Electrochemistry

Activity
MA  M+ + A−

μA= μA0 + RT ln aA
aA=A XA
μA= μA0 + RT ln A XA

μA= μA0 + RT ln A + RT ln XA
In the standard state the mole fraction is 1
For ionic compound:
μA= μ + RT ln A
A
0
Describes the different
interactions between different
ions or dipole in the solution.
Mean activity and activity coefficient
•MA  M
  + + A− (for 1:1 electrolyte)

ai =γi  mi or ai =fici

Experimentally we can calculate mean activity and activity coefficient:

There is no experimental way of separating the product γ+γ− into contributions
from the cations and the anions.
MpXq:

γ ± = (γ p+γ q−)1/s s = p + q
How to calculate activity
theoretically?

Debye-Hückels’ limiting
law
Debye-Hückels’ The ionic strength emphasizes the charges of the
ions because the charge numbers occur as their
limiting law squares.

•a)  1:1 electrolyte and dilute solution

• Ion is dimensionless
• Oppositely charged ions attract one another
• ionic atmosphere

z1, z2, z3-charges number of ion

c- ion molarity (can use also molality)
(in water A=0.509, T=25˚C)
Ex.
•   sulfate ion, SO42-, is an important source of sulfur used in the synthesis of the amino acids
The
cysteine and methionine in plants and bacteria. To estimate the mean activity coefficient for the
ions in 0.0010 m Na2SO4(aq) at 25°C.

NB!
The limiting law is more correct for very dilute solutions and for 1:1 electrolyte solution

More correct I equations:

, - concentration in standard state= 1 M; I is dimensionless
Debye-Hückels’ limiting law
Activity coefficients values

Experimental and calculated data

using the limiting law
Extended Debye-
Hückels’ law law
•b) Ion
  is with specific dimensions
For concentrations <0.001m:

a- mean effective ion radius in the solution

B- measure of the closest approach of the ion, empirical
parameter and depends from the temperature and solvent
aB sometimes are considered together
c) Importance on environment

C – the importance of environment , the system dielectric

constant changes, taking into account the solvent dielectric
properties (orientation of dipoles)
Ex.
Calculate the mean activity coefficient and activity for 0.01 mol kg-1 MgSO4
solution at 25 °C if A = 0,5085 [mol‑1/2 dm3/2], B = 0,328 [1/Å]
and the average ion radius is 3,4 Å.

I = 4m = 2
Vaja rakendada täpsemat valemit (sellise kontsentratsiooni juures võib küll ka see
juba ebatäpseid tulemusi anda (vt raamatus „Lange’s Handbook“ toodud materjale
failist „Andmete tabelid“)
A z  z I 0, 5085  2  2 2
log     = = -1,116
1  Ba I 1  0,328  3, 4 2
 = 0,077

a=0.0007
Activity
• Activity
  is effective concentration
• Takes into account the interaction between solute and solution
molecules
• We can calculate or measure only mean activities and activity
coefficients:
• For very dilute solutions:
=mi or =ci while γ=1 or f=1
• a = γ  m või a = f  c
• γ and f activity coefficients and taking into account the ion
dimensions, charge of ion solution effects
• γ and f are strongly dependent on the ionic strength
 Compare the activity coefficient values and explain why the values are so different at different concentrations
Ex. and for different compounds?

activity coefficient
 

  𝑧 +¿ 𝑧 √𝐼
log 𝛾 ± =− 𝐴 −
+𝐶𝐼 ¿
1+𝑎 𝐵 √ 𝐼
Galvanic element
An electrochemical cell
consists
of two electrodes:
- Anode
Zn – 2 e-  Zn2+
Red – e-  Ox

+ Cathode
Cu2+ + 2e-  Cu
Ox + e-  Red
 Galvanic cell
In the notation for cells, phase boundaries are
denoted by a vertical bar. For example:

Zn (s) | ZnSO4 (aq) || CuSO4 (aq) | Cu (s)

(-) anode | Solution1 || Solution2 | cathode(+)

Oxidation Reduction

Ex.
Write down the following element with the half-
reactions:

Anode: H2(g) – 2e- → 2 H+(aq)

Cathode: Co3+(aq) + e- → Co2+ (aq)

https://www.youtube.com/watch?v=J1ljxodF9_g- Daiell’s element

https://www.youtube.com/watch?v=BJzgnjg4Nok – Daniell’s element and salt bridge
Why to use salt bridge?

In a cell with two different electrolyte solutions in contact, the ions start to
migrate towards the oppositely charged electrode and different ion mobilities
depend on the ion size, charge of the ion and from the environment. Different
ion mobility causes the uneven migration of ions in the system and formation
of electrical double layer. To overcome this electrical double layer we must
apply additional potential called liquid junction potential.
Salt bridge
Why to use the salt bridge?
• The electrolytic contact between the electrodes must be maintained.
• The ohmic resistance RΩ of the electrolyte bridge(s) and diaphragm(s) must be small enough so
that the voltage drop iR Ω is minimal or, if possible, negligible. (Electronic iRΩ compensation will
not be considered here.)
• The diffusion potentials at all places were different electrolyte solutions
• border, must be as small as possible, and they must be as stable (time invariant)
• as possible. It is the major task of a salt bridge to reduce the diffusion potential
• which would build up at the junction of the electrolytes A and A0 of the two
• electrode compartments by interposing the bridge electrolyte B.
• (iv) The electrolyte of the reference electrode should not be contaminated by the
• electrolyte (or generally the solution) of the working electrode and vice versa.
 Isoterm equation and Nernst equation
• 

Nernst equation

standard cell potential

When the system is in equilibrium?

When the process is spontaneous?
Standard potential and
electrochemical series
• 

- how strongly the system is able to add electrons

(the higher is the standard potential value the
stronger oxidizer the agent is)

E0 = E0(oxidizer) - E0(reducing agent)

F22F-
LiLi+
E0=+2.87V – (-3.05 V)=+5.92 V
Ex.

According to the scheme write the half reactions

• mark the oxidizing and reducing agent,

• cathode and anode and
• write the Nernst equation for the system:

Pt(t)|H2(g)|H+(aq)||Co3+(aq),Co2+ (aq)|Pt(t)

Anode: H2(g) – 2e- → 2 H+(aq)

Cathode: Co3+(aq) + e- → Co2+ (aq) E0=+1.82 V
H2(g) + 2 Co3+(aq) → 2 H+(aq) + 2Co2+ (aq)
Ex.

•According
  to the scheme write the half reactions, mark the oxidizer and
reducing agent, cathode and anode and the Nernst equation for the
system:
Zn(s)|Zn2+ (aq, 1.5M)||Fe2+ (aq, 0.1M)|Fe(s)

(Zn2+ |Zn(t))= -0.76 V

(Fe2+ |Fe(t))= -0.44 V

Explain when the reaction is spontaneous and when not?

Daniell’s element
•Metal/metal
  ion
Zn + Cu2+  Zn2+ + Cu

=0.34 V-(-0.76 V)= +1.1 V

SHE- standard hydrogen electrode
•H +(aq) + e– → ½ H2(g)

E0 = 0 V, for all temperatures!

SHE in standard condition:
• H2 pressure1 bar,
• Activity of solution=1

H2 pressure1 bar,

https://www.youtube.com/watch?v=ghvDcbCYJGU
•Metal/ion
  electrode
Application: TD parameter measurement, reference
electrodes

Ag|AgCl| Cl-
AgCl (s)= Ag +(aq) + Cl-(aq)
Ag +(aq) + e- = Ag (s)
Overall reaction:
AgCl (s) + e- = Ag(s) + Cl-(aq)

= 0.22 V (depends on temperature)

http://glossary.periodni.com/glossary.php?en=silver%2Fsilver-chloride+electrode
 How to measure activity coefficient?
(Pt) H2  HCl-lahus  AgCl
 Ag
½ H2 (g) + AgCl (s) = Ag(s) + H+(l) + Cl-

measuring
SHE
How can Ag|AgCl| Cl- electrode work as
Ag|AgCl| Ag+? How to measure solubility constants?
KCl (sat)|AgCl|Ag
Ag|AgCl|KCl (x M)||KCl (sat)|AgCl|Ag Ag|AgCl|KCl (x M)

c
c
constant

Solubility constant:
KL=[Cl-][Ag+]
TD parameter calculations
∆ 𝐺=− 𝑧𝐹𝐸
 

Using cell potential it’s possible to

calculate thermodynamic parameters:
dG=VdP-SdT ∆ 𝐻 =∆ 𝐺 −𝑇 ∆ 𝑆
 

  𝑧𝐹 𝑑𝐸
dG=-SdT ∆ 𝐻 =− 𝑧𝐹𝐸+
𝑑𝑇

For a reaction:
  𝑑 ∆𝐺 𝑧𝐹 𝑑 𝐸
∆ 𝑆=− =−
d(G)=- SdT 𝑑𝑇 𝑑𝑇
Inert electrode
Application: redox titration

Pt|Fe2+ (c1, M), Fe3+ (c2, M)

Fe3+ + e-(Pt)→ Fe2+

= + 0.77 V
https://www.youtube.com/watch?v=-BuqEhhDA8U
Redox titration

Voltage change is a function of added titrant

K. Lust Füüsikaline keemia 2. osa, LOKT.02.038

•   selective electrodes
Ion
Application: potentiometry, different ion measurements

pH electrode:
• Inside Ag|AgCl| Cl- reference electrode
• Glass membrane makes the electrode ion selective
• 0.1 M HCl -membrane inner solution

Ag|AgCl | 0.1M HCl | glass membrane | measured solution || ref. electrode system

H+]

https://photos.google.com/share/AF1QipNJzZBJzeeBOpox1EqZwjUdvi1T9CzYRN1xVsll_1Hn7IlAEoZ6pQbsn
R78NuqfDg?key=RVZSUndnTXdTOHozTDdLRDBTanppaVMxY1R0SUxB
•Other
  ion selective electrodes
• Selective membrane
• Specific inner solution

Equilibrium with inner membrane solution and outer measured solution:

H+(aq) + M+(kl) → H+(kl) + M+(aq) (Nikolsk’s equation)

K- selectivity coefficient (10-10- 10-14)

pH- potentsiometric titration

How to measure equilibrium constant?

K. Lust Füüsikaline keemia 2. osa, LOKT.02.038

Titration
The HCl and the CH3COOH solution
were with the same concentration
and amout. The titrant was NaOH.
• Which curve is for stronger acid
which for weaker acid?
• Why the one curve has initially
higher pH?
• Why there is so big difference in
pH rise?
Contsentration element
•  System works due to the difference of the concentrations in
the system
• Same electrodes (often inert electrodes)

Pt|H2|HCl (a1)|| HCl (a2)|H2| Pt

a1 << a2
Bio-electrochemistry
• Cell potential

• Enzyme redox reactions

 Cell potential   +

• 
• Works like a concentration element:
• Depends on the cell inner and outer activities
Ain ↔ Aout

The equation implies that transport into the cell of either

neutral or charged species is thermodynamically favorable
if <
• An ion also needs to cross a membrane potential
difference

• The :
+

In equilibrium conditions:
+
 Active and passive transport
••Active
  and passive transport can be calculated
with the equation:
+G

•If the Gibbs free energy will be a negative value

and the direction of diffusion is towards the
decrease of concentration gradient then the
transport is passive transport (osmosis)

•Movement against the concentration gradient

and the Gibbs free energy is positive- active
transport (+ ATP hydrolysis Gibbs free energy).
Ex:
Estimate the equilibrium membrane potential of a cell at 298 K by using the fact
that the concentration of K+ inside the cell is about 20 times that on the outside.
Repeat the calculation, this time using the fact that the concentration of Na+ outside
the cell is about 10 times that on the inside.

  +
0 and E=?

 
 Galvanic element Electrolysis

Spontaneous process (∆G<0) Non-spontaneous process

(∆G>0)
(-)
(-) A:
A: –– ee-
-
(+)
(+) A:
A: –– ee-
-

Zn 2 ee- 
Zn –– 2
-
 Zn
2+
Zn2+ 4OH
4OH- -- 4e
-
4e- →
-
→ 2H
2H22O
O++O
O22↑↑
Red –– ee- 
Red  Ox
-
Ox
(-)
(-) C:
C: +e
+e-
-

(+)
(+) C:
C: +e+e-
- 2H
2H+ +
+
+ 2e
2e- →
-
→H
H22↑↑
Cu 2e- 
Cu2+ ++ 2e  Cu
2+ -
Cu
Red ++ ee 
Red  Ox
--
Ox

Nernst equation: Faraday’s

Faraday’s law:
law:
=I 
qq =I  tt
= zz 
qq =  nn 
FF
Electrolysis process
Electrolysis – (∆G>0)

(-) K: reduction +e-

2H+ + 2e- → H2↑
(+) A: oxidation –e-
4OH- - 4e- → 2H2O + O2↑

Faraday's law:
q =I  t
q=znF
 An aqueous solution of gold (III) nitrate, Au(NO3)3, was
electrolyzed with a current 0.0250 A until 1.200 g Au
(atomic weight 197) has been deposited at the cathode.

Exercise • Calculate the quantity electricity passed (Q=?)

• Calculate the duration of the experiment (t=?)
• Calculate the volume of O2 liberated at the anode
(V(O2)=?)
As a self-study topic
Mobility of an ion and conductivity
•mobility
  of an cation
mobility of an anion

Analyze and explain these values:

Resistance and conductivity
• The
  resistance depends on the
thickness of the solution and [1 S, siemens]
surface area of the electrode:
• l
• Electrolytic conductivity or
S specific conductivity
• - resistivity is the resistance of a
solution when the thickness of  [1 S]
the solution is 1m and the
surface area of the electrode is
1m2

• conductivity:
Electrolytic conductivity or specific conductivity
•   depends on:
• concentration of the solution
• temperature
• ion charge
• ion size
Molar conductivity (or molar ionic
conductivity) λ
• 
Molar conductivity -the conductivity
divided by amount-of-substance
concentration

Weak electrolytes:
=0 ×𝛼

Strong electrolytes:
– Kohlrausch equation

can be found as the sum on individual ion

conductivitie:
Conductometry and

Strong acid base titration

conductometric titration
• Electric current is measured
• Inert electrodes are used ( Pt)
• AC current is used

Weak acid strong base titration

- no selectivity
+ ion-chromatography

https://m.tau.ac.il/~chemlaba/Files/conductometry-titrations.p
df