CHAPTER II

ION – DIPOLE
INTERACTIONS AND
SOLVATION

1
 1. Formation of electrolyte solutions

Electrolyte solutions
=

Ionic compound: Ul
Dissociable Solutes
Polar covalent compound: D

+
 : permittivity
r (D) relative
Polar solvents permittivity(dielectric constant)
D = /o:
: Dipole moment
2
 Classification of solvents

- Solvents can be classified as polar, non-polar and apolar, general

classification uses the relative permittivity

Solvent water HCN C2H5OH Aceton Benzen CCl4

r 78 103 24 21 2,3 2,2

- Coulomb Law’s: the force of electrostatic interaction

between two ions in a solution
Z1Z e 2
F =- 2 o

4pereor 2

- Interaction force - F is in inverses ratio to relative permittivity- r

3
 2. Solvation
- Ion compound

Dissolve NaCl crystal in water

A solvated cation and anion 4

- Polar covalent compound

5
 Enthalpy of Dissolution (Hdiss):

Ionic compound:

Hdiss = Ul + Hhyd

Lattice energy Enthalpy of hydration

Ul > 0 (Hhyd)
(Hsol) – solvent
Hsol < 0 ; Hhyd < 0
Polar covalent compound:
Ul is replaced by D – dissociation enthalpy ; D > 0
6
 3. Lattice energy
a) M. Born model (1920)

Lattice Energy: U = −  F dr
ro

F: force of electrostatic interaction between two ions

❖ Attractive force between two ions Z1eo Z1Z 2 eo2

and Z2eo in vacuum: Fatt = -
4peor 2

❖ Repulsive force (Frep, positive) by B

interaction between two electron shells Frep = n+1
r
B và n are factors , n > 1
7
 a) Determination of lattice energy using M. Born
model (1920) 2
Z1Z2 eo B
Total force of ion interactions: F = Fatt + Frep = - +
4peo r 2 r n+1
 ¥æ Z1Z2 eo2 B ö Z1Z2 eo2 B
U = −  F dr DU = - ò ç - + n+1 ÷dr = - n
ro è 4pe o r r ø 4peoro nro
2
ro

Obtain B: Equabrilium, r = ro → F = 0

Z1Z2eo2 B Z1Z2 eo2 ron-1

Fatt r = Frup r ® = n+1 Þ B=
o o 4peoro ro
2
4peo

Z 1 Z 2 eo2  1
- An ionic pair: U = 1 − 
4 o ro  n
8
- For a mole ion:

Z 1 Z 2 eo2  1  NA, Madelung constant

U = 1 −  GL = NA.A.U
4 o ro  n 
ro
Madelung constant : A =  () i
i ri
For example: NaCl face - centered cubic topology
12 8 6 24
A= 6− + − + − ..... = 1,7476
2 3 4 5

9
 a) Calculating lattice energy using the M. Born
model (1920)
Lattice energy: GL= NA.A.U

Z Z e 2
æ 1 ö
A – Madelung constant DGl = N A A 1 2 o
ç1- ÷
ro – shortest distance between two ions 4peoro è n ø
n – the repulsive factor that can be (Born – Landé)
determined from  factor.
18ro2
n = 1+ NaCl: n = 7,5 (5 –12)
Ae o2
Lattice energy of NaCl:

6,022.10 23.1,7476.(1,6022.10 −19 ) 2  1 

G NaCl =  1 −  = 7,624.10 5
J / mol = 762kJ / mol
4.3,14.0,88542.10 −11.(095 + 1,81).10 −10  7,5 

10
 b) Calculation of Lattice Energy using Born – Haber cycle

Na(r) + ½ Cl2 (k) NaCl (r)

Na (k) Cl (k) -U=-788 kJ

Na+(k) Cl-(k)

U = (Hosub + HoIE + HoD + HoEA) – Hof = 788 kJ

GoLe,NaCl = U – TSo = 788 - 15 = 773 kJ/mol Born – Haber (TN)

762 kJ/mol Born – Landé (LT)
11
Lattice Energy of halogenur ankaline metal at 25oC

Cation HL, kJ/mol

F− Cl− Br− I−
Na+ 911 772 741 -
K+ 810 702 678 637
Rb+ 780 - 658 621
Cs+ 744 - - 604

12
 3. Enthalpy of Solvation
a) Enthalpy of solvation – Born – Haber cycle

UL = 772 kJ/mol
UL
NaCl (s) Na+(g) + Cl−(g)

Hdiss Hhyd (**)

Hdiss = 4 kJ/mol Na+(aq) + Cl−(aq)

Hhyd,NaCl = Hhyd,Na+ + Hhyd,Cl− = Hdiss - UL = 4 – 772 = −768 kJ/mol

13
b) Energy of solvation
* Born model

W1 Gosol,Born = NA.W

W = W1 + W2 + W3
W2
For W2 = 0
→ W = W1 + W 3
W3

14
14
 ri
q q
X= j= j = - ò X dr
4peoer r 2
4peoer ri ¥
φ is the electric potential at the surface
of the ion
q q
q q 2
W = ò j dq = ò 4pe e r dq = 8pe e r
0 0 o r i o r i

Z e 2 2
Z e
2 2
W1 = - i o
; W3 = i o (Note W1 ≠ W3 !)
8peo ri 8peoer ri

The energy for transfer of 1 ion (Zieo) from a vacuum into the solvent (r)

Zi2 eo2 Zi2 eo2 Zi2 eo2 æ 1 ö

W = W1 +W3 = - + =- ç1- ÷
8peori 8peoer ri 8peori è er ø

15
 * Born model Gosol,Born = NA.W

Zi2 eo2 æ 1ö
DGsol = -N A ç1- ÷
8peo ri è er ø

d (G sol )
H sol = G sol − T
dT

Zi2 eo2 æ 1 T der ö

-DH sol = NA ç1- - 2 . ÷ Born-Bjerrum
8peo ri è er er dT ø

Increase in ionic charge Zieo

Decrease in ionic radius ri Increase in solvation energy

High dielectric constant r

16
 Determine Hydration Enthalpy of NaCl from Born
Model

Ghyd, kJ/mol Hhyd, kJ/mol

Na+ 722 734
Cl− 379 386
NaCl 1101 1120

Hhyd values determine from Born – Harber cycle and Born model

− Hhyd, 25oC, kJ/mol

LiCl NaCl KCl RbCl CsCl
Born model 1549 1120 910 857 798

Born-Harber Cycle 883 768 685 664 639

17
 - Hhyd , kJ/mol

Li+ Na+ K+ Mg2+ Ba2+ Al3+ H+

F− 959 846 762 2809 1850 5986 1532
Cl− 883 768 685 2658 1700 5768 1461
Br− 850 726 653 2566 1633 5668 1427
I− 804 695 611 2503 1545 5115 1381
OH− 871 762 620

18
 Others model

a) Bernal và Fowler
b) Mishenko
c) Frumkin
d) Izmailov

19
 4. Entropy of solvation
H, G và S at 25oC
− Hhyd, − Ghyd, − TShyd, − Shyd,
kJ/mol kJ/mol kJ/mol J/mol
LiF 1025 925 100 336
NaF 911 825 86 289
KF 827 752 75 252
RbF 806 730 76 255
CsF 782 698 84 282

Shyd < 0 solution is higher order structure

Born model Zi2 eo2 de Best-fit in

DSsol = N A ×
8peoe ri dT
2
experimentation
(d/dt ) < 0 20
 5. Solvation numbers

ns  nk

Experimental data for solvation numbers of cations

nh Z=1 Z=2 Z=3

4 Li Be −
4-6 Na Ca
Mn, Fe, Co, Ni, Cu, Al, Ga, In, Tl, Bi, Ti, V, Cr, Mn,
6 −
Zn, Cd, Hg Fe, Co, Rh, Ir
La, Ce, Pr, Sm, Eu, Gd, Tb, Dy,
8-9 − −
Lu

21
 CHAPTER III.
IONIC INTERACTIONS IN
ELECTROLYTE

22
1. Activity and activity coefficient

➢ Quantities issue of , Kdiss

➢ The expressions are valid in very Why?
dilute solution

ion-ion
ACTIVITY
interactions
➢ ACTIVITY as a function of the composition of the solution
➢ The concentration in the thermodynamic expressions can be replaced
by quantities activity
+
[H ][A ] - aH + a A - K’: Apparent dissociation constant
K'= K= K: real (thermodynamic
[HA] aHA dissociation constant
23
 1. Activity and activity coefficient

Molarity aC = C.C For a very (aC → C)C→0

Molality am = m.m dilute solution (am → m)m→0
Mole fraction aX = X.X (aX → X)X→0
n+ n-
a=a a
❖ The quantity C, m, X (or +fC, fm-, fX): C = m = X = 1
Activity coefficienta = n a = (an + .an - )1/n
± + -
n+ n - 1/n
m = (m
n
a ±= a+ a-+ n
+ -.m- )

ga n n + n -n - 1/n
a± ===a(ng+ +aa.-=
+ g -(a)n + .an - )1/n
Mean quantities ± + -

a = n a n= n + 1/nn - 1/n
+ (an - .a
m±± = (m+ .m-+ ) - )
m = n + n + .m
n - n1/-n)1/n
g ±±= (g + +.g - )-
(m 24
1. Activity and activity coefficient

æ ¶G ö - Chemical potential - i
mi = ç ÷ - Gibbs energy - G
è ¶N i øN - Amount of substance - ni
j¹i ,T,P

m ideal
i
= m (T )+ RT ln Xi
o
i R: molar gas constant
T : thermodynamic temperature
m real
i = m (T ) + RT ln aXi
o
i
Xi : mole fraction
= mio (T ) + RT ln Xi + RT ln g Xi 0 : standard chemical potential

m real
i -m ideal
i = RT ln g i = g *
i

g* is the correction for the real behavior, which can be identified with the
expression containing the activity coefficient. 25
1. Activity and activity coefficient for electrolyte
BA = ++ + −−
BA = + B+ + − A−
mBA
o
= n +m+o + n -m-o
Ideal case Real case

m ideal
BA = m + RT lnCBA
o
BA
m = m + RT ln aBA
r
BA
o
BA

m+ ideal
= m + RT lnC+
o
+
m +r = m+o + RT ln a+
m ideal
- = m + RT lnC-
o
-
m-r = m-o + RT ln a-
a = a+n + a-n -
RT ln aBA = n + RT ln a+ + n - RT ln a-
a = n a = (an + .an - )1/n
1 ±
n n + -
n+ n-
= RT ln a+- a- aBA == (m
m a+ n.a
+
+ -
-
n® an± = a
n
n
- 1/
± + .m - )
Mean activity coefficient: g ± = (g +n .g -n )1/n
+ -

26
 Mean activity coefficient
C, mol/l 10-3 10-2 5.0 x10-2 0.100 0.500 1.00 2.00
 (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

✓Osmotic pressure (1),

✓Raoult‘s law (Freezing point suppression (2))
✓ Potentiometric methods (3)

Quantity I, called the ionic

strength:

å å
1 1
I= mi Zi2 or I= Ci Zi2
2 i 2 i

27
 Mean activity coefficient
For MgCl2
C (M) 0.100 0.200 0.400 0.800 1.00 2.00 5.00
 0.516 0.468 0.442 0.445 0.479 0.668 1.550

➢ Activity coefficient of electrolytes must depend on the electric charge

of all the ions present.
➢ Lewis, Randall, Brönsted: experimentally for dilute solutions the
dependence is described quite adequately by the relationship.

lgg ± = -h I
For 20oC, Water h ~0.5 dm3/2 . mol-1/2

28
➢ Lewis – Randall Brönsted relationship is valid in low
concentration solution, m  0,02

Lg

CaCl2
lgg ± = -h I

K2SO4

29
 Application of activity and activity coefficient
❖ Dissociation constant

BA ⇄ +Bz+ + −Az−

K - thermodynamic or real dissociation constant

K’ – apparent dissociation constants

Water, 25oC, 1-1:

lg  + = lg  − = − A I = −0,5 I
K
K'= = K .10 I

 B A  B =  A = 10 −0 , 5 I
;  BA = 1
30
❖ degree of dissociation (fraction ionized)

[𝐵𝑧+ ]𝜈+ [𝐴𝑧− ]𝜈− 𝛼2 𝐶 𝐾′

𝐾′ = = ≈ 𝐶𝛼 2 𝛼=
𝐶
[𝐵𝜈+ 𝐴𝜈− ] 1−𝛼

𝜈+ 𝜈− 𝜈+ 𝜈−
𝜈+ 𝜈−
𝑎𝐵 𝑎𝐴 [𝐵𝑧+ ]𝜈+ [𝐴𝑧− ]𝜈− 𝛾𝐵 𝛾𝐴 𝛾𝐵 𝛾𝐴 𝐼
𝐾= = =K’ =K’10
𝑎𝐵𝜈+ 𝐴𝜈− [𝐵𝜈+ 𝐴𝜈− ] 𝛾𝐵𝐴 𝛾𝐵𝐴

31
❖ pH, solubility product constant, Ksp

➢ pH =- log aH+ → pH’ = - log [H+] - logH+

𝜐+ 𝜐− 𝜐+ 𝜐−
➢ Ksp= 𝑎𝑀 𝑎𝑋 = [𝑀 𝑧+ ]𝜐+ [𝑋 𝑧− ]𝜐− 𝛾𝑀 𝛾𝑋
= [𝑀 𝑧+ ]𝜐+ [𝑋 𝑧− ]𝜐− 𝛾±𝜐 = 𝐾′𝑠𝑝 𝛾±𝜐

32
 Example 1
• NH3 has a pKb = 4.75 at 25oC. What is the pH
and fraction protonated for a 0.02 M solution
of NH3 (aq)?
• How do these values change if the
concentration drops to 1.00 x10-5 M and the
same approximations are made? Comment on
the result.

33
 Example 2
The pH of a 0.050 M solution of a weak acid is 3.53 at 25oC.
1. Calculate Ka, making the standard approximation that pH
=- log10[H3O+].
2. A conductance measurement on this solution gives
[H3O+]actual = 3.04 x 10-4 M directly. Comment on the
difference between this value and that found using the
approximation in 1. What implications does this have?

34
 Example 3
The same aqueous solution of the acid, HX, of
stoichiometric concentration equal to 6.24 x10-2 M has a pH
of 1.75 at 25 oC.
1. Find pKa if non-ideality is totally ignored.
2. Find pKa when corrections are made for non-ideality.
3. Comment on the results.

35
 Example 4
1. Hg2Cl2(s) is sparingly soluble in water at 25oC, solubility =
6.5x10-7 M. Calculate the solubility product and explain
why it is not necessary to correct for non-ideality.
2. Calculate the solubility in 0.100 M KNO3 solution.
3. Compare the solubilities in the two solutions

36
 The distribution of ion in electrolyte and ionic
atmosphere model
- + - -
➢ Ideal solution: electrostatic interionic forces +
is neglected (Arrhenius) + - - +
➢ 1806, T. Grotthuss: ionic conductivity - + +
➢ Non-ideal solution (Debye - Hückel - 1923 ): Ideal case
electrostatic interionic forces concept of an
ionic atmosphere: Excess charge due to ions
-
with the opposite charge is concentrated + - -
around each ion and the charge density is +
+ - +
distributed in the ionic atmosphere +
-
according to the Maxwell-Boltzmann + -
distribution law
Real case
Atkins, Physical Chemistry. 6th ed. Figure 10.2
37
 The concept of Debye - Hückel Theory

- Ionic atmosphere: an
excess charge due to ions with
the opposite charge is
concentrated around each ion
and the charge density is
distributed in. This excess
charge is equal to the charge
of the ion considered

-Debye and Huckel assumed that a spherical ionic atmosphere of

statistically prevailing ions with opposite charge forms around
each ion
38
2.2 The potential of the spherical ionic atmosphere
The potential of the space charge density p is given by the Poisson
equation:  - 

 d 2 2 d  : potential;  : charge density

  =− = 2 +
2

 o dr r dr

 = niZieo ni : local concentration of i

W: electrostatic energy
W
ni = nio exp( − ) kT: energy of thermal motion kT
kT
Z i eo
ni = nio exp( − )
kT
 Z i eo  
W = Zieo  =  nio Z i eo . exp − 
 kT 
39
  Z i eo  
 =  nio Z i eo . exp − 
 kT 
2
x
e x = 1 + x + + .... e x =1 + x Taylor approximations
2! x << 1
the electrostatic energy eZiφ is small
compared with the energy of thermal
Z i eo motion kT
 1
kT
 Z i eo   nio Z i2 eo2
 =  [nio Z i eo .1 − ] =  (nio Z i eo ) −  ( )
 kT  kT

(nioZieo) = 0  eo2 2 
 = −  (ni o Z i ) 
Electroneutrality condition  kT 
40
 2
1 e
  o kT i io i i
 =
2 o 2
n z

eo2
=
 o kT
 ( n 2
io i )
Z
− r r
 2 d
e e
 = A1 + A2
2
d
=  = 2 + =  2
2

dr r dr r r
r → = 0 A2 = 0
Z i eo e a e − r
A1 =  = A1
4 o (1 + a) r

Z i eo  eo2 2 
A1 = Ion is point charge  = −  (ni o Z i ) 
4o  kT 
41
 Z i eo e − r  : Potential
=
4 o r
a : potential of the ionic atmosphere
a = [ - i]r → 0 i : potential of the central ion  i = Z i eo
4o r

1/ 1/ : effective radius of

Z ie o the ionic atmosphere
− Z ie o

Z i eo e − 1
 − r Z i eo 
a =   a = −
4o  r  r →0 4o
42
 i =
Z i eo Z i eo 
4o r a = −
4o
q1q2
DU = Interactions energy per 1 ion pair
4peor

Z e 
2 2
U = − i o

8o
-
+ - -
+
+ 1/
- + 1/
- Z ie o Z ie o -Zieo
+
- + - + − Z ie o
43
Debye- Hückel limiting law and activity coefficient

Z i2 eo2 
m
real
i - m = RT ln g i = g
id
i
*
i RT ln  i = N A U = − N A
8o

eo2
=
 o kT
 ( n 2
io i )
Z 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
2.103 N A I
o

1 C+ = C− = C
I =  Ci Z i2 I=C
2 i 1−1
44
 lg  i = − Z i2 h I

(1, 6022.10-19 )3 (2.6, 022.10 23.10 3 )1/2 1

h= .
2, 3026.8.3,1416.(0,88542.10 .1, 3807.10 ) (eT )
-11 -23 3/2 3/2

6
1,825.10 -3/2
= (l / mol)1/2
.K
(eT )3/2
+  − 1/
  = ( + . − )
1
lg   = ( + lg  + +  − lg  − )


lg   = − Z + Z − h I  + Z +2 +  − Z −2
lg   = −h I .
 + + −
Debye-Hückel Limiting law
45
 lg   = − Z + Z − h I Debye-Hückel limiting law

1,825.106
lg   = − 3/ 2
C = −0,507 C
Water, dilute 1-1, 20oC:
(80,1.293)

Brönsted pratical eq.

lg f  = −0,5 C

46
 Using of Debye – Hückel limiting law
For NaCl Solution

m 0.0001 0.001 0.005 0.010 0.050 0.100

±p 0.975 0.9649 0.9275 0.9024 0.8205 0.7813

±T 0.971 0.9634 0.9200 0.8890 0.7652 0.6896

❖ Debye – Hückel equation Z + Z − h. I

lg   = −
1+ I
Z + Z − h. I Z + Z − h. I
lg   = − =− Z+ Z- h. I
1 + a 1 + aB I lg g ± = -
1+1.5 I
Bate-Guggenheim
47
 Advanced Debye – Hückel limiting law
For NaCl solution

m 0.001 0.005 0.010 0.050 0.100

− log±P 0.0155 0.0327 0.0445 0.0859 0.072

− log±T 0.0154 0.0325 0.0441 0.0844 0.077

Z + Z − h. I
lg   = − + CI
1 + aB I
C – practical factor
48
 ❑ Dependence
of y± of NaCl
on the
square root
of molar
concentration
c at 25°C

❖ Circles are experimental points.

❖ 1- Debye-Hiickel limiting law, 2 approximation aB = 1; 3 - Debye-Hiickel equation a =
325nm; 4 - Bates- Guggenheim approximation; 5 - Bates-Guggenheim approximation +
linear term 0.1 C; 6 - Advanced Debye – Hückel Eq. for a=0.4nm, C = 0.055 M.
49
 Worked problem
The pH of a 0.050 M solution of a weak acid is 3.53 at 25oC.
1. Calculate Ka, making the standard approximation that pH
=- log10[H3O+].
2. A conductance measurement on this solution gives
[H3O+]actual = 3.04 x 10-4 M directly. Comment on the
difference between this value and that found using the
approximation in 1. What implications does this have?

50
 Worked problem
The same aqueous solution of the acid, HX, of
stoichiometric concentration equal to 6.24 x10-2 M has a pH
of 1.75 at 25 oC.
1. Find pKa if non-ideality is totally ignored.
2. Find pKa when corrections are made for non-ideality.
3. Comment on the results.

51
 Worked problem
1. Hg2Cl2(s) is sparingly soluble in water at 25oC, solubility =
6.5x10-7 M. Calculate the solubility product and explain
why it is not necessary to correct for non-ideality.
2. Calculate the solubility in 0.100 M KNO3 solution.
3. Compare the solubilities in the two solutions

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 Example 1
• NH3 has a pKb = 4.75 at 25oC. What is the pH
and fraction protonated for a 0.02 M solution
of NH3 (aq)?
• How do these values change if the
concentration drops to 1.00 x10-5 M and the
same approximations are made? Comment on
the result.

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