Thermodynamics of Electrolyte Solution

 Electrolytes solutions.
 Activity.
 Activity Coefficient.
 Mean Activity and Mean Activity Coefficient.
 Ionic Strength.
 Relationship between Ionic Strength and Mean Activity Coefficient.
 Mean molal activity coefficient versus Ionic Strength.
 Theories of electrolyte solution:
 Debye – Hückel Theory
 Extended Debye - Hückel equation.

)CH 642( ‫الديناميكا الحرارية لألنظمة غير المثالية‬

‫عبدالحكيم علي جنقر‬/ ‫د‬
‫ قسم الكيمياء – كلية العلوم – جامعة طرابلس‬:‫أستاذ في الكيمياء الفيزيائية‬
 Electrolytes Solutions

A strong electrolyte dissociates completely when dissolved in water.

A weak electrolyte only dissociates partially when dissolved in water.
A nonelectrolyte does not dissociate in water.
 Activity and Activity Coefficient

 Activity: “Effective Concentration” (a):

 A measure of its effective concentration as determined by the lowering of the freezing point of water,
by electrical conductivity and by the mass action effect.
 The activity may be considered as an idealized or effective concentration.
 Concentration can be related to activity using the activity coefficient (𝛄), where; [a] = 𝛄 (c)
 Until now we have assumed that activity, a, is equal to concentration, c, by setting 𝛄 = 1 when dealing
with dilute aqueous solutions.

But ions don’t behave ideally:

 The value of 𝛄 depends on:
• Concentration of ions and charge in the solution.
• Charge of the ion.
• Diameter of the ion.
• Activity coefficient 𝛄z→ 1 as Concentrations→0 and tend to be<1 except for seawaters.
 Activity and Activity Coefficient
Activity (a):
Strong Electrolyte: NaCl (s) → Na+(aq) + Cl- (aq) ; α = 1.0
Weak Electrolyte: HAC (l)  H+(aq) + AC- (aq) ; α = 0.1
Example (1): AB (s) → A+(aq) + B- (aq) ; (salt complete dissolve)
aA+ = Activity of A+ ions & aB- = Activity of B- ions & a± AB &
Mean activity = (aA+ . aB-)1/2 = aA+ . aB−
𝛄A+ = Activity coefficient of A+ ions & 𝛄B- = Activity coefficient of B- ions &
𝛄± AB = Mean activity coefficient = (𝛄A+ . 𝛄B-)1/2 = 𝛄A+ . 𝛄B−

Example (2): A2B (s) → 2A+(aq) + B-2 (aq) ; (salt complete dissolve)
3
aA+ = (aA+)2 & aB- = (aB-2) & a± = [(aA+)2 . (aB-2)]1/3 = (aA+)2.(aB−2)
3
𝛄± = [(𝛄A+)2 . (𝛄B-2)]1/3 = (𝛄A+)2.(𝛄B−2)
 Activity coefficient (𝛄i)
 In electrolyte solutions the activity coefficient is a measure of the deviation of the
idealized concentration {ai} from the stoichiometric or analytical concentration, mj.
 An activity coefficient is a factor used in thermodynamics to account for deviations
from ideal behavior in a mixture of chemical substances.
 This deviation is a result of the electrostatic forces of attraction and repulsion which
are present in electrolyte solutions.
 A discussion of the concept of activity coefficient requires an analysis of the
electrostatic interactions in electrolyte solutions.
 The activity coefficient ‘𝛄i’ is defined as: ai = 𝛄i xi
 Activity Coefficients
 The activity coefficient is a measure for the deviation from ideal solubility.

No direct way to measure the effect of a single ion in solution (charge balance).
Mean Ion Activity Coefficients – determined for a salt (KCl, MgSO4, etc.)
𝛄± (KCl) = [(𝛄K)(𝛄Cl)]1/2 & Ksp= 𝛄± KCl2(mK+)(mCl-)
 MacInnes Convention  𝛄K = 𝛄Cl = 𝛄± KCl

Measure other salts in KCl electrolyte and substitute 𝛄± KCl in for one ion to measure the other
ion with respect to: 𝛄± KCl and 𝛄± salt .

 Account for deviation from ideal behavior of a solution.

 Infinitely dilute solution, no deviations,  = 1.
 Moderately dilute solutions, deviations from Columbic (electric) forces of attraction and
repulsion  < 1.
 Concentrated solutions, deviations caused by ionic interactions,  < 1 or  > 1.
 Properties of Activity coefficients
1. The activity coefficient of a species is a measure of the effectiveness with which that
species influences an equilibrium in which it is a participant. μ → 0 , 𝛄x → 1 , aX → [x],
2. In solutions that are not too concentrated, the activity coefficient for a given species is
independent of the nature of the electrolyte and dependent only on the ionic strength.
3. For a given ionic strength, the activity coefficient of an ion decreases more dramatically from
unity as the charge on the species increases.
4. The activity coefficient of an uncharged molecule is approximately unity, no matter what the
level of ionic strength.
5. The activity coefficients of ions of the same charge are approximately equal. The small
variations among ions of the same charge can be correlated with the effective diameter of
the hydrated ions. The activity coefficient of a given ion describes its effective behavior in all
equilibrium in which it participates.
 Mean Activity and Mean Activity Coefficient

General Formula: AxBy (s) → xA+(aq) + yB- (aq) ; (salt complete dissolve)
x+y
a± = [(aA+)x . (aB-)y ]1/x+y = (aA+)x . (aB−)y
x+y
𝛄± = [(𝛄A+)x . (𝛄B-)y ]1/x+y = (𝛄A+)x . (𝛄B−)y

Example (3): Na2SO4 (s) → 2Na+(aq) + SO4-2 (aq) ; (salt complete dissolve)
3
a± = [(aNa+)2 . (aSO4-2)1 ]1/3 = [(aNa+)2aSO4−2)1
3
𝛄± = [(𝛄 Na+)2 . (𝛄 SO4-2)1 ]1/3 = [(𝛄Na+)2𝛄SO4−2)1
 When known the activity of Na+ and SO4-2 ions can be calculate the a± of Na2SO4 .
Note: The relationship between activity, activity coefficient and composition (x & c):
 Therefore; a1 = 𝛄1 . x1 or ai = 𝛄i . ci
 a± = 𝛄± [A+] [B-] for the reaction: AB (s) → A+(aq) + B- (aq)
 a± = 𝛄± [A+] [B-] for the reaction: A2B (s) → 2A+(aq) + B-2 (aq)
 a± = 𝛄± [A+] [B-] for the reaction: AxBy (s) → xA+(aq) + yB- (aq)
 Ionic strength (μ or I)
Ionic strength: A measure of the total ion concentration in solution; but ions with more charge are counted more
due to stronger electrostatic interactions with other ions! (i.e., can influence the increase “ionic atmosphere” greater
than singly charged ions!). (μ) = 𝟏/𝟐 σ 𝐳𝐢𝟐 𝐜𝐢
Where; ci is concentration of ith species and zi is the charge on ith species.
Example (1): What is ionic strength of 0.01 M NaCl solution ?
1
μ = 2 [0.01 (+1)2 + 0.01(-1)2] = 0.01 M

Example (2): What is ionic strength of 0.01 M Na2SO4 solution ?

1
μ = 2 [2 x 0.01 (+1)2 + 0.01 (-2)2] = 0.03 M

if you have several salts-need to sum all ions present using formula !
Example (3) : Calculate the ionic strength of (a) a 0.1 M solution of KNO3 and (b) a 0.1 M solution of Na2SO4 ?
1
(a) For KNO3 solution: μ= (0.1x 12 + 0.1 x 12 ) = 0.1 M
2
1
(b) For Na2SO4 solution: μ = 2 (0.2 x 12 + 0.1 + 22) = 0.3 M
Example (4) : What is the ionic strength of a solution that is 0.05 M in KNO3 and 0.1 M in Na2SO4 ?
1
μ = 2 (0.05 x 12 + 0.05 + 12 + 0.2 + 12 + 0.1 + 22 ) = 0.35 M
 Ionic Strength (μ)
 Definition of Ionic strength:
 Is the concentration of charge particles in solution.
 Is measure of the interionic effects resulting from attraction and repulsion among ions.
 It’s the unit is (mol kg-1).

Ionic strength (μ) = σ 𝐳𝐢𝟐 𝐜𝐢

 Where; zi = the number of the charges, and Ci = the concentration of ion.

Example (4): for the reaction: NaCl (s) → Na+(aq) + Cl- (aq)
The concentration NaCl is 0.01 M & ZNa+ = +1 & ZCl- = -1 .
Solution:
𝟏
∵ μ(NaCl) = σ 𝐳𝐢𝟐 𝐜𝐢 = ½ [(+1)2 (0.01) + [(-1)2 (0.01)] = 0.01 & μ = C for salt 1:1
𝟐
 Effect Ionic Strength
 The effect of added electrolyte on equilibrium is independent of the chemical nature of the electrolyte but
depends on a property of the solution called the ionic strength, which is defined as:
Ionic Strength (μ) = ½(z2A[A] + z2B [B] + [C] z2C [C] + ….)
 Where; [A], [B], [C], represent the species molar concentrations of ions A, B, C, and zA, zB, zC, are their charges.
 The ionic strength of a solution of a strong electrolyte consisting only of individually charged ions is equal to its
total molar salt concentration.
 For solutions with ionic strengths of 0.1 M or less, the electrolyte effect is independent of the kind of ions and
dependent only on the ionic strength.

 Where; c is the molar concentration of the salt.

 The effect of charge and concentration of ions on Ionic Strength

Note z+ z_ ci μ c:μ

Case I 1 1 1 1 c=μ

Case II 2 1 1 3 3c : μ

Case III 1 2 1 3 3c : μ

Case IV 2 1 1 4 4c : μ

Example (5): for the reaction: Na2SO4 (s) → 2Na+ (aq) + SO4-2 (aq) ;

The concentration of the Na2SO4 is 0.01M, calculate the ionic strength of the salt.
Solution:
zNa+ = +1 & zSO4-2 = -2 & cNa+ = 2 x 0.01= 0.02M & cSO4-2 = 1 x 0.01= 0.01M.
𝟏
∵ μ(Na2SO4) = σ 𝒛𝒊𝟐 𝒄𝒊 = ½ [(+1)2 (0.02) + [(-2)2 (0.01)] = 0.03
𝟐

and μ = 3c or c = 1/3 μ for salt 2:1.

 The effect of charge and concentration of ions on Ionic Strength

Example (6):
For the reaction: CuSO4 (s) → Cu+ (aq) + SO4-2 (aq) ;

The concentration of the Na2SO4 is 0.01M, calculate the ionic strength of the salt.
Solution:
zCu+2 = +1 & zSO4-2 = -2 & cCu+2 = 1 x 0.01= 0.01M & cSO4-2 = 1 x 0.01= 0.01M.
𝟏
∵ μ(CuSO4) = σ 𝒛𝒊𝟐 𝒄𝒊 = ½ [(+2)2 (0.01) + [(-2)2 (0.01)] = 0.04
𝟐

and μ = 4c or c = 1/4 μ for salt 2:2.

Note:
The ionic strength for any salt can be calculate from their concentration direct.
 Mean molal activity coefficient versus Ionic Strength
𝛄± versus μ
Effect of μ on 𝛄±

 At a given ionic strength, a single activity coefficient for cyanide ion describes the influence of that
species on any of the following equilibria:

HCN + H2O ↔ H3O+ (aq) + CN- (aq)

Ag+(aq) + CN- (aq) ↔ AgCN (s)
Ni+2(aq) + 4CN- (aq) ↔ Ni(CN)4-2
 So if solubility increases with ionic strength; meaning that concentrations increase; then activity coefficients
decrease as you increase ionic strength !!

 Activity coefficients do not continue to decrease with increase in ionic strength; as you go beyond μ = 0.5 M
γ increases; solvent changes; solution has greater mole fraction of salt !!
  Debye-Hückel Equation Limiting Law Theory
 The Debye-Huckel limiting law was derived by Debye and Huckel who developed a theory to calculate activity coefficients
of electrolyte solutions.
 Taking into account, the ion size parameter expressed in angstroms, the original Debye-Huckel equation for the mean
activity coefficient (𝛄±) ,for a completely dissociated binary electrolyte, consisting of ν ions (mole of solute)-1, with charges
z+ and z- , Robinson and stokes can be written as: mean Activity coefficient : log (𝜸± ) = 0.5091 z+ z- μ ; and ionic
strength: (μ) = σ 𝐳𝐢𝟐 𝐜𝐢
 where μ is the ionic strength in molality (m) units of concentration.
 This equation is known Debye-Huckel Limiting law : log (𝜸± ) = 0.5091 z+ z- μ
 Condition: This equation is applied for the concentration of Electrolyte solutions ≤ 0.01M at 25oC.

 Debye- Huckel made the following assumptions in their model:

1) Strong electrolytes are completely dissociated into ions.
2) Inter- ionic interactions obey Coulomb’s Law.
3) Ionic distribution is controlled by Coulomb’s forces and thermal motion.
4) There are no external forces.
5) Solvent is a continuous dielectric medium with dielectric constant ‘ε’.
 Methods for Determination the Activity Coefficient
 Method (1): From Dissociation of weak Electrolyte:
 For example acetic acid (HAC) as weak Electrolyte: HAC ↔ H+ + AC-
+ −
𝐚𝐇 . 𝐚𝐀𝐂
Dissociation constant of HAC (Ka) = (1) ; where; aHAC = 1 , but [HAC] ≠ 1
𝐚𝐇𝐀𝐂
+
Ka = 𝐚𝐇 . 𝐚𝐀𝐂- (2) ; ∵ a = 𝛄 . c (3) , subtitle a value from equation (3) to equation (2) we get :

+ [H+][AC−] [H+][AC−]
∴ Ka =γH . γAC- . ; then: Kthermodynamic = Ka (𝜸±) .
2 (4); Kth. = Ka
[HAC] [HAC]

[H+][AC−]
 By take the logarithm for equation (4) we get: logKth. = 2 log (𝛾±) + log [HAC] or

[H+][AC−]
Log Kth. - 2 log (𝛄±) = log (5) ; ∵ log (𝛄± ) = 0.5091 z+ z- μ (6) ;
[HAC]
 By subtitle log (𝛄± ) value from equation (6) to equation (5) we get :
[H+][AC−]
log Kth. - 2 (0.5091 z+ z- μ ) = log (7), by rewrite equation (7) we get :
[HAC]
[H+][AC−]
log = log Kth - 1.082 z+ z- μ (8)
[HAC]
[H+][AC−]
By Graph the equation (8): when plot log against μ ; we get straight line the slope = - 1.082 z+ z-
[HAC]
and the intercept = log Kth
 Methods for Determination the Activity Coefficient
∧
 Degree of Dissociation (α) : where; α= 𝑪
∧𝒐
 For example take the acetic acid: HAC ↔ H+ + AC-
Cα .Cα C2α2
C – Cα Cα Cα ; ∵ Ka = = ;
C – Cα C( 1– α)
Cα2
∴ Ka = (9)
(1– α)
 Equation (9) prove the relationship between Ka and α for weak Electrolyte such as HAC.
1 1
∵ μ = σ zi2 ci ; for HAC μ = +1 2 Cα + ( −1 2 Cα ; Therefore; ∴ μ = Cα (10)
2 2
 By subtitle Ka and μ values from equation (9 & 10) to equation (8) we get :
Cα2
∴ log = log Kth - 1.082 z+ z- Cα (11)
(1– α)
 Equation (11) prove the relationship between Ka , Kth and α for HAC.
∧C
 Calculate the α = ;it known the Arrhenius’ Equation from the measurement of ∧ 𝐂 and∧ 𝐨
∧o
; where; ∧ 𝑪 and ∧ 𝑪 the molar conductivity of solution at any concentration (C=C)and infinite
concentration (C =0) respectively.
Cα2
 In equation (11): when plot log against Cα; we get straight line slope = - 1.082 z+ z-
(1– α)
and the intercept = log Kth
 Methods for Determination the Activity Coefficient
 Method (2): From the Solubility (S):
 For general equation: AB → A+ + B- ; where; [A+ ] = + [B-] = S ; where; S = solubility of solution.
aA+. aB−
 For the activity of aAB , aA+ and aB- ; Then: Kth = ; where; aAB = 1 ∴ Kth = 𝒂𝐀+. 𝒂𝐁− (12)
aAB

∵ γA+. γB− = (γ± )2 and γ± = γA+. γB− = (γA+. γB− )1/2

[A+] [B−]
Kth = (γ± )2 . ; where; [AB] =1 ; then : Kth = (γ±)2 . [A+] [B−]
[AB]
 By using the solubility compensate instead of activity in equation (12):
Kth = (𝛄±)2 . S . S = (𝛄±)2 . S2 (13); where; Ksp = S . S = S2
 By Developing Equation (13) to use more, take the logarithm for equation (13):
∴ log Kth = 2 log (𝛾±) + 2 log S ; rewrite this equation 2 log (𝛾±) = log Kth - 2 log S ; Therefore;
log S = ½ log Kth - log (𝛄±) (14)
∵ log (𝛄± ) = 0.5091 z+ z- μ (6) ; compensate instead of log (𝛄± ) value from equation (6) to equation (14) we get :
log S = ½ log Kth. - 0.5091 z+ z- μ (15)
 By Graph the equation (8): when plot log S against μ ; we get straight line the slope = (-0.5091 z+ z- ) and
the intercept = ½ log Kth .
 Use equation (15) in case the salt 1:1 such as NaCl, but doesn't in other salts such as 1:2 or 1:3 , etc.
 Determination the Kth for relationship between S and μ
 We required drive new formula to use in the other cases for the salts such as 1:2 and 1:3 etc…

 For the case: A2B → 2A+ + B-2 ; where; 2:1 ; such as Na2SO4 → 2Na+ + SO4 -2
 ∵ Kth = 𝛾A+ 2(γB−) [A+]2 [B−] = (γ±)3 . (2S)2 . S
∴ Kth = (𝜸±)3 . 4S3 (16) ; for the A2B salt type ;
where; Ksp = 4S3 and log Ksp = log 4 + 3 log S (17)
 By take the logarithm of equation (16) and compensate instead of log Ksp from equation (17) we get:
∴ log Kth = 3 log (𝛾 ±) + log 4 S3 = 3 log (𝛾 ±) + log Ksp = 3 log (𝛾 ±) + log 4 + 3 log S
∴ log 4 + 3 log S = log Kth - 3 log 𝛄± (18) ; rewrite this equation we get:
1
log S = 3 [ log Kth. – log 4 ] – log 𝛄± ] (19)

∵ log (𝛄± ) = 0.5091 z+ z- μ (6) ; compensate instead of log (𝛄± ) value from equation (6) to equation (19) we get :
1
log S = [ log Kth. – log 4 ] – 0.5091 z+ z- μ (20)
3
 By Graph the equation (20): when plot log S against μ ; we get straight line the slope = (-0.5091 z+ z- ) and the
1
intercept = 3 [ log Kth. – log 4 ] .
 Determination the Kth for relationship between S and μ
 For the A2B3 salt case: A2B3 → 2A+ + 3 B- ; where; 2:3 ; such as Ba3(PO4 )2→ 3Ba+2 + 2PO4 -3

 ∵ Kth = 𝑎A+ 2(aB−)3 = 𝛾A+ 2(γB−)3 [A+]2 [B−]3 = (γ±)5 . (2S)2 . (3S)3 = (γ±)5 . 4S2 . 27S3
∴ Kth = (𝛄±)5 . 108 S5 (21) ; for the A2B3 salt type.
where; Ksp = 108 S5 and log Ksp = log 108 + 5 log S (22)
 By take the logarithm of equation (21) and compensate instead of log Ksp from equation (22) we get:
∴ log Kth = 5 log (γ±) + log 108 + 5 log S ; rewrite this equation we get:
∴ 5 log S = log Kth - log108 - 5 log (γ±) ; divide by 5 we get:
1
∴ log S = [ log Kth. – log 108 ] – log 𝛄± (23)
5
∵ log (𝛄± ) = 0.5091 z+ z- μ (6) ; compensate instead of log (𝛄± ) value from equation (6) to equation (23) we get :
1
log S = [ log Kth. – log 108 ] – 0.5091 z+ z- μ (24)
5

 By Graph the equation (24): when plot log S against μ ; we get straight line the slope =
1
(-0.5091 z+ z- ) and the intercept = [ log Kth. – log 108 ] .
5
 Determination the Kth for relationship between S and μ
Example:
Calculate the solubility of PbCl2 salt in 0.1M NaCl, if the solubility of water is 0;01M at 25oC.
(a) Neglecting effect . (b) Including them but using the simple limiting law.
Solution: PbCl2 (s) → Pb+2 + 2Cl-
(a) S 2S
Ksp = S . (2S)2 =4S3 = 4(0.01)3 = 4.0 x 10-6
(b) Ksp = S . (2S + 0.1)2 = 4S3 + 0.01 S = 4.0 x 10-6 + 1.0 x-4 = 4.0 x 10-10
Ksp = S . (2S + 0.01)2 = 0.01 (2 x 0.01 +0.1 )2 =
S=
μ = ½ σ 𝐳𝐢𝟐 𝐜𝐢 & log Ksp = log Kth - 3 log (𝛾±)
For PbCl2 (s) → Pb+2 + 2 Cl-
0.01 0.01 2x 0.01
𝟏
μ= +𝟐 𝟐 𝟎. 𝟎𝟏 + −𝟏 𝟐 𝟎. 𝟎𝟐 ) = 𝟎. 𝟎𝟑
𝟐
log (𝛄± ) = 0.5091 z+ z- μ = -0.5091 (+2)(-1) 0.03
log (γ± ) = -0.176