Electrochemistry:

Is the study of redox reactions at an electrode.

• Redox reaction is spontaneous (ΔG < 0)

• Redox reaction is non-spontaneous (ΔG > 0)

Faradaic Reaction : An electrochemical reaction that involves charge transfer

 Electrochemical cell:
Are devices in which an electric current (a flow of electrons through a circuit).

In an electrochemical cell, there are two half reactions that are giving and receiving
electrons to electrode respectively, leading to a neutral overall reaction.

Galvanic or voltaic cell:

Electrolytic cell:
Produced by a spontaneous chemical reaction
used to bring about a non-spontaneous reaction
(ΔG < 0)
(ΔG > 0)

Nota: una pila

es una serie
de celdas
galvánica
What is happening in an electrochemical cell??

The reactions are taking place upon metal surfaces, or electrodes.

An oxidation-reduction equilibrium is established between the metal and electrolytes

(ions in solution, usually fluid, that conducts electricity through ionic conduction).

Two possible interactions can occur between the metal atoms on the electrode and
the ion solutions:

1.Metal ion Mn+ from the solution may collide with the electrode, gaining "n"
electrons from it, and is reduced to metal atoms. This occurs in the cathode.

2.Metal atom on the surface may lose "n" electrons to the electrode and enter the
solution as the ion Mn+ meaning that the metal atoms are oxidized. This occurs in the
anode.
 Example of a galvanic cell??
Flow of Electrons:

A
Electrons always flow from the anode to the
cathode or from the oxidation half cell to the
reduction half cell.

e In terms of Eocell of the half reactions, the

& X electrons will flow from the more negative half
reaction to the more positive half reaction.

A cell diagram is a representation of an

·
electrochemical cell.
&

Ens1Z11 Sn ** Snet &

Esto se tiene que
aprender: esto es
como
Galvanic or voltaic cell: &
representamos
Produced by a spontaneous chemical reaction una celda
(ΔG < 0)
 To construct a cell diagram follow these simple instructions. Consider the following reaction:

Step 1: Write the two half-reactions. Reduce

Oxidacion
Step 2: Identify the cathode and anode.
Cu(s) is losing electrons thus being oxidized; oxidation occurs at the anode.
Anode (where oxidation occurs):
Ag+ is gaining electrons thus is being reduced; reduction happens at the cathode.
Cathode (where reduction occurs):

Step 3: Construct the Cell Diagram.

The anode always goes on the left and cathode on the right. Separate changes in phase by | and indicate the the salt
bridge with ||. The lack of concentrations indicates solutions are under standard conditions (i.e., 1 M)
Overall, the electrochemical cell may be represented by:

Where phase boundaries are represented by "| ", and the salt bridge is represented by "| | "

Example?? zn/z II Sna ,

Snip
Another cell has utilizes the following redox reactions:
Zn(s) → Zn2+(aq) + 2 e- Sn4+(aq) + 2 e- → Sn2+(aq)
-
-

The reaction at the anode is: 4

The reaction at the cathode is:
q II Su(n A Sun IPH
+

The electrochemical cell may be represented by:

En + Sn
+
>
- 2724 + Sp2
 Que hacer?
Example??
Si temenos duda de que puede hacer cada uno de ellos de
entrada revisamos los potenciales de reducción.
𝒁𝒏𝟐 + 𝟐𝒆 → 𝒁𝒏 𝑬𝒐𝒓𝒆𝒅 = -0.74
El que se oxida mas fácil es el Zn y el que se puede reducir
𝟒 𝟐
𝑺𝒏 + 𝟐𝒆 → 𝑺𝒏 𝑬𝒐𝒓𝒆𝒅 = 0.15 más fácil es el 𝑺𝒏𝟒

Con estos datos Podemos ya decidir donde ocurre cada

reacción

The reaction at the anode is: The reaction at the cathode is:
Zn(s) → Zn2+(aq) + 2 e- Sn4+(aq) + 2 e- → Sn2+(aq)

The electrochemical cell may be represented by: Nota :NO hay error si
es una coma, ya que el
Zn(s) І Zn2+(aq) І І Sn4+(aq) , Sn2+(aq)PA
element no cambia de
fase sigue en solución
Galvanic cell vs Electrolytic cell
Galvanic cell vs Electrolytic cell
 e - e- e- e- e- e - e-
e- e-
2e-

2e-
i ↑ ↑
&

& ↑

- Y

↑
↑ -

Anode Cathode
 Faradays’ Law: Describes how changing magnetic fields produce electric fields.
Q = I · t.
Q = magnitude of charge in Coulombs (C)
I = current in amperes (A) (amperes =coulomb/second)
t = time (seconds)
Faradays’ Constant:
1 Faraday (F) = 96,485 C/mol

The electrochemical cell: Zn(s) І Zn2+(aq) І І Cu2+(aq) І Cu(s)

Exercise: How much Zn is consumed and how much Cu is deposited if a current of 1.0 A flows for 1.0 hours?

Step 1. Determine the amount of charge that passed though the circuit:
Q = 1 A · 3600 sec = 3600 C
Step 2. Determine the number of moles of electrons to which this charge is equivalent:
3600 𝐶 𝑥 , >
-
= 0.0373 moles of electrons
Step 3. Calculate the number of moles of Zn consumed and Cu deposited and convert to grams.
1 𝑚𝑜𝑙 𝑍𝑛 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑛𝑑 63.59 𝑔 𝑍𝑛
0.0373 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑒 𝑝𝑎𝑠𝑠𝑒𝑑 𝑥 𝑥 = 1𝑔 𝑜𝑓 𝑍𝑛
2 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑒 𝑝𝑎𝑠𝑠𝑒𝑑 1 𝑚𝑜𝑙
1 𝑚𝑜𝑙 𝐶𝑢 𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑 63.55 𝑔 𝐶𝑢
0.0373 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑒 𝑝𝑎𝑠𝑠𝑒𝑑 𝑥 𝑥 = 1𝑔 𝑜𝑓 𝐶𝑢
2 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑒 𝑝𝑎𝑠𝑠𝑒𝑑 1 𝑚𝑜𝑙
Cell potential: The flow of electrons arises from a potential difference, ΔEcell, between the electrodes in the
circuit.

ΔEcell is also known as cell voltage, and electromotive force (emf).

∆𝑬𝒐𝒄𝒆𝒍𝒍 = cell potential (cell voltage) in which products and reactants are in their standard states Units for ΔE

Example: - Calculate ∆𝐸 for 𝑍𝑛( ) | 𝑍𝑛( ) || 𝐶𝑢( ) | 𝐶𝑢( )

Anode 𝑍𝑛( ) ⇒ 𝑍𝑛( ) + 2𝑒 cathode 𝐶𝑢( ) + 2𝑒 ⇒ 𝐶𝑢( )

∆𝑬𝒐𝒄𝒆𝒍𝒍 = 𝑬𝒐𝒄𝒂𝒕𝒉𝒐𝒅𝒆 − 𝑬𝒐𝒂𝒏𝒐𝒅𝒆

(standard reduction potential minus standard reduction potential for the couple at cathode for the couple at anode)

𝒁𝒏𝟐 + 𝟐𝒆 → 𝒁𝒏 𝑬𝒐𝒓𝒆𝒅 = -0.74

∆𝑬𝒐𝒄𝒆𝒍𝒍 = 0.34 –(-0.74) = 1.08
𝑪𝒖𝟐 + 𝟐𝒆 → 𝑪𝒖𝟎 𝑬𝒐𝒓𝒆𝒅 = +0.34

∆𝑮𝒐𝒄𝒆𝒍𝒍 = - 𝐧ℱ∆𝑬𝒐𝒄𝒆𝒍𝒍 so if ∆𝑬𝒐𝒄𝒆𝒍𝒍 is positive ∆𝑮𝒐𝒄𝒆𝒍𝒍 will be negative that means the reaction is spontaneous and we
have a galvanic cell
What do we know already about equilibrium and the components of a reaction?
We know that ΔG changes as the concentrations of the components change until equilibrium is reached, then ΔG = 0

[ ]
ΔG = ΔG° + RT ln [ ]
And we know ∆𝑮𝒐𝒄𝒆𝒍𝒍 = - 𝐧ℱ∆𝑬𝒐𝒄𝒆𝒍𝒍 , if we combine, we get:

[ ]
∆𝑮 = - 𝐧ℱ∆𝑬𝒐𝒄𝒆𝒍𝒍 + RT ln [ ]

[ ]
𝐧ℱ∆𝑬 = - 𝐧ℱ∆𝑬𝒐𝒄𝒆𝒍𝒍 + RT ln [ ]

If we dived by 𝐧ℱ is the Nerst equation

[ ]
∆E = E° + ln
ℱ [ ]
Example: Calculate ΔE (the cell potential, potential difference, emf) at 25 °C of a cell in which the concentration
of Zn2+ ions is 0.10 M and Cu2+ is 0.0010 M.

𝑺𝒕𝒆𝒑 𝒐𝒏𝒆 ∶ ∆𝑬𝒐𝒄𝒆𝒍𝒍

∆𝐸 for 𝑍𝑛( ) | 𝑍𝑛( ) || 𝐶𝑢( ) | 𝐶𝑢( )

Anode 𝑍𝑛( ) ⇒ 𝑍𝑛( ) + 2𝑒 cathode 𝐶𝑢( ) + 2𝑒 ⇒ 𝐶𝑢( )

∆𝑬𝒐𝒄𝒆𝒍𝒍 = 𝑬𝒐𝒄𝒂𝒕𝒉𝒐𝒅𝒆 − 𝑬𝒐𝒂𝒏𝒐𝒅𝒆

𝑪𝒖𝟐 + 𝟐𝒆 → 𝑪𝒖𝟎 𝑬𝒐𝒓𝒆𝒅 = +0.34 𝒁𝒏𝟐 + 𝟐𝒆 → 𝒁𝒏 𝑬𝒐𝒓𝒆𝒅 = -0.74

∆𝑬𝒐𝒄𝒆𝒍𝒍 = 0.34 –(-0.74) = 1.08

𝑺𝒕𝒆𝒑 𝒕𝒘𝒐:
[0.10 ]
∆E = 1.08 V + ln
ℱ [0.0010 ]

( . )( ) [0.10 ]
∆E = 1.08 V + ln
( )( ) [0.0010 ]

∆E = 1.08 V – 0.0592 = +1.0208 V

 [𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔]
What about if want to study at EQUILIBRIUM? K = [𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔] that is ΔG = 0

[𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔]
ΔG = ΔG° + RT ln
[𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔]

ΔG° = - RT ln K
And ∆𝑮𝒐𝒄𝒆𝒍𝒍 = - 𝐧𝓕∆𝑬𝒐𝒄𝒆𝒍𝒍 if we combine

- 𝐧𝓕∆𝑬𝒐𝒄𝒆𝒍𝒍 = - RT ln K

[𝐧𝓕∆𝑬𝒐𝒄𝒆𝒍𝒍 ]
ln K = [RT]

We can know the equilibrium K

 How can I use the reduction
potential????
Si checamos al Fluor 𝑬𝒐𝒓𝒆𝒅 el valor es +
3.03, al ser este positivo significa que
es fácil que reciba electrones, algo que
ya sabemos verdad, no es fácil que los
done y por lo tanto es un buen agente
oxidante

Si comparamos el mismo Potasio con el

Fluor
𝑲 + 𝒆 → 𝑲 𝑬𝒐𝒓𝒆𝒅 = -2.924
𝑭𝟐 + 𝟐𝒆 + 𝟐𝑯 → 𝑯𝑭 𝑬𝒐𝒓𝒆𝒅 = 3.03
Nos damos cuenta de que ambos el
potasio se puede oxidar más fácil
mientras fluor tiende a reducirse
Diagrama de Latimer:

En el diagrama de Latimer se escribe la especie con mayor número de oxidación

a la izquierda.
Veamos los potenciales de reducción de compuestos con Cloro

Si los colocamos en el diagrama de Latimer :

El diagrama nos indica que todos los compuestos son agentes oxidantes y
pueden reducirse. Pero HClO2 es el mejor agente oxidante.
 Veamos los potenciales de reducción de compuestos con Cloro en medio básico
Si los colocamos en el diagrama de Latimer :
0.36 V 0.35 V 0.65 V 0.40 V 1.36 V
𝐶𝑙𝑂 𝐶𝑙𝑂 𝐶𝑙𝑂 𝐶𝑙𝑂 𝐶𝑙 𝐶𝑙

0.88 V

Si lo comparamos con los potenciales de las especies que en condiciones ácidas,

contienen H+, son menores:
1.65 V 1.63 V 0.65 V 0.40V
H𝐶𝑙𝑂 𝐻𝐶𝑙𝑂 𝐶𝑙 𝐶𝑙𝑂 𝐶𝑙𝑂 𝐶𝑙

Lo que nos indica que tienen un poder de oxidación

menor, son malos agentes oxidantes en
condiciones básicas.
 We can use Latimer diagram to know a reaction that is missing from the list of half-cell
𝐶𝑙𝑂 + 2𝐻 𝑂 + 4𝑒 𝐶𝑙𝑂 + 4𝑂𝐻
𝑬𝒐𝒓𝒆𝒅 Δ𝑮𝒐 = −𝐧 Δ𝑭𝑬𝒐
𝐶𝑙𝑂 + 𝐻 𝑂 + 2𝑒 𝐶𝑙𝑂 + 2𝑂𝐻 0.35 -67.5 kJ/mol ( - 2)19 65 x 105 -(0 35)
.
.

𝐶𝑙𝑂 + 𝐻 𝑂 + 2𝑒 𝐶𝑙𝑂 + 2𝑂𝐻 0.65 -125.4 kJ/mol

-193.0 kJ/mol

Importante: Los potenciales de celda no se pueden sumar. “No son aditivos

Pero si podemos utilizar la energía libre de gibbs. 𝛥𝐺 =
E =
- =65 x 10 j /
9 .

ΔG° = -193.0 kJ/mol and n = 4, so the final voltage is 0.50 V. We can now add this new
half-cell to the basic solution Latimer diagram:
0.36 V 0.35 V 0.65 V 0.40 V 1.36 V
𝐶𝑙𝑂 𝐶𝑙𝑂 𝐶𝑙𝑂 𝐶𝑙𝑂 𝐶𝑙 𝐶𝑙

0.50 V 0.88 V
If we analyzed hypochlorite 𝐶𝑙𝑂 , we might think that in solution if is not present any
reducing.
But the hypochorite can act as its own reducing agent

𝑪𝒍𝑶 + 𝑯𝟐 𝑶 + 2𝒆 𝑪𝒍 + 2𝑶𝑯 𝑬𝒐𝒓𝒆𝒅 0.88 V E1

𝑪𝒍𝑶𝟑 + 2𝑯𝟐 𝑶 + 4𝒆 𝑪𝒍𝑶 + 4𝑶𝑯 𝑬𝒐𝒓𝒆𝒅 0.50 V E2

Si multiplicamos la E1 por dos (reacción del cátodo) y 2 𝐶𝑙𝑂 + 2 𝐻 𝑂 + 2𝑒 𝐶𝑙 + 2𝑂𝐻

utilizamos E2 en sentido contrario de tal manera que
sea la reacción que ocurre en el ánodo 𝐶𝑙𝑂 + 4𝑂𝐻 𝐶𝑙𝑂 + 2𝐻 𝑂+ 4𝑒

3𝐶𝑙𝑂 2𝐶𝑙 + 𝐶𝑙𝑂

The cell voltage 𝑬𝒐𝒄𝒆𝒍𝒍 = 𝑬𝒐𝒄𝒂𝒕𝒉𝒐𝒅𝒆 - 𝑬𝒐𝒂𝒏𝒐𝒅𝒆 = 𝟎. 𝟖𝟖 𝑽 − 𝟎. 𝟓𝟎 𝑽 = 𝟎. 𝟑𝟑 𝑽, which means

that the reaction is spontaneous.
A redox reaction where a substance reacts with itself to be both oxidized and reduced is called a
Disproportionation. Hypochlorite is unstable with respect to disproportionation
Latimer diagrams provide a very easy way to determine if disproportionation is
spontaneous. For example, consider just the two reactions important for 𝑪𝒍𝑶
disproportionation:
0.5 V 0.88V
𝐶𝑙𝑂 𝐶𝑙𝑂 𝐶𝑙

Cómo sabemos si un compuesto es

inestable y sufre desproporción?
If the voltage to the right of the species in
question is greater than the voltage to the left of
the species, the species is unstable with respect
La sustancia aun en
cuarentena y solita hace to disproportionation.
su fiesta y reacciona  Revisamos el diagrama de Latimer y si el potencial de
reducción de la derecha de la especie de interés es mayor
al de la izquierda la sustancia reacciona con ella misma
sufre desproporicón.
 For another example, we can determine if 𝑪𝒍𝑶𝟑 is stable or unstable:

0.36 V 0.35 V 0.65 V 0.40 V 1.36 V

𝐶𝑙𝑂 𝐶𝑙𝑂 𝐶𝑙𝑂 𝐶𝑙𝑂 𝐶𝑙 𝐶𝑙

0.50 V 0.88 V
Revisamos el diagrama de Latimer y si el potencial de
reducción de la derecha de la especie de interés es mayor al
de la izquierda la sustancia reacciona con ella misma sufre
desproporicón.

0.36 V 0. 50 V Al ser mayor 0.5o V que 0.36 V quiere decir que el

𝐶𝑙𝑂 𝐶𝑙𝑂 𝐶𝑙𝑂 ion clorato es inestable
Often the stability of substances is very pH dependent. For example, hypobromite
is unstable in acid and stable in basic solution:

Acidic solution:
1.49 V 1. 59V
V𝐵𝑟𝑂 𝐻𝐵𝑟𝑂 𝐵𝑟

Basic solution:
0.54 V 0.45V
𝐵𝑟𝑂 𝐵𝑟𝑂 𝐵𝑟

En solución ácida el 𝐻𝐵𝑟𝑂 es inestable sufre desproporción

En solución básica el 𝐵𝑟𝑂 es estable

Revisa la estabilidad
de y de 𝐻 𝑂 y de
𝑆 𝑂
Often the stability of substances is very pH dependent. For example, hypobromite
is unstable in acid and stable in basic solution:

Acidic solution:
1.49 V 1. 59V
V𝐵𝑟𝑂 𝐻𝐵𝑟𝑂 𝐵𝑟

Basic solution:
0.54 V 0.45V
𝐵𝑟𝑂 𝐵𝑟𝑂 𝐵𝑟

En solución ácida el 𝐻𝐵𝑟𝑂 es inestable sufre desproporción

En solución básica el 𝐵𝑟𝑂 es estable

Revisa la estabilidad
de y de 𝐻 𝑂 y de
𝑆 𝑂