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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:
Recall pH = -log[H+]
{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
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
Page 114
Example: species list
Page 115
Equilibrium Problems (contd)
Page 116
Equilibrium Constraints
Page 117
Example: equilibrium constraints
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
Page 120
Electroneutrality Constraints
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
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
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
Page 145
Example: proton condition
Page 146
When to use the PC?
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
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:
Page 157
pH
0 2 4 6 8 10 12 14
0
6
pC
10
12
14
Open Systems
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