Sarah Alvanipour, CC BY-NC-SA 4.

Electrochemistry

I. Oxidation Reduction Reactions Review

 Oxidation: process of losing electrons, results in an increase in oxidation # (charge)

 Reduction: process of gaining electrons, results in a decrease in oxidation #

 Example:

Zn (s) + 2HCl  ZnCl2 (aq) + H2 (g)

 Rules for Determining Oxidation Number:

o Free elements (in an uncombined state) have an oxidation number of zero

 Na, Be, K, Pb, H2, O2, P4 = 0

o In monatomic ions, the oxidation number is equal to the charge on the ion

 Li+, Li = +1; Fe3+, Fe = +3; O2-, O = -2

o The oxidation number of oxygen is usually –2. In H2O2 is -1 and O22- it is - ½
o The oxidation number of hydrogen is +1 except when it is bonded to metals in
binary compounds. In these cases, its oxidation number is –1
o Group IA metals are +1, IIA metals are +2 and fluorine is always –1.
o The sum of the oxidation numbers of all the atoms in a molecule or ion is equal to
the charge on the molecule or ion.
o Ex. HNO3 Here the oxidation number of nitrogen is the unknown and can
be calculated to be +5 by using the known values for H (+1) and O (-2).

Sample Problem: What is the oxidation number of chromium K2Cr2O4 Here the oxidation #
of Cr is the unknown and can be calculated using the known values for K (+1) and O (-2)

2 K +2Cr + 4 O=0

( +1 x 2 ) +2 Cr+ (−2 x 4 )=0

+2+2 Cr−8=0

2 Cr=+6

Cr=+3

II. Writing Half Reactions:

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Most redox reaction problems require the half reactions to be written to determine what has
been oxidized (written as the oxidation half) and what has been reduced (written as the
reduction half).

 This goes against the past tradition of assuming the reactants are one half and
products are another. Redox reactions are very much looking at a “before” and
“after” scenario for EACH atom involved in the reaction.

 Oxidation and reduction reactions occur simultaneously so there is an exchange of

electrons. Since electrons are matter and must be conserved, however many
electrons are lost in the oxidation half of the reaction must be equal to those gained
in the reduction half.

o Thus electron # must always be balanced or the same in both halves!

 Example:

Mg (s) + 2HCl  MgCl2 (aq) + H2 (g)

Oxidation half: Mg (s)  Mg2+- + 2e- Mg is oxidized by losing 2 electrons

Reduction half: 2H+ + 2 e-  H2 H is reduced as each H+ gains 1

electron

Note: Magnesium loses 2 electrons for each mole of Mg, and since each hydrogen
atom only gains 1 electron, we must have 2 moles of hydrogen present to gain both
electrons from magnesium.
Sarah Alvanipour, CC BY-NC-SA 4.0

III. Balancing Redox Reactions:

 Balancing redox reactions is more complex than balancing normal chemical

reactions. Some differences are as follows:

o Each half reaction is balanced independently and then the two are added
together to give the overall reaction

o Electrons are also balanced in the process

o The balancing is done in either an acidic or basic solution which influenced

how the equation is balanced

o Non oxygen and hydrogen atoms are balanced first

o For both acidic/basic mediums: Water molecules are added to balance the #
of oxygen atoms. For every oxygen needed, add 1 H2O to the opposite side of
the equation.

o For both acidic/basic mediums: Once water is added, excess H atoms may be
present which are then balanced by adding H+ atoms to the opposite side of
the equation

o For both basic medium only: Hydroxide ions are added to balance/neutralize
the H+ atoms (forming water molecules) as well as provide an excess of OH-
to render the reaction basic. Thus, for each H+, 1 OH- is added.
Sarah Alvanipour, CC BY-NC-SA 4.0

Sample Problem:

Balance the following equation in ACIDIC MEDIUM.

Mn2+(aq) + BiO3-1 (s) → Bi3+(aq) + MnO4− (aq)

1) Write the half reactions

Oxidation: Mn2+  MnO4-

Reduction: BiO3-1  Bi3+

2) Determine the oxidation numbers of Mn and Bi as O remain the same (see rules
above).

Mn is +2 before and +7 after; Bi is +5 before and +3 after

Oxidation: Mn2+  MnO4- + 5 e-

Reduction: BiO3-1 + 2e-  Bi3+

3) Balance all NON oxygen and hydrogen atoms…

DONE in this example; otherwise add coefficients to balance.

4) Balance the oxygen atoms by adding H2O (add 1 water molecule for each oxygen).

4 H2O(l) + Mn2+(aq) → MnO4-(aq)

5) Add H+ to balance the # H atoms

4 H2O(l) + Mn2+(aq) → MnO4-(aq) + 8H+

6) Balance the charges by adding back your electrons…

4 H2O(l) + Mn2+(aq) → MnO4-(aq) + 5 e- + 8H+

7) Repeat the above steps for the reduction reaction: BiO3-1

BiO3-(s) → Bi3+(aq) + 3 H2O(l)

6 H+ + BiO3-(s) → Bi3+(aq) + 3 H2O(l)

2 e− + 6 H+ + BiO3-(s) → Bi3+(aq) + 3 H2O(l)

 Sarah Alvanipour, CC BY-NC-SA 4.0

8) Notice that one equation has 5 electrons and the other has 2 electrons. They MUST be
the SAME or equalized. So we must find a common denominator to equalize them.

Equalize the electrons by making electrons in each equation the same, 10e-.

5 x [2 e− + 6 H+ + BiO3-(s) → Bi3+(aq) + 3 H2O(l)]= 10 e− + 30 H+ + 5BiO3-(s) → 5Bi3+(aq) + 15 H2O(l)

2 x [4 H2O(l) + Mn2+(aq) → MnO4-(aq) + 5 e- + 8H+]= 8H2O(l) + 2Mn2+(aq) → 2MnO4-(aq) + 10 e- +16H+

9) Add the two equations together…cancel out the electrons, H+ atoms (30-16= 14 left),
and H2O (15-8 = 7 left)

10 e− +30 H+ + 5BiO3-(s) → 5Bi3+(aq) + 15 H2O(l)

+
8 H2O(l) + 2Mn2+(aq) → 2MnO4-(aq) + 10 e− + 16H+

14 H+(aq) + 2 Mn2+(aq) + 5 BiO3 -1(s) → 7 H2O(l) + 2 MnO4− (aq) + 5 Bi3+(aq)

 IF this were taking place in a BASIC medium, then we would still complete all steps
(1-9) above, but then add 1 OH- ion for each H+ ion we have to form water as
follows:

Sample Problem: Balance the following equation in ACIDIC MEDIUM.

Mn2+(aq) + BiO3-1 (s) → Bi3+(aq) + MnO4− (aq)

10) Picking up with :

14 H+(aq) + 2 Mn2+(aq) + 5 BiO3 -1(s) → 7 H2O(l) + 2 MnO4− (aq) + 5 Bi3+(aq)

Adding 1 OH ion for each H present:

14OH -+ 14 H+(aq) + 2 Mn2+(aq) + 5 BiO3-1(s) → 7 H2O(l) + 2 MnO4− (aq) + 5 Bi3+(aq) + 14OH-

Yielding:

14H2O (l) + 2 Mn2+(aq) + 5 BiO3-(s) → 7 H2O(l) + 2 MnO4− (aq) + 5 Bi3+(aq) + 14OH-

11) Clean up the equations: cancel out waters from both sides, one for one. Since we have
14 water molecules in the reactants, they will cancel out 7 of the water molecules in
products to yield…
Sarah Alvanipour, CC BY-NC-SA 4.0

14H2O (l) + 2 Mn2+(aq) + 5 BiO3-(s) → 7 H2O(l) + 2 MnO4− (aq) + 5 Bi3+(aq) + 14OH-

7 H2O(l) + 2 Mn2+(aq) + 5 BiO3-(s) → 2 MnO4− (aq) + 5 Bi3+(aq) + 14OH-

IV. Standard Electromotive Force (EMF)/Cell Potential:

 Cell voltage, otherwise known as cell potential, “electromotive force” (emf) or Eº ,

can be calculated for a wet cell (battery) to determine how much electrical potential
is generated from the chemical reaction.

o Recall that if a process is nonspontaneous (i.e. a light bulb being lit), then
energy must be input (in the form of chemical energy transferred into
electrical energy) in order to facilitate the process or give it energy (the ability
to do work).

 Standard cell potential (Eºcell) assumes standard conditions: 1M concentration or 1

atm pressure) by comparing the electrical potential difference between the two
nodes of a wet cell (battery): the cathode and the anode.

o Cathode: reduction half

o Anode: oxidation half

o Salt bridge:

o Typical wet cell diagram :

Salt Bridge: e- flow occurs

from anode to cathode

e- → e-

Sarah Alvanipour, CC BY-NC-SA 4.0 Anode Cathode

Sarah Alvanipour, CC BY-NC-SA 4.0

Flowers, P., Theopold, K., Langley, R., & Robinson, W. R. (2019). Electrochemistry. In Chemistry 2e. OpenStax.
https://openstax.org/books/chemistry-2e/pages/17-2-galvanic-cells

 How to calculate cell potential

1) Write the two half reactions of the equation

2) Identifying what was oxidized (which will be considered the anode)

3) Identifying what was reduced (which will be considered the cathode)

4) Find voltage values, called reduction potentials, or E, for each element in the
appendix

5) Take the difference between the E values using the formula:

Eºcell = Ecathode- Eanode

 Guidelines to reading the Standard Reductions Potential Table

o The values are provided for 1 mol of each element in units of voltage

o Unlike enthalpy, entropy, and free energy, the voltage is NOT governed by
rules of stoichiometry; therefore, the voltage is NOT multiplied by the
stoichiometric coefficient in the equation

o Values in the table are written as reduction equations (hence why the values
are called reduction potentials)
Sarah Alvanipour, CC BY-NC-SA 4.0

 The value for an oxidation potential would be the same in magnitude

but opposite in sign
 i.e. +0.74V reduction would be -0.74V

 Signs of reduction potentials are NOT to be reversed, however, prior to

insertion into the equation; rather the subtraction sign in the equation
itself with flip the sign.

o The table follows the activity series presented in early topics in chemistry and
lists the elements in order of reactivity. On one end of the table are those
elements who are the strongest reducers (and which are oxidized) and on the
opposite end are those elements which are the strongest oxidizers (and are
thus reduced).

o A small portion of the Standard Reductions Potential Table

Half-Reactions E0 (V)

Li+(aq) + e- -----> Li(s) -3.05

K+(aq) + e- -----> K(s) -2.93

Ba2+(aq) + 2 e- -----> Ba(s) -2.90

Sr2+(aq) + 2 e- -----> Sr(s) -2.89

Ca2+(aq) + 2 e- -----> Ca(s) -2.87

Na+(aq) + e- -----> Na(s) -2.71

Sarah Alvanipour, CC BY-NC-SA 4.0

 How to Determine the Cathode and Anode

o What is oxidized and reduced must be identified to plug values correctly into
any equation. The anode and cathode can be determined in one of three
methods:

1. The chemical equation or half reactions can be referenced and

oxidation #s can be compared before and after the reaction

Oxidation (anode): Mg (s)  Mg2+- + 2e-

Reduction (cathode): 2H+ + 2 e-  H2

2. The shorthand cell diagram can be read where the left side of the cell
diagram represents the anode (Mg) and to the right of the salt bridge
(||) is the cathode (H)

Mg|Mg2+ || H2|H+

3. The E value of each element can be looked up and as a general trend,

the more positive the E value, the more likely it is to be reduced.

E for Mg= -2.37

E for H= 0

Since the E for H is more positive (0 V), it will be reduced (cathode)

and the Mg (-2.37) will be oxidized (anode), which is the same result
as using the other methods.
Sarah Alvanipour, CC BY-NC-SA 4.0

Voltage or cell potential is

either calculated or measured
with a voltmeter.

Flowers, P., Theopold, K., Langley, R., & Robinson, W. R. (2019). Electrochemistry. In Chemistry 2e. OpenStax.
https://openstax.org/books/chemistry-2e/pages/17-3-electrode-and-cell-potentials

Sample Problem: Calculate the standard emf of a cell that uses Mg/Mg2+ and Cu2+/Cu half
cell reactions.

Step 1: Identify your cathode and anode using whichever means you like. Here we see the
Mg neutral then Mg2+ the problem and Cu2+ to Cu; thus Mg is oxidized and is the anode
while Cu is the reduced and the cathode. You can also look up the E° values for each
element and come to the same conclusion using the trends discussed above or simply look
at their positioning on the Standard Reduction Potentials reference table.

Step 2: Identify the E° values for Mg and Cu from the Standard Reduction Potentials
reference table. Mg= -2.37V (negative node is anode) and Cu= +0.34V (positive node is
cathode).

Step 3: Plug values correctly into the E° equation and solve for the standard reduction
potential. Remember NOT to flip the sign of the anode before inserting into the equation.

E °=E cathode −Eanode

E °=0.34 V −(−2.37 V )

E °=+2.71 V
Sarah Alvanipour, CC BY-NC-SA 4.0

V. Cell Potential and Spontaneity:

 Spontaneity can also be predicted for redox reactions using Ecellº

 This is related to the equilibrium constant, K, just as in free energy discussions
 The following equations can be used to calculate either Ecellº or K; both will yield the
same answer but each uses a difference form of a logarithm. They are simplified
versions of the equation using the Faraday (96,500 C/mol) constant and molar gas
constant R (8.314 J/mol•K)

o RT
E= log K
nF

Ecellº = 0.0592 V log K

OR

Ecellº = 0.0257 V ln K

where n= # electrons exchanged

Sample Problem: Calculate the equilibrium constant, K, for the reaction of a cell that uses
Mg/Mg2+ and Cu2+/Cu.

Step 1: Calculate the standard reduction potential first.

E °=E cathode −Eanode

E °=0.34 V −(−2.37 V )

E °=+2.71 V

Step 2: Plug into the E° and K equation and solve for K. Note the # electrons exchanged is
2; thus n=2.
Sarah Alvanipour, CC BY-NC-SA 4.0

Ecellº = 0.0257 V ln K

0.0257 V
2.71 V = −¿
2 e ln K ¿

2.71=0.0129lnK

210=lnK
210
e =K
91
1.72 x 10 =K

VI. Relating Thermodynamics and Electrochemical Principles

 Recall the following equation from free energy discussions

G° = -RT ln K

 This equation which helped predict spontaneity and describe the relationship
between K and G° can now be used to relate those to E cell
°

o Where n= # electrons
G° =- nFE°
o F= Faraday constant (96,500
C/mol or J/volt mol )
o A Coulomb is the SI unit for electrical charge and represents an
ampere-second or (A s)
 Ampere is a unit of electrical current

Sample Problem: What is the standard free energy in kJ associated with the reaction in a
cell that uses Mg/Mg2+ and Cu2+/Cu. How does the sign of G support spontaneity? Does
this match the K value calculated earlier (K= 1.72 x 1091) and the cell potential?

Step 1: Find the Ecellº.

E °=E cathode −Eanode

E °=0.34 V −(−2.37 V )

E °=+2.71 V

Step 2: Note the # electrons exchanged is 2; thus n=2.

Sarah Alvanipour, CC BY-NC-SA 4.0

G° =- nFE°

G° = - (2) (96,500 J/mol•K) (2.71V)

G° = 523,030 J  - 523 kJ

Step 3: Relate the signs of G, K and E to spontaneity.

Thermodynamics taught us that a -G value translates to a spontaneous reaction.

Additionally, a K>1 does the same. Since in the equation G° =- nFE°

G and E are opposite in sign due to the negative sign in front of “n,” then a -G correlates to
a +E. Since G is negative in this reaction, E is positive, and K>1, thus all point to the
reaction being spontaneous.

 The relationship between the variables G, E, and K and their equations can be
summarized in the following diagram

G
Gº = -nFE° cell G °=−RTlnK

E K
RT
E º= log K
nF

 The relationship between the variables G, E, and K and their equations can be
summarized in the following diagram
Sarah Alvanipour, CC BY-NC-SA 4.0

E° cell K ΔGrxn Equilibrium Favors

Positive >1 Negative Products Favored

0 =1 0 Products and
Reactants Equally
Favored

Negative <1 Positive Reactant Favored

 As always, rather than memorizing the table above, plugging in values and taking
note of how that influences the other variables in the equation is the best approach
to observing these trends

VII. The Effect of Concentration on Cell Emf

 When not operating the wet cell under standard conditions, other than 1M
concentration, the Nernst Equation is employed to calculate Ecellº and is simply a
variation on the previous equation:

Ecell = Ecellº - 0.0592 V log Q

OR

Ecell = Ecellº - 0.0257 V ln Q

“Q” is the ratio of concentrations of:

[oxidized substance ]
Q=
[reduced substance]
Sarah Alvanipour, CC BY-NC-SA 4.0

Sample Problem: What is the potential of a cell made up of Zn/Zn2+ and Cu2+/Cu at 25
degrees Celsius if [Zn2+] =0.25M and [Cu2+] =0.15M ? How does this cell potential compare
with that under standard conditions?

Step 1: Calculate the standard cell potential, Eº.

E °=E cathode −Eanode

E °=0.34 V −(−0.76 V )

E °=+1.1 V

Step 2: Note the cathode is Cu and anode is Zn; thus the concentrations of those ions will
be the ratio for “Q.” Two electrons are exchanged which makes n=2.

[oxidized species]
Ecell = Ecellº - 0.0257 V ln
[reduced species ]

0.0257 0.25 M
E cell=1.1 V − V ln
2 0.15 M
Ecell =1.1 V −(0.01285 V ) ln 1.67

Ecell = 1.1V- (0.01285V) ( 0.510)

Sarah Alvanipour, CC BY-NC-SA 4.0

Ecell = 1.093 V

Step 3: Compare the 1M standard concentration E value of 1.1V to the one

calculated here under non-standard conditions.

As the concentration of ions decreased here, so did the amount of voltage or cell potential
(1.09 at these concentrations of 0.25M/0.15M versus 1.1V at standard concentrations of
1M].

VII. Stoichiometric Relationships Between Cell Potential and Mass

 cell potential can be related to the mass of a metal (since they lose electrons) in the
salt component of a battery based on the strength of the current and the length of
time the battery operates

 Amperes, Coulomb (Faraday constant), and time are utilized along with
stoichiometric fundamentals to calculate mass (or time).

Sample Problem: What mass of Ca (from CaCl2) is required to run a current of 0.70 A for a
period of 1.2 hours?

Step 1: Calculate the Coulomb of charge

Convert time to seconds

60 min 60 s
1.2 hours x x =4320 s
1 hr 1min

Calculate Coulomb

C= A x t

C=( 0.70 A ) ( 4320 s )

C=3024 Coloumbs

Step 2: Convert Coulomb to electrons using Faraday’s constant

−¿
e
3024 C x 1 mol of =0.0313 electrons ¿
96500C
Sarah Alvanipour, CC BY-NC-SA 4.0

Step 3: Convert electrons to mols of calcium based on the charge of Ca2+ (for each 1 mol
Ca, 2 electrons are lost)
1 molCa
−¿ x −¿ ¿
2 e =0.0157 molCa ¿
0.0313 e

Step 4: Convert mols Ca to grams Ca using the atomic mass of Ca

40 g
0.0157 mol Ca x =0.627 g Ca
1 mol Ca

Thus, to run a current at 0.7 amperes for 1.2 hours, 0.627g of calcium are required to
remain in the battery or solution. Once the metal is consumed, then no further conduction
can take place.