Water Chemistry 3
Controls on Water Chemistry
Chemical Equilibrium Activity Saturation Index
Carbonate Equilibrium and Alkalinity
Recall: LAW OF MASS ACTION indicates that a system strives to equilibrium
A + B ↔ C + D
At equilibrium both reactions happen simultaneously
A + B
A + B
C + D
C + D
A chemical reaction can be written as aA + bB ↔ cC + dD a b c d are molar proportions of compounds A B C D
(i.e. stoichiometric coefficients in a balanced chemical equation)
1
EQUILIBRIUM CONSTANT
K =
[
C ]
c [
D
]
d
[
A
][ a
B
]
b
= constant
[A] [B] [C] [D] represent equilibrium molal or molar concentration
a b c d are molar amounts of compounds A B C D
K is the equilibrium constant (tabulated in aqueous chem books)
If one compound changes concentration others adjust to maintain K
For equilibrium evaluations the [ ] of a pure liquid or solid is defined as 1
Depending on the type of reaction, K may be called acidity or dissociation constant for acid/base reactions complexation constant for complexation reactions solubility product for dissolution reaction adsorption constant for surface reactions
[
C ]
c [
D
]
d
2
ACTIVITY
In concentrated solutions, ions interact electrostatically with each other (surrounded by a cloud of opposite charge) so the stoichiometric coefficients do not reflect reactive availability
Activity coefficients γ adjust molal/molar concentrations M to effective concentrations called activities, a a = γ (M)
Activity is proportional to concentration, and the proportionality constant is the activity coefficient, γ
Activity Coef. depends on temperature, pressure & total composition
In dilute solutions, the dissolved components are spread far apart, so interactions among them are very weak then
γ _{i} ≈ 1, so a _{i} ≈ M _{i}
In concentrated solutions a & M may be far from equal
3
A bit of elaboration on the source of the Güntelberg method
DebyeHückel method (accurate up to I ~ 0.01M)
log
γ
= −
i
Az
i
2
A
=
constant depending on P & T, z
i
=
charge
For higher ionic strengths DebyeHückel developed:
log γ
B = 
on P & T, a 
o 
= 
hydrated 
radius 
of ion 

Typically 
B 
a 
o 
≈ 
1.0 

At 
15 o 
C 
A 
@ 0 
o C 
A 
= 0.49 
and @ 60 
o 
C 
A 
0.54 

, 
= 0.5 
= 
Thus we simplify to: Güntelberg method
0.5(z )
2
I 1/2
log γ 
= − 
i 

1/2 
i 1 + I
Determine the Ionic strength and Ca and HCO _{3} activity for Denver water
Constituent 
Conc. (mg/L) 
Conc. (mol/L) 

TDS 
179 
 

Ca ^{+}^{2} 
42 
1.05 
x 10 ^{}^{3} 

HCO _{3} 
 
115 
1.89 
x 10 ^{}^{3} 
pH = 7.9, Temp = 20°C 
Determine the ionic strength in solution based on TDS Determine activity coefficients for HCO _{3} ^{} using Güntelberg method Determine activity coefficients for _{C}_{a} ^{+}^{2} _{u}_{s}_{i}_{n}_{g} Güntelberg method
4
CHEMICAL EQUILIBRIUM
• Thermodynamics vs. Kinetics Thermodynamics tells us where the system should go at equilibrium, and kinetics tells us how fast.
• Definition of Equilibrium 1) A system at equilibrium has none of its properties changing with time, no matter how long it is observed 2) A system at equilibrium will return to that state after being disturbed 3) Thermodynamically speaking, a system is at equilibrium when Δ _{r} G (the change in Gibbs Free Energy) = 0
Gibbs Free Energy is a thermodynamic quantity which can be used to determine if a reaction is spontaneous or not. Gibbs free energy is G = H(enthalpy)  T(temp) * S(entropy)
Enthalpy (useful work you can get from a closed system) InternalE+SurroundingP*Volume Entropy (a quantitative measure of a system’s disorder) when ice melts entropy increases
CHEMICAL EQUILIBRIUM
A and B react to produce C and D (a,b,c,d are number of moles) aA + bB = cC + dD
Reactants
Products
The Gibbs free energy change of reaction is calculated:
Δ G
r
=
∑
Δ G
f
products
−
∑
Δ G
f
reactants
Multiply Gibbs free energies of formation (Δ f G) by stoichiometric coefficients and subtract sum of reactants from sum of products
Δ _{r} G = cΔ _{f} G _{C} + dΔ _{f} G _{D}  aΔ _{f} G _{A}  bΔ _{f} G _{B}
If Δ _{r} G = 0, the reaction is at equilibrium if Δ _{r} G < 0, the reaction will proceed to the right if Δ _{r} G > 0, the reaction will proceed to the left
Gibb’s free energies of formation are determined by experiment
For Some Gibb ’s Free Energy Values
http://inside.mines.edu/~epoeter/_GW\19WaterChem3/GibbsFreeEnergyValues.xls
5
[
C ]
c [
D
]
d
How much of a substance will dissolve in water?
SOLUBILITY PRODUCT
Suppose we have the dissolution reaction for anhydrite:
CaSO _{4} (s) ↔ Ca ^{2}^{+} + SO _{4} ^{2}^{} in this case K equilibrium constant is a solubility product (K _{S}_{P} )
K
= K
a
a
Ca 
2 + 
SO 
2 − 
4 
sp 
= 
= a 
Ca 
2 + 
a 
SO 
2 − 

a 
4 
CaSO (s)
4
activity of most pure solids can be taken equal to unity (so a _{C}_{a}_{S}_{O} _{4} _{(}_{s}_{)} = 1)
Calculate K _{S}_{P} by finding the Gibbs free energy change of reaction:
^{Δ} r ^{G}^{°} ^{=} ^{Δ} f ^{G}^{°} Ca 2+ ^{+} ^{Δ} f ^{G}^{°} SO _{4} 2 ^{} ^{Δ} f ^{G}^{°} CaSO _{4} (s)
and calculating
− Δ G
o
2.303RT
logK
SP
=
r
6
SOLUBILITY PRODUCT
Calculate the solubility product of anhydrite at 25°C CaSO _{4} (s) ↔ Ca ^{2}^{+} + SO _{4} ^{2}^{}
Look up:
http://inside.mines.edu/~epoeter/_GW\19WaterChem3/GibbsFreeEnergyValues.xls
Δ _{f} G° _{C}_{a} _{2}_{+} = 553.6 kJ mol ^{}^{1}
Δ _{f} G° _{S}_{O} _{4} _{2}_{} = 744.0 kJ mol ^{}^{1}
Δ _{f} G° _{C}_{a}_{S}_{O} _{4} _{(}_{s}_{)} = 1321.8 kJ mol ^{}^{1}
R (gas constant) = 8.314 J K ^{}^{1} mol ^{}^{1}
so:
Δ _{r} G° = 553.6 + (744.0)  (1321.8) = 24.2 kJ mol ^{}^{1}
− Δ G
o
− 24,200 J mol
− 1
logK 
= = 
= − 4.24 

SP 
− 
1 
− 
1 
r
2.303RT
2.303 (8.314 J K
mol
) (298.15 K)
assume Kelvin for thermodynamic expressions, unless noted otherwise
7
Will a substance dissolve or precipitate?
THE SATURATION INDEX
The saturation index (SI) is defined as:
SI
⎛ IAP ⎞
⎟ ⎟
= log ⎜
CaSO _{4} (s) ↔ Ca ^{2}^{+} + SO _{4} ^{2}^{}
CaSO (s) ↔ Ca
2+
+ SO
4
2
4
IAP = K _{S}_{P} SI = 0 (0.2 < SI < 0.2) water is saturated with the mineral IAP < K _{S}_{P} SI < 0 water is undersaturated with the mineral Reaction is proceeding from left to right (dissolution) IAP > K _{S}_{P} SI > 0 water is supersaturated with the mineral Reaction is proceeding from right to left (precipitation)
Suppose a groundwater analysis indicates
_{5}_{x}_{1}_{0} ^{}^{2} mol/L Ca ^{2}^{+} and 7x10 ^{}^{3} mol/L SO _{4} ^{2}^{} (ignore activity coefficients)
Is this water saturated with respect to anhydrite?
⎝ ⎜
K SP
⎠
Consider the acidbase reaction
H _{2} CO _{3} ↔ HCO _{3} ^{} + H ^{+}
_{K} _{=} _{1}_{0} 6.35
Which way should the reaction go if
pH = 7
a _{H} _{2} _{C}_{O} _{3} = 10 ^{}^{4}
a _{H}_{C}_{O} _{3} _{} = 10 ^{}^{3} ?
First, calculate the IAP
Recall
pH = log a _{H} _{+}
so
a _{H} _{+} = 10 ^{}^{7}
IAP =
a 
HCO 
− 3 
a H 
+ 
= 
( 10 − 
3 )( 10 
− 
7 
) 

a 
( 10 − 4 
) 

H CO 2 3 
= 10
− 6
IAP > K (10 ^{}^{6} > 10 ^{}^{6}^{.}^{3}^{5} )
The reaction will shift to the left until IAP = K
so more H _{2} CO _{3} will be formed
8
CARBONATE EQUILIBRIUM
Most important acidbase system in water, controls the pH of most waters
Water exposed to the atmosphere dissolves carbon dioxide CO _{2} (g) creating carbonic acid H _{2} CO _{3}
CO _{2} (g) + H _{2} 0 CO _{2} (aq) CO _{2} (aq) + H _{2} 0 ⇔ H _{2} CO _{3}
Gas dissolution Carbonic acid formation
Carbonic acid dissociates in two steps 1) Carbonic acid donates one proton (H ^{+} ) to create bicarbonate HCO _{3} H _{2} CO _{3} ⇔ H ^{+} + HCO _{3} 2) Bicarbonate donates a proton (H ^{+} ) to form carbonate CO _{3} ^{2}^{} HCO _{3} ^{} ⇔ H ^{+} + CO _{3} ^{2}^{}

Reaction
Equilibrium constant (25 ^{o} C)
CO _{2} (aq) + H _{2} 0 ⇔ H _{2} CO _{3}
pK _{H} = 1.46
H _{2} CO _{3} ⇔ H ^{+} + HCO _{3}

pK _{1} = 6.35
HCO _{3} ^{} ⇔ H ^{+} + CO _{3} ^{2}^{}
pK _{2} = 10.33

9
pH < ~4.5 all HCO
_{3} ^{} is gone
pH
pH < ~8.3 all CO
2
3
is gone
In most natural waters, bicarbonate is the dominant carbonate species
CARBONATE SYSTEM
In aqueous solutions, positive & negative charges must balance At pH=7, [H ^{+} ] = [OH ^{} ] At pH>7, [H ^{+} ] < [OH ^{} ]
For a pure CO _{2}  H _{2} O system,
possible species are
_{H} +
_{O}_{H}  _{H} _{2} _{C}_{O} _{3}
_{H}_{C}_{O} _{3} 
_{C}_{O} _{3} 2
the chargebalance equation is:
[H ^{+} ] = [HCO _{3} ^{} ] + 2[CO _{3} ^{2}^{} ] + [OH ^{} ]
Each mole of CO _{3} ^{2}^{} provides two equivalents of negative charge in solution, so carbonate concentration must be multiplied by 2
10
CARBONATE SYSTEM
If we increase partial pressure of CO _{2}
[H ^{+} ] = [HCO _{3} ^{} ] + 2[CO _{3} ^{2}^{} ] + [OH ^{} ]
pH decreases (due to increased H ^{+} activity in solution) What is partial pressure? Air is a mixture of gases Each gas exerts a pressure depending on its proportion This is the partial pressure of that gas Air pressure is the sum of all these partial pressures
If we add sodium to the system, the chargebalance equation is:
[H ^{+} ] + [Na ^{+} ] = [HCO _{3} ^{} ] + 2[CO _{3} ^{2}^{} ] + [OH ^{} ] Then, if we add a strong acid. What would change? The concentration of H ^{+} , OH ^{} , and all the carbonate species would change, but the concentration of Na ^{+} would not change. Thus, Na ^{+} is a conservative ion, and HCO ^{} , CO ^{2}^{} , H ^{+} and OH ^{} are nonconservative and this concept is the basis for the defintion of alkalinity
3
3
ALKALINITY
For all dissolved species, the charge balance equation can be extended:
2[ Ca ^{+}^{2} ] + 2[ Mg ^{+}^{2} ] + [ K ^{+} ] + [ Na ^{+} ] + [ H ^{+} ] + •••••
= [ Cl ^{} ] + 2[ SO _{4} ^{}^{2} ] + [ NO _{3} ^{} ] + [ HCO _{3} ^{} ] + 2[ CO _{3} ^{2}^{} ] + [ OH ^{} ] + ••••
Put conservative ions on left & nonconservative ions on right
In equivalents:
Σ conservative cations  Σ conservative anions
If the lefthand side of the equation is conservative, then the righthand side of the equation must also be conservative
Although none of the individual species on the right is conservative, their mathematical combination as shown is conservative
Therefore, the quantity on the righthand side of the equation is a special combination, and we call this quantity the total alkalinity.
11
Titration for Carbonate System Compents
Add strong acid e.g. 0.0200N H _{2} SO _{4}
For a sample starting at pH ~9.9
Acid Added
pH decreasing Determine the volume of acid solution required to reach the 8.3 and 4.5 endpoints
12
ALKALINITY
Alkalinity is normally reported by the laboratory in units of mg/L as CaCO _{3} (calcium carbonate) Alkalinity (eq/L) = Alkalinity (mg/L as CaCO _{3} ) x 2 eq/mole This does not mean that CaCO _{3} is necessarily present in the
solution. What it means is that the solution has numerically the same alkalinity as a solution in which the same weight of CaCO _{3} per liter has been dissolved.
Calculation of alkalinity from a titration to a pH of 4.5:
mL sample
The equivalent weight of CaCO _{3} :
molar mass of CaCO _{3}
mole
2 eq
eq
recall that an equivalent is essentially a mole of charge
* CaCO _{3} does not carry a charge, but we calculate equivalent weight of a salt as
its molecular weight divided by the valence of the metal ion in the compound
Alk
T
=
mL acid
×
N
acid
×
eq. wt.CaCO
3
100g
×
1mole
= 50
g
ALKALINITY
A 100 mL sample with a pH of 8 is titrated to the methyl orangeendpoint (which goes from yellow at pH 4.4 to red at pH 3.1) with 2 mL of 0.5 N H _{2} SO _{4}
What is the total alkalinity in mg L ^{}^{1} as CaCO _{3} and what is the concentration of HCO _{3} ^{} in mg L ^{}^{1} ?
The total alkalinity in mg L ^{}^{1} as CaCO _{3} is given by:
100 mL = 500 mg/L as CaCO
3
The concentration of HCO _{3} ^{} is given as:
HCO (mg/L) =

3
= 610 mg/L
100 mL
Alk
T
=
2 mL
×
0.5 eq/L
×
50 g/eq
×
(1000 mg/g)
2 mL
×
0.5 eq/L
×
61g/eq
×
(1000 mg/g)
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