Chapter 1

Equilibrium Properties of
Electrolyte

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 I. Terminology
❖ A substance present in solution or in a melt which is at
least partly in the form of charged species – ions is called
an electrolyte.

❖ The decomposition of electroneutral molecules to form

electrically charged ions is termed electrolytic dissociation

❖ Ions with a positive charge are called cations; those with

a negative charge are termed anions. Ions move in an
electric field as a result of their charge - cations towards
the cathode, anions to the anode
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+ Solution concentration
▪ Molarity, M (mol/L);

▪ Molality, m, mol/kg;

▪ Mole fraction, unit less or %;

▪ Normality, N (eq/L).

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II. The differences between nonelectrolytes and
electrolytes
Laws Nonelectrolyte Sol. Electrolyte Sol.

Raoult I P/Po = N2 P/Po = iN2

Tb = Kb Cm Tb = i Kb Cm
Raoult II Tf = KfCm Tf= i Kf Cm

Van’t hoff  = CRT  = i CRT

P n
=N = 2

Po
2 n +n
2 1
With water: Kb =0.52, Kf = 1.86, Cm: molality
✓ : osmotic pressure; R – gas constant (0.082 atm T-1 mol-1; T –
absolute temp. (K); C – concentration mol/l.
✓ i correction factor for electrolyte solutions 4
 III. The Arrhenius theory of electrolytes
1. Substance dissociates in solution to yield ν ions consisting of ν+
cations and ν- anions (ν is electrolytic order)

CH3COOH ⇄ CH3COO− + H+
2. The degree of dissociation is the equilibrium degree of
conversion, the fraction of the number of molecules originally
present that dissociated at the given concentration.
n'
=
n
3. Electrolytic dissociation is reversible reaction, that equilibrium
state is described by the law of mass action.

[𝑀+ ]𝜈 + . [𝐴− ]𝜈−

M  A − =  + M +  − A
+ −
𝐾𝑑𝑖𝑠 =
+ [𝑀𝜈 + 𝐴𝜈 −] 5
IV. Application of Arrhenius theory of electrolyte

1. To distinguish the strong, weak electrolytes

❖ The solution that are fully dissociated so that their
molecules are not present in the solution are called
strong electrolytes,
❖ The solution that dissociate incompletely are weak
electrolytes. Ions as well as molecules are present in
solution of a weak electrolyte at finite dilution.

2. Determination of correction factor – i for electrolyte

i −1
=
 −1
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3. Determine the dissociation constants
HA ⇄ H+ + A-
[H + ].[A- ] C.a 2
K = K =
a [HA] a
1- a
4. Ostwald dilution law
Ka
a=  = K.V
C
5. Definition of pKa, pH

pKa = - log Ka
pH =-log [H+]
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Exp 1. Find the pH of a 20 cm3 sample of a 0.05 M solution of a weak
acid of pKa = 5.75 at 25oC. Calculate the fraction ionised, and
comment on its value. How does this correlate with any assumptions
made in the calculation of the pH?

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Exp.2. If the acid used had instead a pKa value of 1.85 how would
the reasoning be altered? Find the pH, and the fraction ionised.
Explain the approximations made.

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6. Buffer solutions
Cm
𝐴− = 𝑁𝑎𝐴 + 𝐻 + ≈ [𝑁𝑎𝐴]
HA ⇄ H+ + A- 𝐻 + [𝐴− ]
𝐾𝑎 =
[𝐻𝐴] 𝐻𝐴 = 𝐶𝑎 − 𝐻 + ≈ 𝐶𝑎
NaA → Na+ + A-
+
𝐾𝑎 𝐶𝑎
𝐻 =
𝐶𝑚

C
pH = pK − lg a
a C
m Handerson – Hasselbach
C
pH = 14 − pK + lg b
b C
m
Ca, Cb, Cm: Concentration of weak acid, weak base, salt
Ka và Kb: Dissociation constants of acid and base
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 7. Buffer capacity
dc a−c
 = pH = pK − lg
dpH a b+c
dpH 1 1 1 1 a+b
= .( + )= .
dc 2,3 b + c a − c 2,3 (b + c)(a − c)
dc a.b
Khi c=0  = = 2,3.
dpH a+b

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Exp. Using the approximate treatment given above, work out the
pH of a buffer solution containing 0.10 M of NH3(aq) and 0.02 M
NH4Cl(aq). pKa for NH4+ at 25oC is 9.25

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8. Multi step dissociation
K =  Ki

• H3PO4 ⇄ H+ + H2PO4- K1 = 7,6.10−5

• H2PO4- ⇄ H+ + HPO42- K2 = 6,2.10−8
• HPO42- ⇄ H+ + PO43- K3 = 4,4.10−13
H3PO4 ⇄ 3H+ + PO43- K =K1  K2  K3

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 9. The self ionisation of water

2 H2O ⇄ H3O+ + OH− [ H + ].[ OH − ]

K=
or: H2O ⇄ H+ + OH− [ H 2 O]

1000g / l
[H 2 O] = C H 2O = = 55,5(5)mol / l
18g / mol

[H+].[OH−] = K.[H2O] = Kw

ToC 0 10 18 25 50

Kw.1014 0,114 0,292 0,570 1,008 5,474

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10. Hydrolysis
𝐻𝐴 [𝑂𝐻 − ] 𝐶 2 ℎ2
𝐴− + 𝐻2 𝑂 ⇌ 𝐻𝐴 + 𝑂𝐻 − 𝐾ℎ = =
[𝐴− ] 𝐶(1−ℎ)

h << 1 → 1 - h  1
Kh
h=
C

[HX][OH - ][H + ] - + [X - ][H + ]

K = = [OH ][H ] :
[X - ][H + ]
h [HX]

𝐾𝑤
𝐾ℎ =
𝐾𝑎

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11. Solubility Equilibrium

MmXn (s) ⇄ m M+ (aq) + n X− (aq)

Ksp = [M+]m.[X−]n

➢ Saturation: [M+]m.[X-]n = Ksp

➢ Unsaturation: [M+]m.[X-]n < Ksp

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Exp. SrF2 is sparingly soluble in water. The equilibrium constant has a value Ksp =
3,0 x10-9 at 20 oC. Calculate the solubility of SrF2 in:
a) water alone;

b) a solution which is 0.030 M with respect to NaF;

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c) a solution which is 0.030 M with respect to Sr(NO3)2;

d) would precipitation occur if 100 mL of a 0.050 M solution of Sr(NO3)2 is mixed

with 200 mL of a 0.020 M solution of NaF?

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V. Limitations of Arrhenius theory limiting

n'
Degree of dissociation =
n
➢ 01
➢  is Independent of measurement method

Availability with dilute electrolyte solutions and

univalent (v = 2, v+ = v- = 1)

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The dependence of  on conc., dissociation order
and measurement method
Substances C (eq/l) 1 (conductivity) 2 (osmotic pressure)
KCl 0,005 0,956 0,963
KCl 0,010 0,941 0,943
KCl 0,020 0,922 0,918
KCl 0,050 0,889 0,885
BaCl2 0,100 0,751 0,788
MgSO4 0,100 0,434 0,324
La(NO3)3 1,00.10−6 0,920 0,946
La(NO3)3 1,00.10−5 0,788 0,865
La(NO3)3 1,00.10−4 0,635 0,715
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 of HCl depends on concentration and method

C (eq/l) 1 (conductivity) 2 (electrochemical method)

3,00.10−3 0,986 0,990

8,00.10−2 0,957 0,880
3,00.10−1 0,903 0,783
3,00 - 1,4
6,00 - 3,4
16,0 - 13,2

>1
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 Limitations of Arrhenius theories in electrolyte
Dissociation constant Ka
n n-
[M + ] + .[A- ]
Ka =
[Mn An- ]
+

Ka is dependent on nature of electrolyte and temperature

Availability with dilute electrolyte solutions

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The dependence of  on concentration
KCl MgSO4 NH4OH CH3COOH
C (đlg/l)
Ka.102 Ka.105 Ka.105 Ka.105
1,0.10−4 1,28 2,35 1,06 -
2,0.10−4 1,96 3,23 - -
1,0.10−3 4,56 6,01 1,56 1,75
5,0.10−3 10,51 10,5 - -
1,0.10−2 15,10 13,3 1,68
2,0.10−2 - - - 1,74
5,0.10−2 36,0 24,7 - -
1,0.10−1 53,5 33,3 1,92 1,70
2,0.10−1 - - - 1,65 23
VI. Improvement of Arrhenius electrolyte theories

The phenomenon of electrolytic dissociation C. II

Non-ideal behavior of electrolyte solutions C. III

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