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CHAPTER II
CONTENT
ION – DIPOLE INTERACTION
II.1. Formation of electrolyte
IN ELECTROLYTE SOLUTION
II.2. Lattice energy of crystal
SOLVATION PROCESS
II.3. Solvation process. Enthalpy (heat) of
solvation
II.4. Entropy of solvation
II.5. Solvation number

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1. Formation of electrolyte Kind of interactions

How can we form the electrolyte ? What are requirements ?

Polar solvent • ion – ion interaction

Electrolyte • ion – dipole interaction
Solute can dissociate
• dipole – dipole interaction
in ions
• hydrogen bond
Polar solvent Dielectric constant:
• Dispersion force (London force): cation –
 hay r ; D = 4/o
induced dipole; dipole – induced dipole.
Dipole moment 
Solute able to Ionic crystal: Ucrys
dissociate Covalent compound: Do
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Ionic interaction Dielectric constant

• Columbic force: electric repulsion and
attraction

 = 1: vacuum
environment
 : dielectric constant
( hay r – relative dielectric constant C
r = (C: capacitance)
In vacuum In other environment (dielectric constant, relative permitivity) Co
5 6
D (dipole moment) = 4/o

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Role of dielectric constant Ion – dipole interaction

Coulomb force between 2 ions (F) Ionic crystal: Liberated energy calculated for 1 mol solute
2 given by interaction between the ion and
Z1 Z e
F =− 2 o dipole of solvent (solvation energy)
4 ro
2

Free existing ion in solution

F is smaller Stable electrolyte

High r values Highly polar

solvents
Solvents Water HCN C2H5OH Aceton Benzen CCl4
r 78 103 24 21 2,3 2,2

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Dissolution process – Heat of solution

Heat of solution (enthalpy) released by dissolution process

Integral enthalpy: enthalpy releases when 1 mol solute

dissolves in the given volume of solvent
Differential enthalpy: enthalpy releases when 1 mol
solute dissolves in the large amount of solvent (C → 0)

Energy need to break down the lattice energy >> Heat

of solvation
Energy for breaking down the lattice energy ??

9 The interaction between solvent molecules – ions?? 10

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Heat of solution (Hs): Heat releases by dissolution Ion – dipole interaction

process.

Solute has a crystal structure

Hs = Hcrys + Hhyd

Energy for breaking down a Hydration enthalpy (Hhyd) or

crystal lattice Solvation enthalpy (Hsol)
Hcrys > 0
Hsol < 0 ; Hhyd < 0 Negative charge of dipole molecule aligns itself to the cation
Solute has : Positive charge of dipole molecule aligns itself to the anion

Hcrys replaced by Do – energy of dissociation bonding → Hydrated layer aligned to the ion
Hs : experimentally determined by Calorimetry method
Ion-dipole interaction: exothermic process
Hsol Hcrys : can’t be experimentally determined 11
System arranges in order, entropy of system decrease
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Thermodynamics rules 2. Lattice energy of crystal

In case of ion: The thermodynamic state functions are a) M. Born’ model (1920)
similar to the neutral compound.
Lattice energy of crystal: energy requires to break down crystalline
lattice, or particularly convert the crystal into infinitely separated
Hfo: standard enthalpy of formation at 25oC, 1 atm gaseous ions in vacuum.

Gfo: standard Gibb free energy of formation of a U (internal energy) related to the
separation of ions
U = −  F dr
compound ro
F: ionic interaction between two ions in crystal lattice
Sfo: entropy/free probability Z 1 Z 2 eo2
Electrostatic force (attraction, Fhút, negative) Fhut =−
How to calculate the standard enthalpy of formation when between two ions Z1eo and Z2eo in vaccum: 4 o r 2
the substance dissociates completely in the solution?
B
Repulsion force (Fđẩy, positive) due to the Fday =
Standard: Hfo (H+, aq) = 0; Gfo (H+, aq) = 0; Sfo (H+, aq) = 0 interaction of electronic outer-layers r n +1
13 B, n: constant n > 1 14

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a) M. Born (1920) Model: calculate lattice energy of a) M. Born (1920) Model: calculate lattice energy of
crystal crystal
Total force between two ions: For couple of ions : Na+ và Cl-

Z Z e2 Z1 Z 2 eo2  1 NA, A Madelung constant

F = Fhut + Fday
B
= − 1 2 o2 + n+1 U = 1 − 
4 o ro  n Gtt = NA.A.U
4 o r r Calculated for 1 mol

U = −  F dr A: Madelung constant A =  () i
ro
ro
i ri
Examples: NaCl – cubic lattice

 ZZ e B 
2
ZZ e B 2
12 8 6 24
U = −   − 1 + n+1 dr = 1
2 o
− n 2 o
A= 6− + − + − ..... = 1,7476
ro  4 r o
2
r  4 o ro nro 2 3 4 5

equilibrium, r = ro → F = 0
Determine B
Z1 Z 2 eo2 B Z1 Z 2 eo2 ron −1
Fhut = Fday → = n +1  B=
ro ro 4 o ro 2
ro 415o 16

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a) M. Born (1920) Model: calculate lattice energy a) M. Born (1920) Model: calculate lattice energy

Lattice energy of crystal: Gcrys = NA.A.U

A - Madelung constant
Z1 Z 2 eo2  1 
ro – equilibrium distance between two Gtt = N A A 1 − 
nearest opposite charged ions in crystal 4 o ro  n  (*)

lattice (Born – Landé)

n – characterized for repulsion force,
determined by  (press constant) 18ro2
n = 1+ NaCl: n = 7,5 (5 –12)
Aeo2

Energy of crystal lattice:

Hof = Hosub + HoIE + Hod + HoEA + (− Ucrys)
−19 2
23
6,022.10 .1,7476.(1,6022.10 )  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 
Ucrys = (Hosub + HoIE + Hod + HoEA) – Hof
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Hcrys of halide alkaline at 25oC

Cation Hcrys, kJ/mol

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

Gtt,NaCl = U – TS = 788 - 15 = 773 kJ/mol Born – Haber (exp.)

762 kJ/mol Born – Landé (theory)
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3. Solvation process. Enthalpy of solvation b) Energy of solvation

a) Enthalpy of solvation –Born – Haber cycle Definition: energy releases when 1 mol of ion moves from
Hcrys = 772 kJ/mol the vacuum into a given solution
* Born’ model
Htt
NaCl (r) Na+(k) + Cl−(k)
Gosol,Born = NA.W
W1
Hht Hhyd
Hht = 4 kJ/mol Na+(aq) + Cl−(aq) W2
(i) Electric charge is removed completely
in vacuum (work W1);
W3 (ii) Bring the non-charge ion from vacuum
Hhyd,NaCl = Hhyd,Na+ + Hhyd,Cl− = Hht - Hcrys = 4 – 772 = −768 kJ/mol
to the solution (work W2);
(iii) Charging the ion (work W3)
Enthalpy of solvation can’t be experimentally determined
21 W = W1 + W2 + W3 Hypothesis W 2 = 0 22

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q
X = * Born’ theoritical model
q q 4 or 2 Gosol,Born = NA.W
q q2
Wtd =  dq =  dq =
ri ri
q q
 = −  Xdr = −  dr =
4 ori 8 ori 4 r 2
4 o ri
Z i2 eo2  1
0 0   o

Gsol = −N A 1 − 
Z 2e2 Z 2e2 8 o ri   
W1 = − i o ; W3 = i o
8 o ri 8 o ri d (Gsol )
H sol = Gsol − T
dT
(Attention: Different between W1 and W3 !)
Z i2 eo2  1 T d 
− H sol = N A 1 − − .  Born-Bjerrum
8 o ri    2 dT 
Required energy for putting 1 ion Zieo into solvent  :

Z i2 eo2 Z i2 eo2 Z 2e2  1  Ion charge Zieo increase

W = W1 + W3 = − + = − i o 1 −  Energy of solvation
8 o ri 8 ori 8 o ri    Ionic radius ri decrease increases
Dielectric constant : high
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Energy of hydration calculated for NaCl following Born’ model

Enthalpy of hydration, - Hhyd , kJ/mol (**)
Ghyd, kJ/mol Hhyd, kJ/mol
Na+ 722 734 Li+ Na+ K+ Mg2+ Ba2+ Al3+ H+
Cl− 379 386 F− 959 846 762 2809 1850 5986 1532
NaCl 1101 1120
Cl− 883 768 685 2658 1700 5768 1461
Hhyd followed Born’ model and thermodynamic cycle of Born – Harber Br− 850 726 653 2566 1633 5668 1427
− Hhyd, 25oC, kJ/mol I− 804 695 611 2503 1545 5115 1381
LiCl NaCl KCl RbCl CsCl OH− 871 762 620
Born’ model 1549 1120 910 857 798
Born-Harber For the ions having the same valence and quite similar
883 768 685 664 639
cycle property, what’s the tendency of Hhyd ?

What do you think about the large discrepancy?

How to explain it? In increasing the ionic charge, how is Hhyd ?
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* Semi-empirical model: 4. Entropy solvat hóa

H, G and S of fluoride metal hydration at 25oC
a)Bernal và Fowler
− Hhyd, − Ghyd, − TShyd, − Shyd,
b)Mishenko kJ/mol kJ/mol kJ/mol J/mol
c) Frumkin LiF 1025 925 100 336
d)Izmailov NaF 911 825 86 289
KF 827 752 75 252
Self-study at home!!! RbF 806 730 76 255
CsF 782 698 84 282

Shyd < 0 ordered structure of water

Qualitative
Born’ model Z i2 eo2 d
S sol = N A  analysis fitted to
8 o 2 ri dT
27 (d/dt ) < 0 the experiment 28

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5. Solvation number
− Shyd, J/(mol.K), calculated following Born’ model and also
basing on the mass spectroscopy data (in parenthese, using ion H+ Definition: Average number of solvent molecules closely
as standard) at 25oC. bonded to the ion
Symbol: ns (nh).
Li+ Na+ K+ Rb+ Cs+ F− Cl− Br− I− Limit value of solvation number is equal to the coordination
number (nk): ns  nk
46 35 27 25 22 34 24 22 20
(164) (133) (96) (87) (81) (115) (53) (37) (14) Experimental value nh of cation
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
29 8 ... 9 − − La, Ce, Pr, Sm, Eu, Gd, Tb, Dy,
30 Lu

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Some conclusions from experimental investigation: q high Strong electric field

• nh  nk 1 >> 2 nh = nk
r small
• nh could be determined by different methods Example: Li+ : nh = nk = 6
• In some solution, nh decreases in increasing concentration of
solution Weak electric field
q nhỏ
• nh couldn’t be always an integer value 1 << 2 nh = 0
Samoilov : kinetic property of solvation layer r lớn
Example: Cs+ và I−
→ Solvation theory based on dynamic

1 : average time that ions are quiet In the same column (group), from top to down, ri
2 : required time for dipole aligns and connects to the increases :
solvation layer ✓ Solvation capacity decrease gradually : Hsol lower
Samoilov can explain: ✓ Solvation layer is ‘thinner’ : ri, sol lower
nh depends on the determination methods
31 32
nh increas when ionic radius increases and valence decreases

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MIND MAP

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35 36

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37 38

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