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Gen Chem Lecture Notes

Electrochemistry

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Steven Mao
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7 views

Gen Chem Lecture Notes

Electrochemistry

Uploaded by

Steven Mao
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Last Class

• Oxidation states and stoichiometry


• Voltaic and Electrolytic Cells
• Standard hydrogen electrode (SHE)
• Standard reduction potentials
• Electromotive potential
Question Given:
Zn2+(aq) + 2e- Zn(s) -0.76 V
Cr3+(aq) + 3e- Cr(s) -0.74 V
Fe2+(aq) + 2e- Fe(s) -0.41 V
Cd2+(aq) + 2e- Cd(s) -0.40 V
A.) Fe will reduce Zn2+
B.) Cd will reduce Fe2+
C.) Cr3+ will be reduced by Zn
D.) Zn2+ will not be reduced by Cr, Fe, or Cd
E.) Cd will be oxidized as the half well with Cr, Fe, or Zn.
Question
) Use the standard half-cell potentials listed below to calculate the standard cell potential for the
following reaction occurring in an electrochemical cell at 25°C. (The equation is balanced.)

Sn(s) + 2 Ag⁺(aq) → Sn2+(aq) + 2 Ag(s)

Sn2+(aq) + 2 e⁻ → Sn(s) E° = -0.14 V


Ag⁺(aq) + e⁻ → Ag(s) E° = +0.80 V

A) +1.74 V
B) +0.94 V
C) +1.08 V
D) -1.08 V
E) -1.74 V
Using the Standard
o
Reduction - Potentials
Case 1: Calculating E when the electrons cancel.
I2(s) + 2e- ® 2I-(aq) Eo = 0.54 V
Fe3+(aq) + e- ® Fe2+(aq) Eo = 0.77 V
Using the definition of free energy, calculate the standard cell potential for a voltaic cell
consisting of the two half cells shown above.
Using the Standard Reduction - Potentials
Case 2: Calculating Eo when the electrons do NOT cancel.
MnO4- + 8H+ + 5e- ® Mn+2 + 4H2O E1o = 1.57 V Determining the standard
MnO2 + 4H+ + 2e- ® Mn+2 + 2H2O E2o = 1.23 V reduction potential for a new
half-cell from existing half-cell
MnO4- + 4H+ + 3e- ® MnO2+ 2H2O E3o = ? potentials.
Derivation of the Nernst Equation

34
Example
Calculate the cell potential for the following reaction that takes place in an electrochemical cell
at 25°C.

Sn(s) ∣ Sn2+(aq, 1.8 M) Ag+(aq, 0.055 M) ∣ Ag(s)

Ag⁺(aq) + e⁻ → Ag(s) E° = +0.80 V


Sn2+(aq) + 2 e⁻ → Sn(s) E° = -0.14 V

A) -0.94 V
B) -0.85 V
C) +1.02 V
D) +0.98 V
E) +0.86 V
Example
The overall cell reaction in a galvanic cell at 25oC is
Ag+ (aq) + ½ H2 (g) à Ag (s) + H+ (aq)
The reduction occurs in a standard Ag+ | Ag half-cell, and the oxidation occurs at a platinum
wire that has hydrogen bubbling at 1 atm and is immersed in a buffer solution containing
benzoic acid (0.10 M) and sodium benzoate (0.050 M). The measured cell voltage is 1.030
V. Calculate the pH and determine the Ka value for benzoic acid.
Example
Given: Br2 (l) + H2 (g) à 2 Br- (aq) + 2 H+ (aq)

Silver ions are added to the cathode compartment until AgBr precipitates, and [Ag+]
reaches a concentration of 0.060 M. The cell voltage is 1.710 V when precipitation
occurs. The partial pressure of hydrogen is 1 atm and the pH is 0. Calculate the Ksp for
AgBr at 25oC.
Example
A battery operating at 25oC is composed of an anode that contains a Pb rod
immersed in a 0.10 M Pb(NO3)2 solution. The second half-cell contains a Pb rod
immersed in a 0.010 M Pb(NO3)2 solution. Sulfuric acid is the electrolyte for the
cell. Calculate the new battery potential.
Concentration Cells Same half-cell setup, but at different concentrations,
thus giving rise to a potential.

Thermodynamics favors the lower concentration


half-cell.

Electrons flow until both half-cells are equal in


concentration.

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