2.

Electrolytes, Chemistry, Thermodynamics

oxidation state
( z i  3)
oxidation state +3.
−
𝑂 +𝑛 𝑒 ⇄(reductive
(oxidative species)
𝑅 species)

→ reduction reaction
← oxidation reaction

reactants → products + heat

products-reactants

takes care of energy as well as disorder.

favored direction : ,

standard Gibbs free energy

the reverse reaction will be feasible at standard state
For a species ,
𝑜
𝐺𝑖 =𝐺𝑖 + 𝑅𝑇 ln {𝑎𝑖 } activity of species
𝐺𝑖 ≡ 𝜇𝑖 =1 at the standard state
Chemical Potential of species (cf. gravitational potential gz)

Species moves from a location of higher to that of lower via diffusion or

reactions
예)
diffusion

Definition : the rate of change of energy with respect to the number of atoms or molecules
added to the system

U : Internal energy
H : enthalpy U+PV (species 이동에는 PV work 수반됨 (PAL=P V)
F : Helmholtz free energy U-TS
Species 의 diffusion,
G : Gibbs free energy H-TS
reaction 에 의한 변환은
energy 뿐 아니라 ran-
domness 의 증가 (en-
tropy 증가 ) 도 관여함
 surroundings
𝑑𝑛
𝑖
dS
system dW=-PdV (dV : system 의 volume 증가 )
input rate of the species i
dQ
dW

dU=TdS-PdV+
dH=TdS+VdP+
dF=-SdT-PdV+
dG=-SdT+VdP+
At constant T,P, dG=
=

: constant T, P 에서 species 의
이동 , 변환에 가장 편리한 mea-
sure 는 G
 Consider a binary system =1 (total mole 수 =1)

+
1 mole
A, B, Mixing

=+ G= + +

At constant T, P
𝐺 𝑠𝑒𝑡 𝐺 °𝐵
G= + +(
° : 분자간의 interaction energy 가
𝐺 𝐴 결정
A : 분자간의 configuration 수 (ran-
B(=1)
(=1) domness) 가 결정
모든 분자간의 interaction energy 가 같으면 (A-A, B-B, A-B)
=0 ideal solution
(cf. ideal gas : 충돌할 때를 제외하면 interaction 없음
ideal solution
*random configuration 수에 따른 entropy
S=kIn (k : the Boltzmann constant , : configuration 의 수 )

+ 1 mole
A( B(
Ω𝑏𝑒𝑓𝑜𝑟𝑒 =1 , : A,B 의 분자 수

전체가 1 mole 이므로 :=avogadro number

=, = 체상수 )=k

lnx!=xlnx-x (for large x) :Stirling’s approximation

= kIn kIn !-kIn -kIn !

=k[In - - + + ]
=k[In - - + - )+ ]
=-R( +
 =
For an ideal solution

0 0
∆ 𝑆𝑚𝑖𝑥 𝐺 °𝐵
°
𝐺 𝐴
A B
(=1) (=1) A B
(=1) (=1)
° dG= (+ (
𝐺𝐵
= +
𝐺 °𝐴 Slope=( Total 1 mole 이라서
dG= d+ d
A
(=1) B(=1)
=+
(+ (=+=
(G is Euler’s homogeneous function of order 1)
G= +
Total 1 mole 인 경우
G= +
cf. Gibbs-Duhem equation
 Ideal solution (

G= ++RT(ln + ln )
=(+RTln ) +(+RTln )
=+ =+

= +RTln , = +RTln

A simple example of non-ideal solution is the “Regular solution”.

Interaction energy Number

A-A
+
B-B
𝜀
𝜀 𝜀Mixing 𝐴𝐵
𝐴𝐴
A-B 𝐵𝐵

= -+ )

= (for an ideal solution, = = )

~ :Λ
For a regular solution (a kind of non-ideal solution)
G= ++ Λ +RT(ln + ln )

= (1)= ( +) + = +

G= +RTln + Λ} +RTln + Λ }

yln
G= [+RT(ln + ln)]+ [+RT(ln + ln)]

= [+RT(ln )]+ [+RT(ln )]

Define activity and activity coefficient

,

=1 for ideal solutions

different

G= (+RTln )+ (+RTln )

Chemical po- Chemical po-

tential of A tential of B
= =
If 1, interaction energy of the mixture is determined mainly by A-A
ideal solution = (=1) : Raoult’s law
1 implies 0 : B 의 interaction energy 는 B-A 에 의해 결정됨
: = =constant (Henry’s law)

cf. Regular solution 인 경우

= as 1
= as

Henry's constant
Liquid-Vapor Equilibria in Binary Systems

Vapor pressure

∗ ∗ ∗
Pi Pi Pi
i i i i i i
i i i i
Vacuum
chamber
i i i i i i i i i i i i i i i i

pure i

𝑇1 𝑇2 𝑇3
𝑇 1< 𝑇 2 <𝑇 3
( 𝑃∗𝑖 ) 𝑇 < ( 𝑃 ∗𝑖 ) 𝑇 < ( 𝑃 ∗𝑖 )𝑇
1 2 3

if is the boiling point at atmospheric condition.

(interaction of pair determines )

(mixtures)
: solvent
: solute

Raoult’s law i
i
i
i

for i i i i j i
( is the vapor pressure of pure solvent)
Raoult’s law (interaction of pair
determines as in the pure case)

Henry’s law i
j i
i
for
i i i j i i
( is the Henry’s constant)

Henry’s law (interaction of pair

: partial pressure of species i
determines or
is not the vapor pressure of solute)
 For ideal solutions, the Raoult’s law is valid over all range of X.
( is constant with respect to )

Ideal solution : interaction potential between pair is identical to that

between and pairs.
 For nonideal solutions

activity
= for ideal solutions
for nonideal solutions

1 at the standard state

(Standard state Gibbs free energy of formation: compound from elements)

Standard state Gibbs free energy of elements=0
 (activity of a molecule is high,
Activity when at a high concentration or at a high potential energy state)
changes occur to lower the activity of species involved.
species Activity
pure solid

pure liquid cf. =

pure gas or component of gas mixture ( ) cf. Raoult’s law (gas is an ideal solution)

cf. Raoult’s law (

solvent ( ) cf. Henry’s law

nonionic solute at low or

moderate concentration (must be measured)

nonionic solute at moderate or

high concentration cf. Henry’s law

(Debye–Hückel)
ionic solute in a solution of extremely
low ionic strength
( is a part of )
ionic solute in aqueous solution of
low or moderate conc.
 species i stan-
transfer
species i condi- 1 molecule
dard state
tion of interest

: work expended per molecule =

=
ideal gas constant
𝑜
(𝐺¿¿ 𝑖 −𝐺𝑖 =∆ 𝐺= 𝑅𝑇 ln ⁡𝑎𝑖 )¿

activity of electrons (work per mole of electrons expended )

: 낮은 에서 전자는 더 active 함
: 전자는 낮은 에서 높은 쪽으로 이동

For a chemical species ,

𝐺𝑖 = 𝐺𝑜
𝑖 + 𝑅𝑇 ln ⁡{𝑎 𝑖 }

Gibbs free energy when (standard state)

 Consider
−

H g2 Cl 2 ( s ) +2 H 2 O (l )+ H 2 ( g ) ⟶ 2 Hg ( l ) +2 H 3 O + ¿ ( aq )+2 Cl (aq)¿

At equilibrium,

or
 equilibrium constant

Figure 2.4 The transfer of an uncharged substance i, between reservoirs L and R, can be made directly but, for a
charged species, it is convenient to imagine travel through an intermediate Reservoir I.

for molecules transferring from L to R reservoir

( for neutral i )

( for ions i )
=
At equilibrium,

electrochemical activity

at equilibrium
~ 0
𝐺=𝐺 + 𝑅𝑇𝑙𝑛𝑎+ 𝑧𝐹 𝜑=𝐺 + 𝑅𝑇𝑙𝑛 ~𝑎
0

At equilibrium, assuming

: electric work needed to move one molecule of from to

(Boltzmann distribution valid at equilibrium)

-
 −
+¿ ( aq ) +2 N O3 ( aq ) ¿
N 2 O5 ( s ) + H 2 O ( l ) ⟶ 2 H
strong electrolyte
−
+¿ ( aq ) +OH ( aq ) ¿
NH 3 ( aq )+ H 2 O ( l ) ⇄ NH 4
( equilibrium constant )
weak electrolyte

Z +¿ C + ¿ = −Z − C − ¿ ¿ ( binary ionic species )

electroneutrality relationship
counter ion or co ion

Ionic strength
§ Electrolytes

전해질
electroneutrality

이온의 이동에 의해 전류가 용액 중을 흐르는 경우에도 전기적 중성 유지됨 ( 나중에 증명 )

: : activity
: activity coefficient
𝑎 𝑖 =𝛾 𝑖 𝑚𝑖
dimensionless
dimensionless
dimensionless

lim 𝛾 𝑖 =1
𝑚𝑖 → 0

molar +
농도 m m+=pm , m-=qm
−
+¿ +𝑞 𝑧 =0 ¿
𝑝𝑧
Gi=Gi0 + RT

G= pG+ + qG-
= pG+0+qG-0+ pRT + qRT

mean activity

mean activity coefficient

mean concentration

(We cannot measure and separately.

We measure .)
Then

for the species ,

G𝑖 =G0𝑖 +𝑅𝑇 ln 𝑚𝑖 +𝑅𝑇 ln 𝛾𝑖

nonideality (interaction between ions)

How to find ? : through experiments for concentrated electrolytes

and using the Debye-Huckel theory for dilute electrolytes.
Ionic atmosphere ( 이온 분위기 )
≡ ion cloud
- - -
- +- +
- -
Figure 2.6 The ionic atmosphere is pic-
ionic strength tured as a cloud of electricity, of sign op-
posite to that of the central ion.
이온 분위기의 크기↓ as I↑
KCl
CaSO4 (2-2)
Al2(SO4)3 (2-3)

consider

T 의 함수 Ion 의 전기적 interaction 에 의존

NaCl 첨가는 변화
∴ 변함
 ..
Debye – Huckel theory

이온의 activity coefficient 를 이온전하 상호작용 에너지를 이용해서 구한다

E ,E

특정이온을 원점

number concentration of cation

number concentration of anion
(elementary charge)
) Boltzmann 분포

Boltzmann constant)
electroneutrality

: Avogadro 수

(I ionic strength)

( ionic strength appears!! )

(cation 근처에는 가 큼 )

( 크면 negative 큰 값 )

( 따라서 cation 주위에 anion 이 모임 : ionic atmosphere 형성 )

( 이 경향은 I ( ionic strength ) 에 의해 결정됨 )

(linearized expression of -)

()

( =- )

( electroneutrality )

𝑧𝑖 𝑒
 : Debye length
(ionic atmosphere 의 크기 )

이온분위기 이온자체

Figure 2.6 The ionic atmosphere is pic-

tured as a cloud of electricity, of sign op-
posite to that of the central ion.
𝑟0
에 전하 를 1mol 충전하는데 들어가는 추가의 일 (caused by the ionic atmosphere)
(potential=work per charge)
가 도 의존하므로 , consider differential increment of

⇒ energy increase due to solution nonideality

(𝑅=𝑁 𝐴 𝑘)

𝑝 𝑧 +¿ +𝑞 𝑧 − =0 ¿
𝑝 𝑧 +¿ 2
+𝑞 𝑧 2 = − 𝑞 𝑧 − 𝑧 +¿ ¿
− −𝑝 𝑧 +¿ 𝑧 = −( 𝑝+𝑞 ) ¿ ¿ ¿
−
(limiting law of Debye-Huckel) ..

as C↓, ↑, , →1
Concentrated solution :
가 성립하지 않음

CI

용매가 이온의 solvation 에 의해 묶임