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CONTENT
PHYSICAL CHEMISTRY 2
1. Electrochemical cells
2. Thermodynamics of electrochemical cells and electrodes
CHAPTER 2:
3. Classification of cells and electrodes
ELECTROCHEMICAL CELLS & ELECTRODES
4. Junction (diffusion) potential
5. Measurement of emf (electromotive force)
6. Electrochemical sources

Assoc. Prof. Dr. Nguyen Van Dung

Faculty of Chemical Engineering, Ho Chi Minh City University of Technology (HCMUT)

Email: nvdung@hcmut.edu.vn

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1. Electrochemical cells 1. Electrochemical cells

What reaction would occur if a Zn bar was immersed in CuSO4 (aq) solution?
Zn + CuSO4 → ZnSO4 + Cu H0298 = -210.8 kJ/mol, G0298 = -209.9 kJ/mol
Anode (-) Cathode (+)

Anodic zone Cathodic zone

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1. Electrochemical cells 1. Electrochemical cells

Spontaneous reaction Nonspontaneous reaction

✓ A galvanic cell is an electrochemical cell that produces electricity as a

result of the spontaneous reaction occurring inside it.
✓ An electrolytic cell is an electrochemical cell in which a
nonspontaneous reaction is driven by an external source of current.

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1. Notations 1. Notations

(-) Zn ZnSO4 CuSO4 Cu (+)

Rule

Negative charge (Anode) – Left hand

| → Electrode – Solution
|| → Solution – Solution (without diffusion potential)
→ Solution – Solution (with diffusion potential)
| or , → Electrode’s components

(-) Zn  ZnSO4 CuSO 4  Cu (+)

When electrodes/electrolytes were composed with various components,
using “,” to notice the components:
Cu (s) | Cu2+ (aq) (0.010 M) || Cu2+ (aq) (2.0 M) | Cu (s)
Ex: (-) Pt, H2 H+ Fe3+, Fe2+ Pt (+)
Fe (s) | Fe2+ (aq) || MnO4 (aq), Mn2+ (aq), H+ (aq) | Pt (s)
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1. Electrical double layer & Electrode potential 1. Electrode potential

Cations from the metal surface will
transfer to the solution and will leave
The surface has (-) charge
→ Attract cations Block the transfer
of the cations
→ At equilibrium: “EDL”
- EDL an electric potential jump between
e- electrode and solution. The electric potential
jump depends on: electrode, solvent, ionic
concentration, temperature.
- The potential difference is called the electrode
potential ( or ).

electrolyte electrolyte - To measure the electrode potential →

Electrode potential: The potential
standard electrode as reference electrode.
difference only appears on the contact
surface between an electrode and an
electrolyte.
+
M > +
solution
+
M < +
solution

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1. Electrode potential 1. Standard hydrogen electrode

HOW TO MEASURE ELECTRODE POTENTIAL ( ) Denote: Pt, H2 | H +

aH+ = 1 mol/L; PH2 = 1 atm
Electrode potential, , is the
Set oH+/H2 = 0 at any T (oC)
electromotive force of a cell built of
two electrodes:

+ On the left-hand: standard hydrogen

electrode (SHE; oH+/H2 = 0 V)

+ On the right-hand: the electrode in

question (working electrode).

Ecell = right − left (SHE) = electrode

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1. Measure electrode potential 1. Electrode potential ( )

Ecell = right − left (SHE) = electrode

Oxidation

Reduction

o o( Zn 2+/Zn) = - 0.76 V
( Cu2+/Cu) = + 0.34 V

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1. Electromotive force 1. Electromotive force

Consider cell: (A): (-) M2  M1  L1  L2  M2 (+)

E = (electric potential jumps) And 2 cells: (B): (-) M0  L0  L1  M1  M0 (+)
(C): (-) M0  L0  L2  M2  M0 (+)
Electrochemical cell:
M1  L1  L2  M2 EA= M2/M1+M1/L1+L2/M2
L1/L2: liquid junction potential (diffusion
EB= M0/L0+L1/M1+M1/M0 EC - EB = EA
potential) often small and negligible (1 – 2 mV) EC= M0/L0+L2/M2+M2/M0

If M0  L0 is the standard electrode (H2H+): EB = (-) & EC = (+)

Therefore, EA = (+) - (-) (Without diffusion potential)

Emf of a electrochemical cell is equal to potential of (+) electrode

subtract potential of (-) electrode (without diffusion potential).
E = M2/M1 +M1/L1+L1/L2+L2/M2
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2. Electric work 2. Nernst equation

Electrical work for conversion of 1 mole reactants: Effect of concentration on E &

A’max = q.E = n.F.E
Rxn. in cell: aA + bB = dD + lL Products
At const. T & P, applying 2nd thermodynamic law for reversible process:
G = - A’max a Dd .aLl At 298 K:
− G = RT ln K a − RT ln( ) = nFE
a Aa .a Bb
0.059 𝑎 . 𝑎
G = -n.F.E 𝐸=𝐸 −
𝑛
𝐥𝐠
𝑎 .𝑎

n: number of electrons interchange

For Daniel cell Reactants
E: electromotive force of cell (V)
F (96485 C/mol): Faraday’s constant 0.059 aZn 2+
E = ( ECu
0
2+
/ Cu
− EZn
0
2+
/ Zn
)− lg
G (J/mol) 2 aCu 2+
(NERNST equation)
1 J = 1 W.s = 1 V.(A.s) = 1 V.C

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2. Nernst equation 2. Nernst equation

Caculate E for Rxn. on electrode: Oxidant + n.e  Reductant

At 298 K

𝑅𝑇 𝑎 0.059 𝑎
𝜑=𝜑 − ln 𝜑=𝜑 − lg
𝑛𝐹 𝑎 𝑛 𝑎
0.059 [Fe ]
E=E − lg
n [Fe ][Ag ]
o: electrode potential at ai = 1
E = 0.799 − 0.771 = 0.028 V o298 checked in Data section

0.059 0.20
E = 0.028 − lg = 0.01 V
1 0.10x1.0
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2. Gibbs – Helmholtz equation 2. Effect of temperature

S = ST2 – ST1
G = H - T.S
emf’s temp. coefficient
Emf’s temp. dE S
For cell
coefficient:
= is proportional to the
– dT nF entropy change.

 ( G )  (G )
G = H + T. − n.E.F = H − T. For electrode:
In the narrow temp. range
T P T P emf’s temp. → d/dT = const.
coefficient
H T  (−nFE ) H E d
E=− − =− + T.
o
T = o
298 + (T − 298)
n.F n.F T P n.F T P dT

H dE
E=− +T Ex: φ | = 0.7991 − 1.00.10 55 − 25 = 0.769 V
n.F dT
( )

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2. Effect of temperature 2. Effect of temperature

Determine H, S, G for the reaction: Ag + 1/2 Cl2 = AgCl at 25 oC

Give (-) Ag, AgCl HCl Cl2, Pt (+) with E = 1.132 V; dE/dT = -0.000477 V/K
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2. Luther relation 3. Classification of cells and electrodes

Considering on M metal have 2 cations of Mh+ và Mn+ TYPE 1: Reversible cationic/anionic electrodes consist of metal
(or non-metal) in a solution containing its ion.
Mh+ + he → M (1) G1 = -hF1
Reversible cationic electrode: Mn+ M: Mn+ + ne = M
Mn+ + ne → M (2) G2 = -nF2 ne
𝑅𝑇 𝑎
Mh+ + (h-n)e → Mn+ (3) G3 = -(h-n)F3 𝜑 / =𝜑 / − ln
𝑛𝐹 𝑎
𝑅𝑇
rxn. (1) = rxn. (3) + rxn. (2) 𝜑 =𝜑 + ln 𝑎
/ /
−h. F. φ1 = −(h − n). F. φ3 − n. F. φ2 → G1 = G3 + G2 𝑛𝐹
Cu2+/Cu
Reversible anionic electrode:
(h-n). 3 =h 1 -n 2
(Luther relation) A An-: A + ne = An-
𝑅𝑇 𝑎
𝜑 / =𝜑 / − ln
𝑛𝐹 𝑎
𝑅𝑇
𝜑 / =𝜑 / − ln 𝑎
𝑛𝐹

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3. Classification of cells and electrodes 3. Classification of cells and electrodes

TYPE 2 Metal coated by an insoluble salt immersed in a solution

containing the anion of the salt.
Notation: An-  MA  M

❑ RXN. on the electrode: MA + ne = M + An-

RT
❑ Nernst equation: MA / M , A n− = o
MA / M , An−
− ln a An−
nF
Electrode Ag-AgCl: Cl-  AgCl  Ag
Half rxn. : AgCl + e = Ag + Cl-

𝜑 / , =𝜑 / , − 0.059 lg 𝑎 𝜑 = 0.2678 − 0.059 lg 𝑎

Besides normal hydrogen electrode (NHE), calomel and silver chloride
electrodes are considered as typical reference electrodes.
𝜑 / , = 0.197 𝑉 At saturated KCl 𝜑 = 0.241 𝑉
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3. Classification of cells and electrodes 3. Classification of cells and electrodes

TYPE 3 A metal coated by two insoluble salts with common GAS ELECTRODES
anion in a solution containing cation of the second salt. An inert metal in contact with both a gas and its ion
2
RT a H +
M’n+  M’A, MA  M TMA < TM’A = o
+ ln
H2 gas electrode: H+  H2  Pt H + / H2 H + / H2
2 F PH 2
Ca 2+CaCO3, PbCO3Pb
0.059
25 o C  H + / H2
= −0.059 pH − lg PH 2
Reaction: PbCO3 + Ca2+ + 2e = Pb + CaCO3 2
R.T
= 0
Pb 2+ / Pb
+ . ln aPb2+ = o
+
RT PO
ln 4 2
n.F O2: OH-|O2, Pt → O2 + 2H2O + 4e = 4OH- OH − / O2 OH − / O2
4 F aOH −

TPbCO3 = aPb2+ .aCO 2− ; TCaCO3 = aCa 2+ .aCO 2−

3 3
RT PCl
Cl2: Cl-|Cl2, Pt → Cl2 + 2e = 2Cl-  Cl =  Clo − / Cl + ln 2 2
TPbCO3 R.T −
/ Cl 2 2
2 F aCl −
a Pb2+ = aCa 2+ = '0
+ . ln aCa 2+
TCaCO3 n.F

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3. Classification of cells and electrodes 3. Classification of cells and electrodes

AMALGAM ELECTRODES: REDOX ELECTRODES

An amalgam is an alloy of mercury with another metal. It may be a liquid, a An inert metal (e.g., Pt) in a solution containing both oxidative and
soft paste or a solid, depending upon the proportion of mercury. reductive forms.
Ox, Red  Pt Ox + ne = Red
Mn+  M, Hg; Mn+ + ne = M(Hg)
RT aKh
RT aM ( Hg ) Re dox = o
Re dox − ln
n+ = o
− ln nF aOx
M / M , Hg M n+ / M , Hg
nF a M n+
RT aFe2+
Simple redox electrode: Fe3+, Fe2+  Pt 3+ 2+ = o
− ln
Cadmium amalgam electrode: Cd2+ Cd, Hg Cadmium amalgam electrode
Fe / Fe , Pt Fe3+ / Fe 2+ ,Pt F aFe3+
Electrode rxn. (Cd 12.5%) is used to make
MnO 4– , Mn2+, H+|Pt → MnO4– + 8H+ + 5e = Mn2+ + 4H2O
Weston battery, which has
RT aCd ( Hg ) constant E and is used in
Cd 2+
/ Cd , Hg
= o
Cd 2+ / Cd , Hg
− ln emf measurement.
2F aCd 2+
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3. Classification of cells and electrodes 3. Classification of cells and electrodes

COMPLEX REDOX ELECTRODE GLASS ELECTRODE

pH meter
Electrode: MnO4-, H+ , Mn2+  Pt MnO4- + 8H+ + 5e = Mn2+ + 4H 2O a H + aM +
K= tt

8 RT RT a 2+ a H + .a H +
MnO4− , H + / Mn 2+ , Pt
= o
MnO4− , H + / Mn2+ , Pt
+ ln a H + − ln Mn tt
5F 5 F aMnO−
4
𝑎
o OH 𝜑 = 𝜑 + 0.059 lg
C6H4O2,H + C6H4(OH)2,Pt : + -
+ 2H + 2e =
𝑎
(Quinhydrone electrode) o OH

Quinone (Q) Hydroquinone (Hq) pH = 10 – 12

 =  + 0.059𝑝𝐻
RT a Hq
= o
− ln RT aH + (a − a H + )
Quinh Quinh
2 F aQ aH2 + Quinh = o
Quinh + ln aH + K= tt

F aH + a H +
RT RT aHq Alkaline medium
tt

Quinh = o
Quinh + ln aH + − ln (As indicator electrode for pH measurement)
F 2 F aQ  = + 0.059𝑝𝐻
𝜑 = 𝜑 + 0.059 lg 𝑎

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4. Junction (diffusion) potential 4. Junction (diffusion) potential

df: exist in loaded circuits, at interface of the two electrode solutions

Eload = E + df
Reason: velocities of ions are different an electrical double layer
appears an electric potential jump junction (diffusion) potential
− − + RT a''
 df = ln '
Ex: (-) Ag  AgNO3 (a’) ⋮ AgNO3(a’’) Ag (+) (a’ < a’’) − + + F a
- AgNO3 diffuse from (+) to (-) (because of
concentration difference) If t- > t+ - > + → df > 0 Eload > E
- Velocity of NO3- > velocity of Ag+ → NO3- If t- < t+ - < + → df < 0 Eload < E
-
moves faster through the membrane If t- = t+ - = + → df = 0 Eload = E
-
→ (-) charges, left of the membrane has -
-
-
(+) charges → df -
- df is often small (< 0.1 V) 3’(a’ (a”
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4. Junction (diffusion) potential 5. Measurement of emf

Measurement of emf
Methods to avoid df
AC
Ex = .Ew
1/ Use salt bridge: an agar form of AC '

concentrated salt containing cation Ew: a known, highly stable emf cell (Weston cell)

and anion which have similar velocity. Weston cell:

Ex: KCl, KNO3, NH4Cl, NH4NO3 (-) Cadmium amalgam electrode
(+) Hg electrode type 2
Temperature coefficient: 5.10-5 V/oC (very small)
2/ Make double cells:

(-) Ag, AgCl  HCl(a’) : HCl(a’’) AgCl,Ag (+)

(-) Ag,AgCl  HCl(a’) H2, Pt, H2 HCl(a’’)  AgCl,Ag (+)

(-) Cd(Hg) (12.5%)CdSO 4 ,CdSO 4.8/3H2O(s)Hg2SO4  Hg,Pt (+)

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5. Applications 5. pH measurement

Principle: measurement of emf of a cell consists:

pH measurement
Determination of activity coefficients ()
Determination of solubility product (T)
- A known  electrode: Calomel, or silver chloride electrode (reference
electrode)
- A electrode which potential depends on pH: Hydrogen electrode,
quinhydron electrode, glass electrode (indicator electrode)
(-) Hg, Hg2Cl2 | KCl || H+ (x) | glass electrode (+)

E= tt − cal = 0
tt − 0.059 pH − cal

0
− cal − E
pH = tt
0.059

Advantage: no chemicals needed

Disadvantage: fragile due to the very thin glass membrane (0.01–0.03 mm)
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5. Determination of activity coefficients 5. Determination of solubility product

Determination of activity coefficients ( ) Determination of solubility product (T)

Ex: Determine of HCl with molarity m Ex: Determine T AgCl

Consider a cell: (-) Pt, H2 (1 atm) | HCl (m) | Hg2Cl2, Hg (+) Consider a cell: (-) Ag, AgCl | HCl | Cl2, Pt (+)
Reaction: 1
Reaction: Hg2Cl2 + H2 = 2Hg + 2HCl Cl 2 + Ag → AgCl 
2
E =  Cl −  AgCl / Ag ,Cl − = 0
− 0.059 lg aCl − − 0
− 0.059 lg aCl −
R.T a2 R.T 2 / Cl − Cl 2 / Cl − AgCl / Ag ,Cl −
NERNST equation: E = E0 − . ln HCl = E 0 − ln a HCl
2F PH 2 F 0
= 0
+ 0.059 lg TAgCl
AgCl / Ag , Cl − Ag + / Ag
R.T R.T
= E0 − ln a2HCl = E 0 − 2 ln(  .  .m)
F F E= 0
Cl 2 / Cl −
− 0
Ag + / Ag
− 0.059 lg TAgCl

R.T R.T 0
= 1.358V ; 0
= 0.799V
E = E0 − 2 ln(  .m) − 2 . ln(  ) Cl 2 / Cl − Ag + / Ag
F F
Emeas. = 1.136 V → TAgCl = 1.77x10-10

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6. Electrochemical sources 6. Electrochemical sources

Primary cells/batteries
- Primary cells/batteries: One-time use (non-rechargeable)
Ex: La Clanché (Zn-C)

- Secondary cells/batteries: Rechargeable

Ex: Lead acid, NiCd, NiMH, Li-ion

- Fuel cell/batteries: Work continuously

Ex: Hydrogen – oxygen cell
(-) Zn  NH4Cl (20%), ZnCl2  MnO2, C (+) Eo = 1.6 V

(-) Zn – 2e = Zn+2 (+) 2MnO2 + H2O + 2e = Mn 2O3 + 2OH-

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6. Electrochemical sources 6. Electrochemical sources

Secondary cells/batteries Secondary cells/batteries

A nickel metal hydride battery (NiMH) cells are
often used in digital cameras and other high-drain
devices.
Negative electrode:
H2O + M + e− ⇌ OH− + MH
Positive electrode:
Ni(OH)2 + OH− ⇌ NiO(OH) + H2O + e−

(-) Pb  PbSO 4  H2SO 4 (25-30%)  PbO2  Pb (+)

(-) Pb + SO42- – 2e  PbSO4

Eo = 2.037 V

(+) PbO2 + 4H+ + SO42- + 2e  PbSO4 + 2H2O

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6. Electrochemical sources 6. Electrochemical sources

Secondary cells/batteries Fuel cell

1.23 V