Redox Reactions

● Oxidation-reduction reactions
● Involve the transfer of electrons from one atom/molecule/ion to another
○ Track oxidations numbers of elements in species to determine if redox
● Oxidation numbers: The charge that an atom would have if bonding electrons are
assigned to the more electronegative atom
○ In MgCl2, the electrons go to Cl, Mg has +2, Cl has -1
● Oxidation is loss of electrons, reduction is gain
○ The species that is oxidized is reducing agent, vice versa
● Oxidation and reduction always occur together
Assigning oxidation numbers
● An atom in its elemental state has ON=0
○ Sodium, dihydrogen, dibromo, etc.
● An atom in a monoatomic ion has ON=ionic charge
○ Cl-=-1
● An atom in a polyatomic ion has usually the same ON it would have if it were a
monoatomic ion
○ H2O, H is +1 O is -2
● ON(H) can be either +1 or -1
● Oxygen usually has ON=-2
○ Major exception are the peroxides where ON=-1
■ H2O2
● Halogens usually have ON=-1
○ The major exception is with Cl, Br, or I, when the halogen is bonded to oxygen
■ Cl2O
● The sum of the ON is 0 for a neutral compound, and is equal to the net charge for an ion
Redox Reactions in terms of Half Reactions
● We can focus on ionic species that participate, and separate into reduction and oxidation
○ Take out witness species/spectator ions
○ Add electrons to have balanced half reactions
■ Can also see electrons in terms of compatibility of half reactions
● Half reactions are very clear in terms of electron exchange
○ Balance electrons of half reactions to have compatible reaction
Half reaction method for balancing oxidation reduction reactions
1. Identify the species being oxidized or reduced
2. Write separate half reactions for the oxidation and reduction processes
3. Balance the half reactions with respect to atoms and electrical charge
4. Combine the balanced half reactions to form the overall net oxidation reduction reaction
5. For acidic conditions, can add H+.
a. H+ is not stable, so at the end add water to both sides to create hydronium
6. For basic conditions, also add H+
a. At the end, at OH- instead of water, hydrogen will turn into water
7. Simplify the overall reaction
notes
Electrochemical cells
● And oxidizing agent and a reducing agent are arranged in such a way that they can react
only if electrons flow through an outside conductor
○ Oxidation and reduction occur in different places
■ Oxidation in anode
■ Reduction in cathode
○ Reactions occur in separate compartments, so there must be a connection
○ Electrons, ions migrate
■ Usually use wire for electrons, salt bridge of ions
■ Anions move to abiotic compartment, cations move to cathodic
compartment
● Reaction occurs at interface between solution and metal
○ Electrons move from anode to cathode
○ Ions shift to balance charges
■ Maintain the electroneutrality of each half-cell
● The containers are called half-cells
● shorthand notations for representing an electrochemical cell
2+ 2+
○ 𝑍𝑛(𝑠)|𝑍𝑛 (𝑎𝑞)||𝐶𝑢 (𝑎𝑞)|𝐶𝑢(𝑠)
■ Lines represent interface
■ Double line is salt bridge
■ By convention, anode on left, cathode on right
Voltage
● Electrons flow in the external circuit from anode to cathode, driven by a voltage
difference or electromotive force (emf) ∆V
○ 𝑤 = 𝑞∆𝑉
○ The emf, or cell voltage, is a measure of how much work the cell can produce per
Coulomb of charge that passes through it
● Cell voltages depend on a number of factors
○ Temperature, composition, nature of the electrode, etc.
● Generally use standard conditions to tabulate cell voltages
○ Pure solids, liquids, gases, pressure 1 bar, solutes at 1M
○ In such conditions voltages are referred to as standard voltages
○ Cell voltages for product favored reactions are positive
● Standard cell voltage is a result of the standard voltages of the half cells
● By convention, voltage given to particular reference electrode
○ Other electrodes are given voltages based on that single electrode
■ Reaction is reversible
● Can function as both anode and cathode
○ Allows for construction of table of half cell voltages
■ Taken at 25 ºC
■ Solvent is water, aqueous solutions
○ Voltages are taken as a reduction reaction
● E (cathode) and Eo(anode) are standard voltages of the half -reactions
0
 ● Standard electrode
○ Standard hydrogen electrode
○ H2 gas at 1 bar bubbled over a Pt electrode immersed in a 1 M aqueous acid
solution
○ Voltage of 0.0 V is assigned to the electrode
● If a half reaction occurs as an oxidation when paired with the standard hydrogen
electrode, the half reaction voltage is negative, for reduction, is positive
○ On table, reduction will occur at the half cell voltage with a higher number
Notes
● Electrode potentials depend on the nature and concentration of reactant and product,
not on the quantity of each that reacts
○ E standard are electrostatic potential differences
○ Potentials are intensive properties
𝑤
○ 𝐸º = ∆𝑉 = 𝑞
Relation to Thermo
● When Eºcell>0, the reaction is product favored
○ ∆Gº<0
○ ∆G=wmax
● Faraday constant=charge of mol of protons=96485.3 C/mol
● ∆Gº=(-electrons exchanged)F Eºcell
○ ∆Gº=-nF Eºcell
○ Also valid under nonstandard conditions
○ ∆G=-nFEºcell
𝑅𝑇
○ 𝐸º𝑐𝑒𝑙𝑙 = 𝑛𝐹
𝑙𝑛𝐾
● At 25 ªC
.0592
○ 𝐸º𝑐𝑒𝑙𝑙 = 𝑛
𝑙𝑜𝑔𝐾
Notes
Effect of concentrations on cell potentials
● ∆𝐺 = ∆𝐺º + 𝑅𝑇𝑙𝑛𝑄
.0592
● 𝐸 𝑐𝑒𝑙𝑙
= 𝐸º𝑐𝑒𝑙𝑙 − 𝑛
𝑙𝑜𝑔𝑄
○ Nernst equation
● Can mix concentrations and partial pressures in Q
● Can do nernst equation of each half reaction, then subtract later
Concentration cell
● Anode and cathode are identical
○ Species in solution is the same
○ Only concentrations are different
● Using Nernst equation, cell potentials of the cells are different
● Overall E
.0592 𝑐𝑎𝑡ℎ𝑜𝑑𝑒
○ 𝐸 𝑐𝑒𝑙𝑙
= 𝑛
𝑙𝑜𝑔 𝑎𝑛𝑜𝑑𝑒
Changes in Potential During Cell operation
● Daniel call, zinc and copper 2+
○ Can use Ricebox table
2+
[𝑍𝑛 ]+𝑥
○ 𝑄= 2+
[𝐶𝑢 }−𝑥
○ Large amount of copper, small amount of Zinc
■ 2 M copper, 10^-3 M zinc
○ As x increases, the cell potential decreases, sideways S curve
○ Voltage doesn’t change much, until reaching near the end
○ When this point is reached, voltage decreases extremely fast
.0592
○ 𝐸 𝑐𝑒𝑙𝑙
= 𝐸º𝑐𝑒𝑙𝑙 − 𝑛
𝑙𝑜𝑔𝑄
○ At first, the potential is greater than the standard cell potential
○ When ratio between concentrations is 1, the potential is equal to the standard cell
potential
■ In this case at around 1M each, average between the two concentrations
○ Voltage of the cell eventually reaches 0, the cell is discharged
■ Reach equilibrium
𝑛(𝐸º𝑐𝑒𝑙𝑙−𝐸𝑐𝑒𝑙𝑙)/.0592
■ 𝑄 = 10