Updated: 6 March 2018 Print version

Lecture #4
Kinetics and Thermodynamics: Fundamentals of water
and Ionic Strength
(Stumm & Morgan, pp.1-15
Brezonik & Arnold, pg 10-18)

(Benjamin, 1.2, 1.3, 1.5)

David Reckhow CEE 680 #4 1
 Molecular Weight and boiling point
 Organic Compounds: Homologous series

Image from:
http://chemed.chem.purdue.edu/genchem/topicrevie Image from: https://socratic.org/questions/how-does-molar-mass-
w/bp/ch14/liquids.php affect-boiling-point
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Water and related heteroatoms
 Water is different

Groups

“hydrides”

Image From: http://schoolbag.info/chemistry/central/100.html

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Structure of Water
S&M: Fig. 1.3
 sp3 hybridization
 2 bonding and 2 non-bonding
orbitals
 Dipolar Character
 Origin of Water’s Unusual S&M: Fig. 1.4

properties
 High melting and boiling point
 High heat of vaporization
 Expands upon freezing
 High surface tension
 Excellent polar solvent

B: Fig 1.2

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Water’s intermolecular
structure
 Dominated by Hydrogen
Bonds Fig. 1.5a
Pg. 8
 Ice
 Open tetrahedral structure
 Water
 Flickering cluster model
 100 ps lifetime

 0.1 ps molecular vibration

Fig. 1.5b
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Solutes in Water
 Great solvent for ionic or
ionizable substances
 Ion-dipole bonds improves
stability S&M: Fig. 1.6
 Energy increases with charge of ion
and decreases with size
 Solvent hole model
 As solute-water bonding strengthens B: Fig 1.4
compared to water-water bonding,
solubility goes up
 Hydrophilic solute
 Weak solute-water bonds reduce
solubility
 Hydrophobic solutes

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Periodic Table

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 H 4.5
H2O
-1.74 -1.74
“680 Periodic Table” 8.8
He

Li 6.3 Be B 7.0 C 4.9 N6.3 4.5O 5.7 F Ne

Li+ BeOH+ (?) H3BO4 HCO3- N2, NO3- H2O, O2 F-, MgF+
4.6 9.2 3.39 2.64 3.0 1.97 -1.74 -1.74 4.17 5.3 8.15

Na 7.7 Mg 7 Al 2 Si 3.8 P 4 S 6.9 Cl

7.9 Ar
Na+ Mg+2, MgSO4 Al(OH)4- H4SiO4 HPO4-2 SO4-2,NaSO4- Cl-
0.33 3.57 1.27 3.77 7.1 4.15 3.8 5.3 1.55 3.92 0.26 3.66 6.96

K 6.7 Ca 5.9 As Se 4 Br 8 Kr
K+ Ca+2, CaSO4 HAsO4-2 SeO3-2 Br-
1.99 4.23 1.99 3.42 7.3 8.6 3.08 8.6

Sr 6.6  Ocean residence time (log yr) I 6

Sr+2  Predominant species I-, IO3-
4.05 6.3
 River Water conc. (-log M)
Ba 4.5  Seawater conc. (-log M)
Ba+2
6.8
David Reckhow CEE 680 #4 After S&M:Fig. 1.7, Pg. 10 8
Law of Mass Action
 The rate of an elementary reaction is proportional to
the product of the concentrations of the participating
molecules, atoms or ions
 Chemical equilibria comes from the combination of
two competing rates
 Consider the autodecomposition of water

𝐻𝐻2 𝑂𝑂 ↔ 𝐻𝐻 + + 𝑂𝑂𝑂𝑂 − Equilibrium

Quotients
 Other examples
 acid dissociation, Precipitation, Redox, Adsorption,
volatilization

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Effect of pH, water temp, chlorine concentration and log reduction
on required “Ct” for disinfection of Giardia with free chlorine
(US EPA SWTR Guidance Manual)

from US EPA SWTR Regulations (units of Ct are mg L-1 min )

Ct Values for 1 log Inactivation of Giardia by free Chlorine
C pH (temp = 5.0 degrees C) pH (temp= 20 degrees C)
(mg/L) 6.0 6.5 7.0 7.5 8.0 6.0 6.5 7.0 7.5 8.0
0.1 32 39 46 55 66 12 15 17 28 33
0.5 33 40 47 56 67 12 15 18 28 34
1.0 35 42 50 60 72 13 16 19 30 36
1.5 37 44 52 63 77 14 17 20 32 38
2.0 39 46 55 67 81 15 17 21 33 41

Ct Values for 3 log Inactivation of Giardia by free Chlorine

C pH (temp = 5.0 degrees C) pH (temp= 20 degrees C)
(mg/L) 6.0 6.5 7.0 7.5 8.0 6.0 6.5 7.0 7.5 8.0
0.1 97 117 139 166 198 36 44 52 83 99
0.5 99 119 141 169 201 37 45 53 85 101
1.0 105 125 149 179 216 39 47 56 90 108
1.5 110 131 157 190 230 42 50 59 95 115
2.0 116 138 165 200 243 44 52 62 100 122
Borrowed
David Reckhowfrom John Tobiason
CEE 680 #4 10
Activity
 Activity is the “effective or apparent”
concentration, which may be slightly different
from the true “analytical” concentration
 These two differ substantially in waters with high TDS,
such as sea water.
 We identify these two as follows:
 Curved brackets ({X}) indicate activity
 Square brackets ([X]) indicate concentration
 Usually this is molar concentration

 This may also be used when we’re not very concerned about the
differences between activity and concentration

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Why the difference?
 Mostly long-range interactions between uninterested bystanders
(chemical species that are not involved in the reaction) and the two
dancers of interest (those species that are reacting)

 Relative importance in determining activity

 Concentration >> charge > polarity > MW

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Activity & Ionic Strength
K=
{C} {D}
c d

 Equilibrium quotients are really

{A}a {B}b
written for activities, not
concentrations
 in most natural waters activities are {A} ≈ [A]
nearly equal to the molar
concentrations
 In saline waters, we must account for
{A} = f A [A]
differences between the two
 activity coefficients (f or γ) are used for
{A} = γ A [A]
this
 Ionic Strength (I) is used to determine the
extent of correction

David Reckhow CEE 680 #4

I= 1
2 ∑m z 2
i i
13
Correlations for ionic strength
 µ vs. specific conductance: Russell Approximation
 µ = 1.6 x 10-5 x K (in µmho/cm)
 µ vs. TDS: Langlier approximation
 µ ~ 2.5 x 10-5 x TDS (in mg/L)

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Equilibrium Constants
{H }{A } [H ]γ [A ]γ
+ − + −
 Consider a simple acid/base K= = H +
A−

reaction {HA} [HA]γ HA

 HA = H+ + A- [ ][ ] γ
 H + A−
=  H+

γA 
−

 γ
 The activity-based constant is:  [HA]  HA 
 The concentration-based constant
is: c
K=K
 γ HA
 = [ ][ ]
  H + A−
 γ +γ −   [HA] 
 H A  
 And a mixed constant would be:

K′ = K
{ }[ ]
 γ HA   H + A−
=
 γ −   [HA] 
 A   

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 Corrections to Ion Activity
Approximation Equation Applicable
Range for I
Debye-Hückel log f = −0.5 z 2
I <10-2.3

Extended I <10-1
log f = −0.5 z 2
Debye-Hückel 1 + 0.33a I
Güntelberg I <10-1, solutions
log f = −0.5 z 2
1+ I of multiple
electrolytes
Davies  I  <0.5
log f = −0.5 z 
2
− 0.2 I 
1+ I 

Based on: S&M, Table 3.3; B, Table 1.4a

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note: Mihelcic cites 0.3 16
 Ion Size Parameter
Ion Size Ions
Parameter, a (Å)
9 H+
8 Al+3, Fe+3
6 Mg+2
5 Ca+2, Zn+2, Cu+2, Sn+2 Mn+2, Fe+2
4 Na+, HCO3-, H2PO4-, CH3COO-, SO4-2, HPO4-
2
, PO4-3
3 K+, Ag+, NH4+, OH-, Cl-, ClO4-, NO3-, I-, HS-

See also: B, Table 1.4b

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Debye-Hückel
 Effect of charge (z)

1.2
1
0.8 z=1
z=2
0.6
f

z=3
0.4 z=4
Debye-Hückel
0.2
0
-5 -4 -3 -2 -1 0
Log I

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Extended Debye-Hückel
 Benjamin: Figure 1.6a

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Activity Coefficients compared
 Different approximations at low charge
 a=3

1.2
1
0.8 DH
EDH
0.6
f

Guntelberg
0.4 Davies
a=3
0.2
z=1
0
-5 -4 -3 -2 -1 0

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Log I 20
Act. Coeff. Comparison (cont.)
 Different Approximations at low charge
 a=9

1.2
1
0.8 DH
EDH
0.6
f

Guntelberg
0.4 Davies
a=9
0.2
z=1
0
-5 -4 -3 -2 -1 0
Log I
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Act. Coeff. Comparison (cont.)
 Different Approximations at high charge

1.2
1
0.8 DH
EDH
0.6
f

Guntelberg
0.4 Davies
a=3
0.2
z=3
0
-5 -4 -3 -2 -1 0
Log I
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 Comparison: CaCl2 dissolution
 Benjamin, Figure 1.6b

 SIT is the specific

interaction model
 Incorporates
interactions between
specific ions
 Quite accurate for high
brines, but requires
more coefficients

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Activity Coefficients (cont.)
 For neutral species:
 logγ = kI
 k is a function of species, T and P
 k=0.13 for O2 in NaCl

 in fresh water, I=0.002, γO2 = 1.0006

 Molar vs. Molal

 in principle, activity predictions are based on molal
concentrations (mole/kg solvent), but since we are often most
concerned with dilute solutions, we frequently use molar
concentrations

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 Salting out Coefficients
Compound ks (L/mole) Reference
Tetrachloroethene 0.213 Gossett, 1987

Trichloroethene 0.186 Gossett, 1987

1,1,1-Trichloroethane 0.193 Gossett, 1987

1,1-Dichloroethane 0.145 Gossett, 1987

Chloroform 0.140 Gossett, 1987

Dichloromethane 0.107 Gossett, 1987

Benzene 0.195 Schwarzenbach et al., 1993

Toluene 0.208 Schwarzenbach et al., 1993

Naphthalene 0.220 Schwarzenbach et al., 1993

Oxygen 0.132 Snoeyink & Jenkins, 1980

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Activity for isotopes
 Most subtle of the effects
 For saline waters (chloride is counterion)
 Deuterium
𝛾𝛾 2
𝐻𝐻 1𝐻𝐻 16𝑂𝑂
𝑙𝑙𝑙𝑙 = 0.0022 𝑁𝑁𝑁𝑁+ + 0.0025 𝐾𝐾 +
𝛾𝛾 1𝐻𝐻 1𝐻𝐻 16𝑂𝑂

+0.0051 𝑀𝑀𝑀𝑀+2 + 0.0061 𝐶𝐶𝐶𝐶+2

 Oxygen-18
𝛾𝛾 1
𝐻𝐻 1𝐻𝐻 18𝑂𝑂
𝑙𝑙𝑙𝑙 = 0.0016 𝐾𝐾 + − 0.0111 𝑀𝑀𝑀𝑀+2
𝛾𝛾 1𝐻𝐻 1𝐻𝐻 16𝑂𝑂

−0.0047 𝐶𝐶𝐶𝐶+2
 Where () represents the molal concentration (moles/Kg-water)

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  To next lecture

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