Updated: 6 March 2018 Print version

Lecture #4
Kinetics and Thermodynamics: Fundamentals of
water

nd Ionic Strength
(Stumm & Morgan, pp.1-15
Brezonik & Arnold, pg 10-18)

David Reckhow (Benjamin, 1.2, 1.3, 1.5)

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

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w/bp/ch14/liquids.php affect-boiling-point
David Reckhow CEE 680 #4 2
Water and related heteroatoms
Water is
different Groups

“hydrides”

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l
David Reckhow CEE 680 #4 3
Structure of Water
S&M: Fig. 1.3
sp3 hybridization
 2 bonding and 2 non-bonding
orbitals
Dipolar Character
S&M: Fig. 1.4 4
Origin of Water’s
Unusual properties
 High melting and boiling
point
 High heat of vaporization
 Expands upon freezing
 High surface tension
 Excellent polar solvent

B: Fig 1.2

David Reckhow CEE 680 #4

Water’s intermolecular structure

Dominated by
Hydrogen Bonds e Fig. 1.5a
Ice Pg. 8
Open tetrahedral
structur
Water
Flickering cluster model
 100 ps lifetime
 0.1 ps molecular vibration 5

Fig. 1.5b
David Reckhow CEE 680 #4
Pg. 8
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 thens
 As solute-water bonding strengng, B: Fig 1.4
compared to water-water
bondi solubility goes up
 Hydrophilic solute e
 Weak solute-water bonds
reduc solubility
 Hydrophobic solutes
6
David Reckhow CEE 680 #4
Periodic Table

CEE 680 #4
David Reckhow 7
 H 4.5 He
H2 O
-1.74
“680 Periodic Table” 8.8
-1.74
Be B 7.0 C 4.9 N 6.3 O 4.5 5.7 Ne
Li 6.3 BeOH+ (?) H3BO4 HCO3 - -
F , MgF+
-

4.6 Li+ 9.2 3.39 2.64 N2, NO3 3.0 -1.74F -1.74 5.3 8.15
1.97 4.17
H2O, O2
Na 7.7 Mg 7 Al 2
-
Si 3.8 P -2
4 S
-2
6.9
-
7.9 Cl Ar
Na + Mg , MgSO4 Al(OH)4
+2
H4SiO4 HPO4 SO4 ,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 As -2
Se -2
4 Br -
8 Kr
HAsO4 SeO3 Br
Ca
4.235.9 K +
7.3 8.6 3.08
Ca , CaSO4
+2

1.99
3.42
1.99  Ocean residence time (log 8.6 I
yr) I , 6IO3 -
-

 Predominant species 6.3

Sr 6.6
Ba
Sr 4.5
+2

 River Water
Seawater conc.
conc. (-log M)
(-log
4.05 Ba+2 M)
David Reckhow 6.8 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

𝐻 ↔ 𝐻𝐻+ +𝐻𝐻
− Equilibrium
2𝑂
𝐻
𝑂 𝑂𝑂
Quotients
Other examples
acid dissociation, Precipitation, Redox,
Adsorption, volatilization

David Reckhow CEE 680 #4 9

 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
minC) Ct Values for 1 log Inactivation of Giardia by free Chlorine
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

C Ct Values for 3 log Inactivation of Giardia by free Chlorine

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
BDoavrird oRweckehdowfrom John 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

David Reckhow
the differences
CEE 680 #4
between activity and concentration 11
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

David Reckhow CEE 680 #4 12

Activity & Ionic Strength C c
K
Equilibrium quotients are AD
a
d

really written for activities, not B b

concentrations
in most natural waters activities A
are nearly equal to the molar
A
concentrations
In saline waters, we must account A f A
for differences between the two
 activity coefficients (f or γ) are used
AA A A
 1 2
for this
 Ionic Strength (I) is used to determine
the extent of correction

David Reckhow CEE 680 #4

I 2 m z 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)

David Reckhow CEE 680 #4 14

Equilibrium Constants
Consider a simple H 

H

 A




 HA
H A

acid/base reaction HAA  HA

K
 H A
 HA = H+ + A-   

 
H A
The activity-based constant  HA    HA
 
is:
The concentration-based  
is:
constant c
  HA   H  A
K  K   
    
  H A   HA 
And a mixed constant would   


be:
   
  HA   H 
KK   HA 
 

 AA  
 

  
David Reckhow CEE 680 #4 15
Corrections to Ion Activity
Approximation Equation Applicable
Range for I
-2.3
Debye-Hückel log f  0.5z 2
I <10

-1
Extended 2 I <10
log f  0.5z
Debye-Hückel 1  0.33a I
Güntelberg I <10-1, solutions
log f  0.5z 2
1 I of multiple
electrolytes
Davies  I  <0.5
log f  0.5z 2  0.2I 

  1 I


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

1.4a 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
Na+, HCO -
, H
HPO 3 2
- -
-PO , CH COO , SO ,
-2
4 4 3 4 4
4
K+, -Ag+, NH +, OH-, Cl-, ClO -, NO -, I-,
3 HS
4 4
3

See also: B, Table

1.4b
David Reckhow CEE 680 #4 17
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

David Reckhow CEE 680 #4 18

Extended Debye-
Hückel
Benjamin: Figure
1.6a CEE 680 #4

David Reckhow 9
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

David Reckhow CEE 680 #4

Log I 20
Act. Coeff. Comparison (cont.)
Different Approximations at low
charge
 a
1.2 =9
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
David Reckhow CEE 680 #4 21
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
David Reckhow CEE 680 #4 22
 Comparison: CaCl2 dissolution
E 680 #4 23

Benjamin, Figure
1.6b

 SIT is the specific

interaction
model
 Incorporates
interactions
between specific
ions
 Quite accurate for
high brines, but
David Reckhow
requires more CE
Activity Coefficients (cont.)
For neutral species:
log = kI
 k is a function of species, T and P
 k=0.13 for O in NaCl
2

 in fresh water, I=0.002, O2 = 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

David Reckhow CEE 680 #4 24

 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

David Reckhow CEE 680 #4 25

Activity for isotopes
Most subtle of the effects
For saline waters (chloride is
counterion)
 Deuterium 𝛾𝛾 1216
𝐻𝐻𝑂
𝐻𝑂 +
= 0.0022𝑁
𝑁𝑁𝑁 + 0.0025 𝐾𝐾+
𝑙𝑙𝑙𝑙
𝛾𝛾
𝐻116
𝐻
𝑂
𝐻𝑂
+0.0051 𝑀
𝑀+2
𝑀 + 0.0061 𝐶
𝑁
𝑁+2
𝐶
 Oxygen-18
𝛾𝛾
1118
𝐻𝐻
𝑂
𝐻
𝐻𝑂
𝑙𝑙𝑙𝑙 = 0.0016 𝐾𝐾+ − 0.0111𝑀
𝑀+2
𝑀
𝛾𝛾
𝐻1116
𝐻
𝑂
𝐻
𝐻𝑂
−0.0047

𝐶
𝑁
𝑁+2
𝐶
David Reckhow CEE 680 #4 26

 To next lectur
e

David Reckhow CEE 680 #4 27