Alright — let's do this.
1 (a) What is electrochemistry?
Electrochemistry is the branch of chemistry that studies the relationship between electrical energy and chemical changes. It deals with chemical reactions that produce electricity (voltaic or galvanic cells) and chemical reactions that are driven by electricity (electrolytic cells).
1 (b) Derive the Nernst equation and explain all terms.
Step 1: The change in Gibbs free energy (ΔG) for a reaction is related to the standard Gibbs free energy change (ΔG∘) and the reaction quotient (Q) by the equation:
ΔG=ΔG∘+RTlnQ
Step 2: For an electrochemical cell, the Gibbs free energy change is also related to the cell potential (Ecell) and the standard cell potential (Ecell∘) by:
ΔG=−nFEcell
ΔG∘=−nFEcell∘
where n is the number of moles of electrons transferred, and F is Faraday's constant.
Step 3: Substitute these expressions for ΔG and ΔG∘ into the first equation:
−nFEcell=−nFEcell∘+RTlnQ
Step 4: Divide the entire equation by −nF:
Ecell=Ecell∘−nFRTlnQ
This is the Nernst equation. For the given reversible reaction aA+bB⇌cC+dD, the reaction quotient Q is:
Q=[A]a[B]b[C]c[D]d
Substituting Q into the Nernst equation:
Ecell=Ecell∘−nFRTln([A]a[B]b[C]c[D]d)
Step 5: Convert the natural logarithm (ln) to base-10 logarithm (log) using lnx=2.303logx:
Ecell=Ecell∘−nF2.303RTlog([A]a[B]b[C]c[D]d)
Explanation of terms:
- Ecell: The cell potential (or electromotive force, EMF) under non-standard conditions, measured in Volts (V).
- Ecell∘: The standard cell potential under standard conditions (1 M concentration for solutions, 1 atm pressure for gases, 298 K temperature), measured in Volts (V).
- R: The ideal gas constant, 8.314Jmol−1K−1.
- T: The absolute temperature in Kelvin (K).
- n: The number of moles of electrons transferred in the balanced redox reaction.
- F: Faraday's constant, the charge of one mole of electrons, approximately 96485Cmol−1 (given as 96500Cmol−1 in constants).
- Q: The reaction quotient, which expresses the relative amounts of products and reactants at any given time. For the reaction aA+bB⇌cC+dD, Q=[A]a[B]b[C]c[D]d.
1 (c) Calculate the potential of the zinc electrode.
Step 1: Identify the half-reaction and given values.
The half-reaction for zinc reduction is:
Zn2+(aq)+2e−⟶Zn(s)
Given:
- Standard electrode potential, E∘(Zn2+/Zn)=0.52 V
- Temperature, T=27°C=27+273.15=300.15 K
- Initial concentration of zinc sulphate, [ZnSO4]=0.1 M
- Dissociation of zinc sulphate = 76%
- Number of electrons transferred, n=2
- Faraday's constant, F=96500Cmol−1
- Gas constant, R=8.314Jmol−1K−1
Step 2: Calculate the actual concentration of Zn2+ ions.
Since ZnSO4 dissociates into Zn2+ and SO42−, and it's 76% dissociated:
[Zn2+]=[ZnSO4]×dissociation percentage
[Zn2+]=0.1M×0.76=0.076 M
Step 3: Apply the Nernst equation for a half-cell.
For a reduction half-reaction Mn++ne−⟶M(s), the Nernst equation is:
E=E∘−nFRTln([Mn+]1)
Or, using log10 and substituting 2.303×R×T/F at 298 K as 0.0592 V:
E=E∘−n0.0592log10([Mn+]1)(at 298 K)
Since the temperature is 300.15 K, we must use the full RT/nF term.
E=E∘−nFRTln([Zn2+]1)
E=0.52V−(2)(96500Cmol−1)(8.314Jmol−1K−1)(300.15K)ln(0.0761)
E=0.52V−193000Cmol−12495.0571Jmol−1ln(13.1579)
E=0.52V−(0.012927V)×(2.577)
E=0.52V−0.0333 V
E=0.4867 V
The potential of the electrode is 0.487V.
2 (a) Use an unambiguous diagram to illustrate how a beam of radiation is attenuated by an absorbing substance, and define the terms Pt and Po.
Step 1: Diagram.