquid H2CO3*; HCO3-; CO32-
Solid CaCO3
Concepts revisited:
alkalinity (bases acids) & acidity
hardness
buffering capacity
Page 151
CO2(aq)
CO2 is in the atmosphere
78% N2
21% O2
0.968 others
0.032 CO2

CO2 (g) transfers into solution:

in the earths atmosphere.

CO2 (g) = 10-3.5 atm
beneath a landfill.
CO2 (g) = 0.5 atm Page 152
Hydration of CO2

For convenience.
[CO2(aq)] + [H2CO3] = [H2CO3*]

Page 153
Diprotic Acids
An acid which has two protons
available to donate (e.g., H2CO3, H2SO4)
Could derive graphical equilibrium
solution similar to our method for
monoprotic acids
Use a simple plotting procedure based
on the above-mentioned derivation
employing:
equilibrium equations
mass balance equations
Page 154
Steps to plotting diprotic acids
1. Plot H+ & OH-
2. Plot both system points:
pC & pKa,1
pC & pKa,2
3. Plot species
H2A
pH<pKA,1: H2A = pCT,A
pKA,1<pH<pKA,2: 1:1 slope
pH>pKA,2: 2:1 slope

Page 155
Steps to plotting diprotic acids
(contd)
HA-
pH<pKA,1: 1:1 slope
pKA,1<pH<pKA,2: HA- = pCT,A
pH>pKA,2: 1:1 slope
A2-
pH<pKA,1: 2:1 slope
pKA,1<pH<pKA,2: 1:1 slope
pH>pKA,2: A2- = pCT,A
when pH = pKA,1 or pH = pKA,2
pC = pCT + 0.3, OR
pC = pKA,1 + 0.3
Page 156
 Example:

Plot the equilibrium diagram for a closed

carbonate system with CT,A = 10-2.2M.
Find equilibrium points for:
1) H2CO3 addition
2) MHCO3 addition
3) M2CO3 addition

Page 157
 pH
0 2 4 6 8 10 12 14
0

6
pC

10

12

14
Open Systems

Open to atmosphere with a constant

CO2 (g) partial pressure
Produces a constant [CO2 (aq)]
([H2CO3*])
Consider standard atmosphere

Page 159
 pH
plot p[H2CO3*] 0 2 4 6 8 10 12 14
0

6
pC

10

12 [H+]
[OH-]

14
plot p[HCO3 -]
pH
0 2 4 6 8 10 12 14
0

4
[H2CO3*]

6
pC

10

12 [H+]
[OH-]

14
plot p[CO3 2-]
pH
0 2 4 6 8 10 12 14
0
[HCO3-]
2

4
[H2CO3*]

6
pC

10

12 [H+]
[OH-]

14
Carbonate System open pH
to Atmosphere 0 0 2 4 6 8 10 12 14

[HCO3-]
2

4
[CTA] [H2CO3*]

6
pC

10

12 [H+]
[OH-]
[CO32-]
14