Interactions in an electrolyte

Shkkemian peruseet
KE-31.4100
Tanja Kallio
tanja.kallio@aalto.fi
C213

CH 2.4-2.5

Solvent ion interactions

Solvent ion interactions

W1 = discharging an ion
ze

ion

neutral
1
vacuum
3

ze

qdq
z 2e 2
w1 V (q )dq

a
8 0 a
0
0
0

total
W2 = cavity formation +
surface tension
W2 ~ negligible

solvent

W3 = charging an molecule
z 2e 2
w3
8 0 r a

z 2e2
1
1
wel GIS
80 a
r

Experimental values for hydration

energy

Ion ion interactions

Debye lenght
Spatial distribution of ions around the central ion obeys
Boltzmann distribution

ci (r ) cib e zi ( r )

(2.32)

Charge density around the central ion is obtained by

summarizing charge densities of all the ions

( r ) z i Fci
i

z ( r )
z i Fcib e i

z i F(r )
F 2 ( r )
1
z i2 cib

RT
RT

z i Fcib

electroneutrality

first term of Taylor series

Dependence of potential on charge density is given by Poisson equation

0 r
2

F2
;
0 r RT
2

z i2 cib
i

(2.34)

Debye length = thickness of the double layer

(2.33)

Falloff in the electrostatic potential

z c e e ( r a ) 1
(r )
4 0 r 1 a r
(2.36)

Debye-Hckel limiting law (1/2)

Electrostatic work done to move the central ion inside the
ion cloud
zc e

wion ion N A atm (a )dq ; atm (a) (a) V (a)

0

potential distribution
around the central ion
(2.36)
N A zc e 2
wion ion
(2.39)
8 0 r 1 a

zc e

4 0 r 1 a

potential field crated by the

central ion at distance a (2.37)

When diluting the solution from concentration c1 to c2 (infinite dilute) work is done
a
c

wdil RT ln 2 RT ln 2 RT ln 2 wosm wion -ion
(2.40)
a1
c1
1
By combining (2.39) and (2.40)

zi e 2
wionion

ln i

RT
8 0 r k T 1 a
2 = 1 (infinite dilution)

activity coefficients origins from

electrostatic interactions between ions
(2.41)

V (r )

zc e 1
(2.37)
4 0 r r

Debye-Hckel limiting law (2/2)

Sifting to log system

log i zi2

A I
1 Ba I

; I

1
zi2 ci

2 i

(2.42)

ion strength
Utilizing definition of mean activity:
log z z

A I
1 Ba I

(2.43)

experimental
D-H law
D-H limiting law

1,8246 106
mol1/ 2 dm 3 / 2 K 3 / 2
3/ 2
rT

50,29 108
cm 1mol1/ 2dm 3 / 2 K1/ 2
1/ 2
rT

Ionpairs
Equilibrium constants for ion assosiation/dissosiataion
Kd

A c A B c B
c AB

c 1

= 1 Kd = 2c/(1 )

Bjerrumin theory
Ions around the central ion obey Maxwell-Bolzman distribution
Potential profile immediately around the central ion obeys (2.37)
Hypothesis: ions form ion pair when distance is smaller than q
2 3b
z
z
e

K a 4000N A
x 4 e x dx
4 0 r kT

Fouss theory
Ions must be in contact to form an ionpair
Probability of forming an ion pair depends on number of ions, solvent volume,
space occupied the species and electrostatic energy on the surface of the ion
1
2c

1000 N A

4
a 3 e E (a ) / kT K a
3

Super acids and Hammett acid function

very acidic acids extension to the conventional pH scale
is needed
a weak indicator base B is added into the acid solution
B + H+ BH+

measurable

unknown
concentration depends on the pH of the
super aid

Hammet acid function is defined so that it becomes

equal to pH in ideally diluted aqueous solutions
H 0 log

cH c B
c BH

log

aBH
aB

log(cH ) log

equilibrium
measurable
constant for the
indicator acid

B
BH

Hammett acid function H0 for 0.1 M HClsolutions. Abscissa: content of the organic
component in mol-%

for super basis

BH + OH(H2O)n B + (n + 1)H2O

H pK w log [OH ] (n 1) log [H 2 O]

M.A. Paul and F.A. Long, Chem. Rev. 57 (1957) 1-45

Summary

Interaction in electrolyte solutions

solvent ion interactions

ion ion interactions

superacids

z 2e 2
1
1
wel GIS
80 a
r

pK d log

[B]
H0
[BH ]

H pK w log [OH ] (n 1) log [H 2 O]

ion

neutral
1

F2

0 r RT
2

vacuum 2
3
solvent

zi2cib
i

Debye length
Debye Hckel law
log z z

A I
1 Ba I