CHAPTER III

ION – ION INTERACTION IN

THE STRONG ELECTROLYTE

1
 CHAPTER III

III.1. Thermodynamic equilibrium in the

solution.
Activity and activity coefficient
III.2. Debye – Hückel theory

2
1. Thermodynamic equilibrium in the
solution. Activity and activity cofficient
ion-dipole interaction : Formation and stability of
electrolyte.
However, quantitative description of electrolyte was
incomprehensive

Some missing details on , Kpl

WHY?
Only use Kpl in diluted solution of weak
electrolyte.

ACTIVITY, a ion-ion interaction

Description
3
Csol increases => coverage between the solvation
spheres of ions
=> association of cation – anion due to
approach => ionic association. 4
All interactions in Use activity instead
solution of concentration

Using the same thermodynamic equations

for ideal solution by replacing the
concentration by activity

  a H  a A
[ H ][ A ] K
K a HA
[ HA]
5
 Activity and activity coefficient

aC = C.C
am = m.m C, m, X, Activity
coefficien
aX = X.X (hay fC, fm, fX) (molarity, molality
and mol fraction)

Symbol
Types of
Unity Activity
concentration Concentration Activity
coefficient
Molarity mol/l C, M aC f, 
molality mol/kg m am m
solvent
Mol fraction X, N aX, aN  X,  N
6
 Chemical potential

Chemical potential of i specie, i – describing the work to

bring a mol of i from vacuum to the solution without
changing the temperature, pressure and number of
molecules j in the system ( i)
 G 
 i   
 N i  N j i ,T , P
G – Gibbs free energy;
Ni – number of species i; Nj – number of other species, including solvent

 U   H   G   F 
 i            
 N i  S ,V , N j  i  N i  S , P , N j  i  N i  T , P , N j  i  N i  T ,V , N j  i
7
Ideal solution    (T )  RT ln X i
lt
i i
o

Real solution  thuc   io (T )  RT ln ai

i

ithuc  io (T )  RT ln ai  io (T )  RT ln Ci  RT ln  i

ithuc  ilt  RT ln  i  g i

gi* represent all interaction between species i and

other molecules in the solution  work needs to bring
one molar (i) from ideal solution to real solution

8
 BA = ++ + 
BA = + B+ +  A
 BA
o
    o     o
Ideal solution Real solution

 lt
BA  o
BA  RT ln C BA  BA
thuc
  BA
o
 RT ln aBA
    RT ln C 
lt

o

 thuc

  o  RT ln a
 lt   o  RT ln C   thuc   o  RT ln a

RT ln aBA    RT ln a   RT ln a
 
aBA  a .a
Activity of each ion can‘t be
experimentally identified Average activity
9
 Average activity (a) và
Average coefficient activity (f hay ±)

a  a  a 
a  
a  (a .a  )   1 /

   1 /
m  (m .m )
   (  .  )1 /
 

Infinitely diluted solution:

(aC  C)C0 ; (am  m)m0 ; (aX  X)X0

C = m = X = 1
10
Comparison
between
electrolyte
and non-
electrolyte
solution

Log m

J. Koryta, Principles of Electrochemistry, John Wiley &

Sons Ltd. (1993).
11
 Determine activity coefficient by different methodes :
osmotic pressure , freezing point depression, boiling
point elevation and electromotive force.

Average acitivity of KCl solution at T = 25oC

C, mol/l 0,00010 0,0100 0,0500 0,100 0,500 1,00 2,00

f (1) 0,965 0,900 0,813 0,763 0,638 0,596 0,563

(2) 0,965 0,899 0,809 0,762 - - -
(3) 0,965 0,899 0,815 0,764 0,644 0,597 0,569

(1) Osmotic pressure measurement

(2) Decrease of freezing point
12
(3) Electromotive force
 Activity coefficient - concentration
Lewis–Randall–Brönsted equation
Average activity coefficient of MgCl2 as a function of concentration

C 0,100 0,200 0,400 0,800 1,00 2,00 5,00

f 0,516 0,468 0,442 0,445 0,479 0,668 1,550

Lgf Lewis và Randall :

Average activity of diluted
HCl NaCl solution depends on all
ions in solution and its
charge .

Ionic strength: is a
KCl
KNO3 measure of the amount of
C ions present 13
Ionic strength 1 1
I   mi Z i2 hay I   C i Z i2
2 i 2 i
Experimental equation Lewis – Randall:

lg f   h I
Average activity coefficient ( , f ) of electrolyte solution is
generally a function of ionic strength causing by its ions.
Activity coefficient of electrolyte solution depends on the concentration of
all existing ions and its charges but not depends on its nature and
concentration.

Experimental equation of Brönsted

water, 20oC, 1-1, diluted: A  0,5 litre3/2

lg f   0,5 C mol1/2 14
The ionic strength of a solution is a measure of the amount of ions
present. As you might guess a divalent ion (a 2+ or 2- ion, like Ca2+)
does more to make the solution ionic than a monovalent ion (e.g.,
Na+). This must be taken into account. The other very critical thing
to remember is that the ionic strength of a solution depends on the
concentrations of all the ions in the solution, not just the ion pair
that you are calculating the activity coefficient for. Thus, if you are
calculating the average activity coefficient of dissolved CaCl2, but
there is also dissolved NaCl present, the ionic strength you use has
contributions from all the ions.The formula for ionic strength is:

Ionic strength is sometimes stated as having units of molality

(or molar) and other times stated as being unitless, depending on
the book you read. The easiest way to see how to apply this
formula is to consider a few examples. First consider 100 mM
NaCl. Upon dissolving, one obtains 100 mM Na+ and 100 mM Cl-.
Thus 15
 Lgf

CaCl2

Experimental Lewis –
Randall equation is
suitable only in the low
concentration region
m  0,02 K2SO4
ZnSO4

16
Apply activity coefficient into Arrhenius’ electrolytic
theory
B+A_ +Bz+ + Az

Dissociation constant K:

K’ – Apparent dissociation constant

Water, 25oC, 1-1: + =  = 1 lg    lg     A I  0,5 I

K
 B   A  10 0 , 5 I
;  BA  1 K'  K .10 I

 B A
17
 Dissociation degree:

   .   .  .C   .C 1
K' 
C (1   ) (1   )

For weak electrolyte, diluted concentration:

K’ << C

18
 

K’ = K’ = K’ =

Dependence of dissociation degree on concentration of

weak electrolyte within the different dissociation constants
19
 2. Debye – Hückel theory

2.1 Ion distribution in the electrolyte solution.

“Ionic atmosphere” concept
2.2 Potential of “Ionic atmosphere” – Energy of
interaction
2.3 Debye- Hückel theory and activity coefficient
2.4 Advantages, missing point of Debye-Hückel
theory và perspective
2.5 Debye – Hückel theory employed in case of
weak electrolyte 20
 III.2.1 Ion distribution in the electrolyte. “Ionic
atmosphere” concept
- + - -
• Ideal electrolyte solution: No +
+ - - +
interaction between ions (Arrhenius)
- + +
• 1806, T. Grotthuss: first theory
about the electrolysis Ideal electrolyte
solution
• Real electrolyte solution (Debye và
-
Hückel - 1923 ): Electrostatic force of + - -
+
ions  Each ion is surrounded by + - +
+
some opposite charged ions -
+ -

Real electrolyte
solution
Atkins, Physical Chemistry. 6th ed. Figure 10.2 21
Characteristics of Debye – Hückel law

(i) Electrolyte dissociates completely ( = 1; there

haven’t non-dissociated molecules in solution);
(ii) Solution: homogenous ambient with constant
dielectric constant 
(iii) Interaction between ions respects Coulomb
electrostatic law.
(iv)Ion distribution is followed “ionic atmospheric”, a
kind of spherical symmetry.
22
 • It can be generally defined as
the area at which a charged
entity is capable of attracting an
entity of the opposite charge.
• Central/reference Ion)
• Spatial Ion distribution around
ion central obeys Maxwell -
Boltzmann: depend on the
interaction energy between
central ion and others
“Ionic Atmosphere” concept • Due to thermal movement: ions
employed in Debye-Hückel are always mobiles, change the
position  ionic atmosphere is
theory
statistic
Energy given by electrostatic interaction of specific ion versus
other ions in solution is equally defined as interaction energy of
this ion within the surrounded ionic atmosphere 23
2.2 Potential of “Ionic atmosphere” – Energy of
interaction
“ionic atmosphere” is a kind of spherical symmetry: Poisson
equation  - 
 d 2 2 d  : potential;  : charge density

2
  2 
 o dr r dr
 = niZieo ni : local concentration of ion i
ni relates to volume concentration nio by Boltzmann distribution

W W: Energy of electrostatic interaction

ni  nio exp( ) kT: Energy of thermal movement
kT
Z i eo 
ni  nio exp( )
W = Zieo kT

 Z i eo  
   nio Z i eo . exp  
 kT  24
  Z i eo 
   nio Z i eo . exp  
 kT 
2
x
e  1  x   ....
x
e x
 1 x
2! x << 1
W << kT
.
Z i eo
 1
kT
 Z i eo   nio Z i2 eo2
   [nio Z i eo .1  ]   (nio Z i eo )   ( )
 kT  kT
Eletroneutrality solution

(nioZieo) = 0  eo2 
    (ni o Z ) 
i
2

 kT 
25
 2
1 e
  o kT  io i i
2
  o
n z 2

eo2
Đặt: 
 o kT
 io i )
( n Z 2

 r r
d  2 d
2
e e

2
 2    2   A1  A2
dr r dr r r
Boundary condition: r  0 A2  0
Zi eo e  r
A1    A1
4o r

Ion is a charged point 26

 Z i eo e  r
  Potetial of ionic atmosphere
4 o r
Potential caused by ionic
atmosphere at the position of
 a = [ - i]r  0 central ion
i : Potential of electric field caused by central ion
Zi eo
i 
4o r 1/ : Radius of ionic
atmosphere

Zi eo er 1 Z i eo 
a    a  
4o  r  r0 4 o

27
 Zi eo Z i eo 
i  a  
4o r 4 o
Interaction between central ion and ionic atmosphere =
electrostatic interaction between two opposite charged ion,
Zieo and Zieo at a distance of 1/.
q1q2 Energy of interaction calculate for 1
U 
4 o d mol ion

Z i2 eo2 
U  
8 o
-
+ - -
+
+ 1/
- + 1/
- Z ie o Z ie o -Zieo
+
- + - +  Z ie o
28
 2.3 Debye- Hückel theory and activity
coefficient
The real solution is distinguished to the ideal solution by the
energy of interaction between the ion and ionic atmosphere.

 thuc
   RT ln  i  g
lt  Z i2 eo2 
i i i RT ln  i  N A U   N A
8 o
eo2

 o kT
 io i )
( n Z 2
k = R/NA

Z i2 eo2 Z 2 2
i eo
ln  i  
8 ( o kT ) 3 / 2
 (nio Z i )   8 ( kT ) 3 / 2
2
2.10 3 N A I
o

1 C+ = C = C
I   Ci Z i2 I=C
2 i 11
29
 lg  i   Z h I i
2

(1,6022.10 19 ) 3 (2.6,022.10 23.10 3 )1 / 2 1 1,825.10 6 3 / 2

h .  (l / mol ) 1/ 2
.K
2,3026.8.3,1416.(0,88542.10 11.1,3807.10  23 ) 3 / 2 (T ) 3 / 2 (T ) 3 / 2

Activity coefficient of each ion depends on the charge of ion,

temperature, dielectric constant and ionic strength
Unable to verify by the experiment  Average activity coefficient

   1/ 1
   (  .  ) lg    (  lg      lg   )


lg     Z  Z  h I   Z 2    Z 2
lg     h I .
   

Debye-Hückel limiting law 1

30
 lg     Z  Z  h I

Adapt to the experimental Lewis-Randall equation

Activity coefficient of electrolytes having similar ionic strength
must be equal
Debye-Hückel limiting law 1
1,825.10 6
lg     C  0,507 C
Water, electrolyte 1-1, 20oC: (80,1.293) 3/ 2

Experimental Brönsted equation lg f   0,5 C

Water, electrolyte 1-1, 20oC, diluted solution:

31
 2.4 Advantages, missing points of Debye-Hückel
theory and perspectives

• Describe exactly the dependence of activity coefficient

on I and T
• Calculate the thermodynamic values of ionic solution:
entropy, molar heat capacity, mol compression degree,
mol dilation degree, ...
• Predict Hdilution of electrolyte solution (ion interaction
decrease). Following Debye- Hückel theory: at low
concentration, Hdilution of solution is proportion to the
C1/2  experimental determination.

Debye-Hückel limiting law doesn’t contain any

experimental factor 32
 Some missing points
Experiment values of activity coefficient and values calculated following
the Debye-Hückel theory for NaCl solution

m 0,0001 0,001 0,005 0,010 0,050 0,100

±TN 0,975 0,9649 0,9275 0,9024 0,8205 0,7813

±LT 0,971 0,9634 0,9200 0,8890 0,7652 0,6896

• Only adaptable in case of solution concentration  0,01 m

• The higher Zi is, the larger deviation between theory and
experiment is.
Why?
33
 Problems
• Ignore the ion size toward to the distance between two ions
• Hypothesis: Zieo << kT
• Don’t count the changing of solvent during dissolution process
• Consider ion as charge point
• Consider just the ionic interaction, ignore other interactions

Only adaptable for diluted solution

Debye và Hückel law limiting 2: ion size 34

 lim[ - i]ra
Z  Z  h. I Z  Z  h. I
lg     
1  a 1  aB I
Z i eo e a
A1 
4 o (1  a)
B = /I1/2)

NaCl solution 0,1 m, 25oC  a = 4,8 Ǻ

1-1, water at 25oC Z  Z  h. I

Guntenberg lg    
a  3,04 Ǻ, a.B  1 1 I

35
Comparison the coefficient activity given by the experiment and the calculated
values from Debye – Hückel for NaCl solution at 25oC, a = 4,8 Ǻ.

m 0,001 0,005 0,010 0,050 0,100

 log±TN 0,0155 0,0327 0,0445 0,0859 0,072

 log±LT 0,0154 0,0325 0,0441 0,0844 0,077

Debye – Hückel:

Z  Z  h. I
lg      CI
C – empirical constant 1  aB I
m=12 36