Dissociation and pH

Dissociation of weak acids/bases

controlled by pH
Knowing the total amount of S and
pH, we can calculate activities of all
species and generate curves
Example: H2S

Hydrogen Sulfide Activity Diagram

Hydrogen Sulfide Activity Diagram

Solubility of Quartz
The oxides of many metals react
with H2O to form bases
SiO2(s) + 2H2O H4SiO4

Quartz Activity Diagram

When including a solid, the activity
diagram looks a little different
Showing fields of stability for each
species

Note: we dont need to define initial

log[SiO2] concentration
Activity of solid = 1

Quartz Activity Diagram

log a SiO2(aq)
3

H2SiO4

--

H3SiO4

SiO2(aq)

H4SiO4

2
4
6

25C

pH
10
12
Walt T ue Feb 14 2006

----

Diagram SiO 2(aq), T = 25 C , P = 1.013 bars, a [H 2O] = 1; Suppressed: H 4(H 2SiO 4) 4

Quartz

14
7

Buffering of pH
Weak acids and bases can buffer pH of a
solution
pH changes very little as acid (or base) is
added
Need both a protonated and unprotonated
species present in significant concentrations
e.g., H2CO3(aq) and HCO3 Carbonic acid-bicarbonate is the major buffer in
most natural waters
Organic acids and sometimes silicic acid can be
important buffers
8

pH Buffering capacity of an aquifer:

Minerals as well as aqueous species
Reactions with minerals: carbonate
most important, fastest
CaCO3 + H+ Ca2+ + HCO3-

Silicates, slower, less important

2KAlSi3O8 + 2H2CO3 + 9H2O
Al2Si2O5(OH)4 + 2K+ + 4H4SiO4 + 2HCO3 H2CO3 consumes acid, HCO3- creates alkalinity

Ion exchange of charge surfaces

Negatively charged S- + H+ SH
9

Dissolved Inorganic Carbon

(DIC)
Initially, DIC in groundwater comes from CO 2
CO2

(g)

+ H2O H2CO3

Equilibrium expression with a gas is known as

Henrys Law

PCO2: partial pressure (in atm or bar); pressure in

atmosphere exerted by CO2
Assuming atmospheric pressure of 1 atm, PCO2 =
10-3.5; concentration of CO2 = 350 ppm
At atm = 1, N2 is 78%, PN2 = 0.78, O2 21%, PO2 = 0.21
10

Dissolved Inorganic Carbon

(DIC)
PCO2 of soil gas can be 10-100 times the
PCO2 of atmosphere
PCO2 for surface water controlled by
atmosphere and biological processes
Photosynthesis (day): drives PCO2 down,
less H2CO3, pH increases
6CO2 + 6H2O + Energy C6H12O6 + 6O2

Respiration: increases PCO2, more H2CO3,

pH drops
11

Dissolved Inorganic Carbon

(DIC)
In groundwater, no photosynthesis, no
diurnal variations
CO2 usually increases along a flow path
due to biodegradation in a closed system
CH2O + O2 CO2 + H2O
CH2O = generic organic matter

12

DIC and pH in Open System

CO2 can be dissolved into or volatilize
out of water freely
Surface waters

PCO2 is constant = 10-3.5 atm at

Earths surface

13

DIC and pH in Open System

What is the pH of natural rainwater?
Controlled by DIC equilibrium

At 25C, KCO2 = 10-1.47

14

DIC and pH in Closed

System
In a closed system (no CO2 exchange),
for a given amount of TIC, speciation is
a function of pH
CO2 + H2O H2CO3 HCO3- + H+
CO32- + H+
At pH = 6.35, [H2CO3] = [HCO3-]
At pH = 10.33, [HCO3-] = [CO32-]

We can do same calculations we did for

H2S
15

Total DIC = 10-1 M

0

CO2 (aq)

--

HCO3

CO3

pH = 10.33

pH = 6.35

Species with HCO (log molal)

Common pH range
in natural waters

10

12

14

16
2

10

11

12

pH
Walt Tue Feb 21 2006

16

Rainwater pH and PCO2

What if we double PCO2 (10-1.75 atm)
[H2CO3] = [10-1.47] [10-1.75] = 10-3.22

Doubling the PCO2 does not have a large

effect on pH
Acid rain can have pH < 4
Due to other acids (nitric and sulfuric) that are
injected into the atmosphere by vehicles and
smokestacks

17

Special points about DIC, pH, and

other weak acids
At pH 6.35, Ka1 = [H+], therefore
[H2CO3] = [HCO3-]

Likewise, at pH 10.33, Ka2 = [H+],

therefore [HCO3-] = [CO32-]
18

Special points about DIC, pH, and

other weak acids
When pH = pKa, concentration of
protonated in reactant = deprotonated
in product
pKa = -log Ka
for H2CO3 HCO3- + H+, Ka = 10-6.35, pKa =
6.35
so for H4SiO4 H3SiO4- + H+, pKa = 9.71
And for H3SiO4- H+ + H2SiO42-, pKa =
13.28
19

Alkalinity
Alkalinity = acid neutralizing
capability (ANC) of water
Total effect of all bases in solution
Typically assumed to be directly
correlated to HCO3- concentration in
groundwater

20

Alkalinity
Total alkalinity = [HCO3-] + 2[CO32-] + [B(OH) 4-]
+ [H3SiO4-] + [HS-] + [OH-] [H+]
Typically in groundwater, [HCO3-] >> [CO32-], [B(OH)
+
4 ], [H3SiO4 ], [HS ], [OH ], [H ]
Whenever there are significant amounts of any of
these other species, they must be considered

Carbonate alkalinity = [HCO3-] + 2[CO32-] + [OH-]

[H+]
Directly convertible to [HCO3-] when it is >> than
others

Measured by titration of solution with strong acid

21

Total DIC = 10-1 M

0

CO2 (aq)

--

HCO3

CO3

Species with HCO (log molal)

10

12

14

16
2

10

11

12

pH
Walt Tue Feb 21 2006

22

Alkalinity Titration
Determine end-point pH:
The pH at which the rate of change of pH
per added volume of acid is at a maximum
Typically in the range 4.3-4.9
Function of ionic strength
Reported as mg/L CaCO3

HCO3- = alkalinity
0.82
23

Determining Alkalinity by Titration

Initial
pH = 8.26

Rapid
pH change

Rapid
pH change
Slow pH change:
Buffered

Determine maximum pH change by: pH mL acid added

24