Electrolyte Conductivity and Solubility Equilibrium

M.HEG.03.
1 Inorganic Hydrogeochemistry 2012/13

Topic 3
Electrolytes, Activities, Ionic strength
Solubility Equilibrium K
sp
WS 2012/13
The soft water beats the hard rock
M.HEG.03.1 Inorganic Hydrogeochemistry 2012/13
3-2
Electrolyte
AC A + C
- +
Dissociation
Isolators: amber,
paraffin, porcelain,
PVC
Glass
Pure Water
Semiconductors
Electrolytes:
solutions and melts
of ionic compounds
Graphite Metals at
room
temperature
Metals close to
critical
temperature
Specific conductivity[1/Ohm*cm]
Super
conduction
Strong Electrolytes dissociate completely in water
Weak Electrolytes dissociate incompletely in water
Degree of dissociation:
3-3
HCl
Konzentration in % w/w
0
400
30

i
n

m
S
/
c
m
HCl
NaOH
0
400
30

i
n

m
S
/
c
m
HCl
NaOH
0
400
30

i
n

m
S
/
c
m
HCl
NaOH
0
400
30

i
n

m
S
/
c
m
HCl
NaOH
0
400
30

i
n

m
S
/
c
m
Concentration in % w/w
Concentration, Conductivity
Strong or weak?
?
III-4
Electrical Conductivity is a Sum Parameter for ions in (aqueous) solution
Electrical Conductivity is a Sum Parameter for ions in (aqueous) solution
depends on:
Concentration (Activity!)
Temperature
Ion Mobility
Type of Electrolyte
depends on:
Concentration (Activity!)
Temperature
Ion Mobility
Type of Electrolyte
Isolators: amber,
paraffin, porcelain,
PVC
Glass
Pure Water
Semiconductors
Electrolytes:
solutions and melts
of ionic compounds
Graphite Metals at
room
temperature
Metals close to
critical
temperature
Superconduction
Specific conductivity[1/Ohm*cm]
3-5
Mobility of Protons
+
-
+
-
Mobility of Ions
O
H
H H
O
H
H H
O
H
H
O
H
H
+
O
H
H H
O
H
H H
O
H
H
O
H
H
+
O
H
H H
O
H
H H
O
H
H
O
H
H
+
O
H
H H
O
H
H H
O
H
H
O
H
H
+
O
H
H H
O
H
H H
O
H
H
O
H
H
+
O
H
H H
O
H
H H
O
H
H
O
H
H
+
O
H
H H
O
H
H H
O
H
H
O
H
H
+
Ion
Cloud
-
-
-
-
-
-
-
-
-
-
-
+
Mechanisms of Ion Mobility
3-6
Limiting molar conductivity
0
/[cm
2
/
1
mol
-1
], ion mobility u
0
/[cm
2
V
-1
s
-1
], effective ion
radius (derived from mobility) r
eff
/[pm = 10
-12
m] and crystallographic ion radius
r
ion
/[pm] of various cations and anions.
Ion mobility
3-7
~ T
Empirical determination (polynomial fit)
depends on :
Temperature Range
Concentration
Type of Electrolyte
~ T
Empirical determination (polynomial fit)
depends on :
Temperature Range
Concentration
Type of Electrolyte
Rule of Thumb
For Groundwater:
1.7 % per C
(Range: 5-40 C)
Rule of Thumb
For Groundwater:
1.7 % per C
(Range: 5-40 C)
It is more reasonable to rely on original data considering its respective
temperature than on adjusted data, e.g. to 25 C.
Temperature Dependency
3-8
c
eq
=
? ?
-
eq
-
eq eq
z z + =
+ +
c k -
eq
=
c
K

eq

Kohlrauschs Square Root Law
S
tr
o
n
g
e
le
c
tr
o
ly
te
Weak electrolyte
( )

6 10 9
/ z z e N

q 1
/ q

kT 3
e z z

11
- 2
0 A
2
0
-
eq
+
=
+ +

z z

z z
z z
q
- -
-
+ +
+
+
+
+
+
=

Debye-Onsager-Approach
Estimation of TDS from EC
3-9
[ ]
value al theoretic i.e. dilution, unlimited in
mol
cm
cation the of ty conductivi molar Limiting :
anion the of ty conductivi molar Limiting :
mol/l ion Concentrat : c
[mS/cm] ty Conductivi :
0
2
0
0
-
=
(
( )
+

c
Valid for Most Groundwater and
Surface Water:
[ ]
[ ]
|
|
\
|
(
+
=
mol
cm

mS/cm
mol/l c
2
-

(I < 0.01)
Estimation of TDS from EC
3-10
Graphs end at saturation point
E
l
e
c
t
r
i
c
a
l
C
o
n
d
u
c
t
i
v
i
t
y
[
m
S
/
c
m
]
Concentration [%]
Concentration, Conductivity
3-11
Dissociation process
1. Braking of lattice
2. Hydration of ions, to keep
ions apart (shield charges)
Has each ion the same number of water molecules in its hydrate shell?
3-12
Ideal vs. non ideal solution
What happens if there are less water molecules available than required for shielding?
Ideal solution
ions so well shielded by hydrate shell that there is no electrostatic forces between them
Non-ideal solution
Electrostatic forces between ions exist
3-13
Lets calculate some ionic strength
Data in mg/L
bicarbonate
3-14
Activity and non-ideal solutions
i i i
c f = a
a
i
: (chemical) activity of i [mol/L]
f
i
: activity coefficient [correction factor (0.1)]
c
i
: concentration of substance in solution [mol/L]
for solutions I > 0.01 M concentration of free ions is no longer equivalent to total
concentration
in non-dilute solutions I > 0.01 M ions interact electro statically with each other
These interactions are modeled by using activity coefficients (f) to adjust molar
concentrations to effective concentrations.
often f
i
is given as
i
3-15
Ionic strength
I=
1
2
i =1
n
c
i
z
i
2
n: number of ion types [1]
c: concentration of the respective ions [mol/L]
z: charge of the respective ion [C]
measure for ions and charge in solution
3-16
Activity coefficients
simple Debye-Hckel equation (I < 0.005 M) :
All models to correct for ion ion interaction are empirical and temperature dependent!
Models to predict Activity Coefficients
A: constant (0.5093 (l/mol)
0.5
@ 298K); z
i
: ion charge; I: ionic strength of the solution
I 1.4 1
I
z A - log
2
i i
+
=
I z A - log
2
i i
=
Gntelberg equation (I < 0.1 M) :
3-17
The extended Debye-Hckel equation is used to increase the solution
strength for which estimates of f can be made:
This equation extends the estimates to solutions where I < 0.5 M
B is a further constant,
r
i
is the ionic radius
Extended Debye-Hckel Equation
3-18
More Activity Coefficient Models
The Davis equation further extends the ionic strength range to about 1 M
(roughly 50,000 mg/L) using empirical curve fitting techniques
The Pitzer equation is a much more sophisticated ion interaction model that has
been used in very high strength solutions up to 20 M
3-19
Activity and Ionic Charge
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0.001 0.01 0.1 1 10
Ionic Strength
A
c
t
i
v
i
t
y

C
o
e
f
f
i
c
i
e
n
t
Debye-Huckel
Extended
Davis
Pitzer
Monovalent
Divalent
3-20
Activity and Ionic Charge
3-21
(1) Salts are generally more soluble in HOT water (Gases are more
soluble in COLD water)
(2) Alkali Metal Salts are very soluble in water.
NaCl, KOH, Li
3
PO
4
, Na
2
SO
4
etc...
(3) Ammonium Salts are very soluble in water.
NH
4
Br, (NH
4
)
2
CO
3
etc
(4) Salts containing the nitrate ion, NO
3
-
, are very soluble in water.
(5) Most salts of Cl
-
, Br
-
and I
-
are very soluble in water - exceptions are
salts containing Ag
+
and Pb
2+
.
Soluble Salts: FeCl
2
, AlBr
3
, MgI
2
etc...
Insoluble salts: AgCl, PbBr
2
etc...
Solubility (S)
3-22
Compound
Solubility
Temperature
in C
g/kg liquid mol/kg liquid
NaCl 359 6.14 20
NaNO
3
883 10.39 20
MgCl
2
6 H
2
O 546 2.69 20
CaSO
4
2.1 1.2 10
-2
20
CaCO
3
1.4 10
-2
1.4 10
-4
20
MgCO
3
1.0 10
-1
1.2 10
-3
25
Solubility
3-23
A n M m A M
n m
+
[ ] [ ]
n m
SP
A M K =
n m
n m
SP
sa
K
c S
+
= =
n m
[ ] [ ]
sa
c m M =
+
[ ] [ ]
sa
c n A =
- 2
4
2
4
SO Ca CaSO +
+
[ ] [ ]
- 2
4
2
SP
SO Ca K
+
=
SP sa
K c S = =
[ ] [ ] [ ]
sa
- 2
4
2
c SO Ca = =
+
Mass Act Law for Solubility (S); salts of low solubility
3-24
A n M m A M
n m
+
[ ] [ ]
n m
SP
A M K =
n m
n m
SP
sa
K
c S
+
= =
n m
[ ] [ ]
sa
c m M =
+
[ ] [ ]
sa
c n A =
Mass Act Law for Solubility (S)

3-25
Saturation Index
When a mineral is in equilibrium with the aqueous solution SI = 0
For Under-saturation SI < 0
For Super-saturation SI > 0
[ ]

K
IAP
log SI
SP
=
3-26
compound
compound
K
sp
K
sp
pK
sp
pK
sp
Selected Constants
3-27
Salt Ksp
Solubility
(mol/L)
CuS 8.5 x 10
-45
9.2 x 10
-23
Ag
2
S 1.6 x 10
-49
3.4 x 10
-17
Bi
2
S
3
1.1 x 10
-73
1.0 x 10
-15
Do you see the problem here ?
Solubility vs. K
sp
3-28
Solubility control
Ions for which concentration in water is controlled by the
concentration of other ions: F, HCO
3
, Ca, Mg, PO
4
, SO
4
Look for K
sp
(S) for least soluble salt, its counter ions
control each other
compound compound
K
sp
K
sp
pK
sp
pK
sp
3-29
What is the effect of
adding NaF?
CaF
2
(s) Ca
2+
+ 2F
-
The Common Ion Effect, Le Chatelier
3-30
What is the effect of adding NaCl here?
CaSO
4
(s) Ca
2+
+ SO
4
2
-
Addition of Different Ionic Species
3-31
What is the effect of adding NaCl here?
CaSO
4
(s) Ca
2+
+ SO
4
2
-
Addition of Different Ionic Species
[c
Ca
* f
Ca
] [c
SO4
* f
SO4
] = K
sp
If I increases, f decreases,
and c can increase to match Ksp again
3-32
Solubility vs. Temperature
Temperature dependency of Equilibrium constants
G
o
= -RT ln K
Do not use: since G
o
= f (T)
vant Hoff equation:
accounts for
exothermic & endothermic
2
RT
H
dT
K d
o
=
ln
T = Temperature in K
K = Equilibrium Constant
H = Enthalpy
R = Gas constant
|
|
\
|
2 1 1
2
1 1
T T R
H
T K
T K
o
) (
) (
ln
Approx. for temperature range of
ground/surface waters :
be aware: H
o
is still
temperature dependent

=
2
1
2
1
2
T
T
o
dT
RT
T H
T K
T K ) (
) (
) (
ln

=
2
1
2
1
2
T
T
o
T
T
dT
RT
T H
K
) (
ln
Solving the vant Hoff equation:
4 2
ET CT BT A H
o
T
+ + + =
Geothermal systems :
approx. for H = f(T) such as
are required
3-33
3-34
550
500
25 20 15 10 5
25
30
G
y
p
s
u
m
C
a
lc
i
t
e
C
a
2
+
[
m
g
/
l
]

c
a
l
c
i
t
e
C
a
2
+
[
m
g
/
l
]

g
y
p
s
u
m
Temperature [C]
Solubility of calcite and gypsum
in water, under standard atmospheric
pressure.
Compound Solubility in mass %
20 C 80 C
Sodium chloride 27,5 (Table salt)
Potassium chloride 25,5 33,6
Ammonium chloride 27,0 40,0 (Sal ammoniac)
Potassium sulfate 10,0 17,5
Calcium sulfate 0,199 0,10 (Gypsum)
Calcium hydroxide 0,17 0,087
Calcium carbonate 0,0015 0,002 (100 C)
Zinc chloride 78,7 84,5
26.5
25.5
27.0
10.0
0.199
0.17
0.0015
78.7
27.5
33.6
40.0
17.5
0.10
0.087
0.002
84.5
3-35
Endothermic Solubility Process:
Lattice Enthalpy > Hydration Enthalpy
Solubility increases with
increasing temperature
Exothermic Solubility Process:
Lattice Enthalpy < Hydration Enthalpy
Solubility decreases with
increasing temperature
3-36
Ion
Hydration
Enthalpy
[kJ/mol]
H
3
O
+
-1084
Li
+
-508
Na
+
-398
K
+
-314
Rb
+
-289
Cs
+
-256
Ag
+
-468
NH
4
+
-293
OH
-
-364
F
-
-510
Cl
-
-376
Br
-
-342
I
-
-298
CN
-
-349
NO
3
-
-255
Ion
Hydration
Enthalpy
[kJ/mol]
Mg
2+
-1908
Ca
2+
-1577
Sr
2+
-1431
Ba
2+
-1289
Zn
2+
-2054
Cd
2+
-1791
Hg
2+
-1820
Fe
2+
-1958
Al
3+
-4602
Fe
3+
-4485
3-37

Electrolyte Conductivity and Solubility Equilibrium

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Electrolyte Conductivity and Solubility Equilibrium

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M.HEG.03.

1 Inorganic Hydrogeochemistry 2012/13

Mass Act Law for Solubility (S)

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