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Ionic Strength

In dilute solutions, the ions that are present behave independently of


each other. However, as the concentration of ions in solution
increases, the activity of the ions decreases because of ionic
interaction. The ionic strength may be determined using the
following equation (Lewis and Randall, 1921)









I = ionic strength of solution, mole/L
C
i
= concentration of species i, mole/L
Z = Charge








2
1
2
i i
i
I C Z =
!
Ionic Strength

If the concentration of individual species is not known, the ionic
strength may be estimated from the total dissolved solids
concentration using the correlation.









TDS = mg/L

Quiz) try to calculate the ionic strength for ocean seawater









I = 2.5!10
"5
( )
(TDS)
Activity is a tendency to react or effective concentration
and is used to account for nonideal

Activity of substance: standard state conditions of the substance and
is based on commonly used standard conditions.

The standard reference conditions for zero free energy are: 1 atm of
pressure a temperature of 298.15 K (25C), elements in their lowest
energy level, and 1 molal hydrogen ion (1 mole of hydrogen ion per
1000 g of water).

Activity is a tendency to react <= to account for nonideal

Acnv|ty coemc|ent of a chem|ca| |n water may be g|ven by

{!} = y
|
[!] for |ons and mo|ecu|es |n so|unon

where
{!} = acnv|ty of |on|c spec|es, mo|e]L
y
|
= acnv|ty coemc|ent for the |on|c spec|es
[!]= mo|ar concentranon of the |on|c spec|es |n so|unon, mo|e]L

Genera| dehn|non of acnv|ty coemc|ent:
y
|
>1.0 for non-e|ectro|ytes
y
|
< 1.0 for e|ectro|ytes

fresh water, y
|
= 1.0 for non-e|ectro|ytes
a so|vent |n a so|unon, {!} = y
|
x
|
where x
|
|s the mo|e fracnon
pure so||ds or ||qu|ds |n equ|||br|um w|th a so|unon, {!} = 1
gases |n equ|||br|um w|th a so|unon, {!} = y
|
"
|
where "
|
|s the parna| pressure
of the gas |n atmosphere
m|xtures of ||qu|ds {!} = x
|
where x
|
|s the mo|e fracnon









I < 0.005 M, the activity coefficient can be estimated from the Debye-
Hckel limiting law




I < 0.1 M (less dilute solution)
modification of the DeBye-Hckel equation which is known as the Davies
equation can be applied with acceptable error (Davies, 1967).
Accurate to within 10% up to 0.5 M





The constant A for water:

0.49 @ 0C
0.5 @ 15C
0.51 @25C












log
10
!
i
=" AZ
i
2
I
1/2
1+ I
1/2
"0.3I
1/2
#
$
%
&
'
(

log
10
!
i
=" AZ
i
2
I
1/2

A=1.29 !10
6
2
D
"
T
( )
1.5
Lxerclse 1

CalculaLe Lhe acuvlLy coemclenL of na
+
, Ca
2+
, Al
3+
aL lonlc
sLrengLhs of 0.001 M and 0.003 M aL 23C


!
c
[C]
( )
c
!
d
[D]
( )
d
!
a
[A]
( )
a
!
b
[B]
( )
b
=
C
{ }
c
D
{ }
d
A
{ }
a
B
{ }
b
= K
Equilibrium constant based on the activities:
lonlc sLrengLh < 0.003 mole/L for mosL waLer supplles
lonlc sLrengLh ~ 0.7 mole/L for seawaLer
lonlc sLrengLh ~ 0.001-0.003 mole/L for lake and rlver waLer
lonlc sLrengLh: 0.001-0.003 mole/L for poLable ground waLer
lonlc sLrengLh: > 3 for oll eld brlnes
Influence of Ionic Strength on Activity of Molecules
lor nonelecLrolyLe, y
A
ls a funcuon of lonlc sLrengLh and can be
calculaLed uslng Lhe followlng emplrlcal equauon:

log
10
y
A
= ks
where
ks = SeLschenow or salung-ouL" consLanL, 1/mol
= lonlc sLrengLh of Lhe waLer, mol/L


Inuence of Ion|c Strength on nenry's Constant
Gases or VOCs in water supplies high in dissolved solids have higher
volatility (or have an higher apparent Henrys law constant) than those
with low dissolved solids. This results in a decrease in the solubility of the
volatile component (i.e., salting-out effect), which can be represented
mathematically as an increase in the activity coefficient of component A,
!
A
in aqueous solution.

!
A
will increase with increasing ionic strength and this in turn causes the
apparent Henrys law constant, H
app
, to be greater than the
thermodynamic value of H.

For most water supplies, the ionic strength is less than 10 mM and the
activity coefficient is equal to one. Significant increases in volatility and
the apparent Henrys constant are only observed for very high ionic
strength (0.7 mole/L) waters such as seawater.




1hermodynam|cs of Chem|ca| keacnons
rlnclples from equlllbrlum Lhermodynamlcs provlde a means for deLermlnlng
wheLher reacuons are favorable, and are also used ln process deslgn calculauons Lo
deLermlne Lhe nal equlllbrlum sLaLe.

1o deLermlne wheLher a reacuon wlll proceed, Lwo fundamenLal Lhermodynamlc
crlLerla musL be consldered.
1. Change ln enLropy of Lhe sysLem and lLs surroundlngs musL be greaLer Lhan zero
for a reacuon Lo proceed. When evaluaung chemlcal reacuons, Lhe enLropy
requlremenL generally does noL need Lo be consldered because lL ls Lyplcally
saused, especlally when heaL ls produced by Lhe reacuon.
2. 8equlremenL LhaL Lhe change ln free energy of Lhe reacuon musL be less Lhan
zero. 1hls ls because Lhe change ln free energy ls dened as Lhe nal sLaLe mlnus
lnlual sLaLe and Lhe nal sLaLe musL be lower Lhan Lhe lnlual sLaLe.
lL ls useful Lo examlne Lhe LoLal free energy of reacuon
as a funcuon of Lhe reacuon exLenL. 8ecause Lhe
absoluLe free energy of reacuon cannoL be easlly
deLermlned lL ls mosL common Lo deLermlne Lhe change
ln free energy of a reacuon. Accordlngly, Lhe free energy
of reacuon curve ls compared Lo convenlenL sLandard
condluons.

1hermodynam|cs of Chem|ca| keacnons
The convenient standard conditions:

1) Elements in their natural state at 25C and 1 atm of pressure
2) The reference temperature is 25C
3) The reference temperature for gases is 1 atm of pressure
4) The reference concentration for ions and molecules in solution is 1
molal hydrogen ion.
For most applications, molar concentration equals molal concentration and
a 1 molal solution is 1 mole per 1000 g of solvent. It is noted that some are
not stable such as Na or K
Iree Lnergy of Iormanon
1he expresslon for free energy was developed by !.W. Clbbs and ls
oen referred Lo as Clbbs free energy, C.
1he free energy change of formauon of a subsLance, l, ls glven by
Lhe followlng expresslon.



!G
F, i
=
lree energy change of Lhe formauon of specles !, k!/mol
!G
F, i
=!G
F, i

+ RT ln{i}

!G
F, i

=
lree energy change of Lhe formauon of specles !, k!/mol, aL
sLandard condluons
8 = unlversal gas law consLanL, 8.314 x 10
-3
k!/mol k

1 = absoluLe LemperaLure, k
[l} = acuvlLy of specles l
Iree Lnergy of Iormanon

A+
b
a
B !
c
a
C +
d
a
D
Lxerclse: calculaLe Lhe free energy change of reacuon for Lhe followlng reacuon
Iree Lnergy of keacnon
Iree Lnergy at Lqu|||br|um
1emperature Dependence of Iree Lnergy Change

1emperature Dependence of Iree Lnergy Change

Lxerc|se 1

CalculaLe Lhe pP of neuLrallLy and free-energy change of
Lhe reacuon aL 10 degree Celslus assumlng LhaL Lhe
enLhalpy of reacuon does noL change wlLh LemperaLure
Lxerc|se 2

Can M18L be degraded anaerob|ca||y (|.e., |n
groundwater) |n the presence of n|trate?
Lnergy Lqulvalences

SLandard unlLs for expresslng Lhls energy lnpuL are:
LlecLron volLs,
Cell poLenual,
WavelengLh of llghL
8and gap

Lnergy = ev = L ! number of electrons transfer


-19
-19
1.60!10 coulomb Joule
1eV=1electron! !1Volt !
electron coulombvolt
=1.60!10 Joules
Energy
where
wavelength
h
c
!
"
!
=
=
-34
10
-19
6.26!10 Jsec
3.0 10 cm/sec
Energy 1.60!10 J
1172
c h
c
nm
!
"
= = # = # #
=
WhaL ls Lhe equlvalenL
wavelengLh for Lhls energy?