3.5 - Measuring Cell Potential and Calculating Standard Cell Potentials

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Standard Cell Potential

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0:00
Teacher
Teacher

Welcome class! Let's discuss how we can calculate standard cell potentials. Do any of you recall the formula for this?

Student 1
Student 1

Is it Eยฐcell equals the difference between the reduction potentials of the cathode and the anode?

Teacher
Teacher

Correct, Student_1! The formula is Eยฐcell = Eยฐ(cathode) โ€“ Eยฐ(anode). Remember, the cathode is where reduction occurs.

Student 2
Student 2

What does it mean if the Eยฐcell value is positive?

Teacher
Teacher

Good question! A positive Eยฐcell indicates a spontaneous reaction. You can think of it as a sign that the reaction has enough 'push' to occur naturally. Can anyone come up with a mnemonic to remember the signs of the cathode and anode?

Student 3
Student 3

We could use 'Red Cat' for reduction at the cathode and 'Ox' for oxidation at the anode!

Teacher
Teacher

Excellent mnemonic, Student_3! To summarize, Eยฐcell is crucial as it tells us about the spontaneity of a redox reaction.

Example of Daniell Cell

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0:00
Teacher
Teacher

Now, let's look at a practical example, the Daniell Cell. Can anyone recall the half-reactions occurring in this cell?

Student 4
Student 4

I think zinc is oxidized to zinc ions and copper ions are reduced to copper metal.

Teacher
Teacher

Exactly! The half-reactions are: Zn(s) โ†’ Zn^2+(aq) + 2 eโˆ’ and Cu^2+(aq) + 2 eโˆ’ โ†’ Cu(s). So, how do we calculate Eยฐcell for this reaction?

Student 2
Student 2

We use Eยฐcell = Eยฐ(cathode) โ€“ Eยฐ(anode). So we should plug the values into the equation?

Teacher
Teacher

Correct! For Zn it is -0.76 V and for Cu it is +0.34 V. Overall, Eยฐcell = 0.34 V โ€“ (-0.76 V) yielding 1.10 V. Can anyone explain what this voltage indicates?

Student 1
Student 1

This means the reaction is spontaneous!

Teacher
Teacher

Well done, everyone! The spontaneity confirms that the Daniell cell can function as a power source.

Gibbs Free Energy and Cell Potential

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0:00
Teacher
Teacher

Let's connect Gibbs Free Energy with cell potential. Who can explain the relationship?

Student 3
Student 3

It's ฮ”Gยฐ = -nF Eยฐcell, which shows how the cell potential affects the free energy change in the reaction.

Teacher
Teacher

Right! A negative ฮ”G signifies a spontaneous process. Can anyone tell me how to determine n in the equation?

Student 4
Student 4

n is the number of moles of electrons exchanged during the reaction!

Teacher
Teacher

Exactly! Understanding these relationships helps to predict the feasibility of reactions and the energetics involved. Does anyone have questions?

Student 2
Student 2

Can we use these equations in practical scenarios like batteries?

Teacher
Teacher

Absolutely! Each battery essentially operates on these principles. Great engagement today!

Nernst Equation in Non-Standard Conditions

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Teacher
Teacher

Finally, letโ€™s discuss the Nernst equation. It helps us calculate cell potential under non-standard conditions. Who wants to share what the equation looks like?

Student 1
Student 1

Itโ€™s Ecell = Eยฐcell โˆ’ (RT/nF)ln(Q)!

Teacher
Teacher

Spot on! Remember R, T, n, and F represent universal gas constant, temperature, number of electrons transferred, and Faraday's constant, respectively. Who can explain what Q represents?

Student 2
Student 2

Q is the reaction quotient that compares the concentrations of products to reactants.

Teacher
Teacher

Exactly! It tells us how far along the reaction is. Using this equation allows us to see how changes in concentration affect potential. Can you explain how?

Student 4
Student 4

If products increase or reactants decrease, Q increases and Ecell decreases.

Teacher
Teacher

Excellent understanding! This is crucial for practical applications like batteries and biological systems!

Concentration Cells

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0:00
Teacher
Teacher

Last topic today is concentration cells. Who can give a brief rundown of what these are?

Student 3
Student 3

They're cells that have the same metal electrode but different ion concentrations!

Teacher
Teacher

Correct! They're designed to exploit concentration gradients to generate a potential. How does the cell potential relate to the concentrations?

Student 1
Student 1

We can use the Nernst equation, and Ecell depends on the concentration difference!

Teacher
Teacher

Great! These cells are used in measuring ion concentrations, and in biochemical applications. A wonderful discussion today, class.

Introduction & Overview

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Quick Overview

This section covers how to measure cell potential in electrochemical cells and calculate standard cell potentials using reduction potentials.

Standard

In this section, students learn how to measure the cell potential of electrochemical cells through the formula Eยฐcell = Eยฐ(cathode) โ€“ Eยฐ(anode). They also explore the significance of standard electrode potentials in determining reaction spontaneity and the resulting cell voltage.

Detailed

Measuring Cell Potential and Calculating Standard Cell Potentials

This section elaborates on the measurement of cell potential in galvanic cells, showcasing how the difference in standard electrode potentials between oxidation and reduction half-reactions translates to overall cell voltage.

Key Points:

  1. Standard Cell Potential: The standard cell potential (Eยฐcell) is calculated using the equation:

Eยฐcell = Eยฐ(cathode) - Eยฐ(anode). This formula infers that Eยฐ values are always taken with respect to the more positive electrode being the cathode (site of reduction) and the less positive the anode (site of oxidation).

  1. Example (Daniell Cell): Through an example involving the Daniell Cell, where Zn is oxidized and Cu is reduced, the students can calculate the standard cell potential:
  2. Zinc half-reaction: Zn^2+ + 2 eโˆ’ โ†’ Zn(s) (Eยฐ = -0.76 V)
  3. Copper half-reaction: Cu^2+ + 2 eโˆ’ โ†’ Cu(s) (Eยฐ = +0.34 V)
  4. Therefore, Eยฐcell = 0.34 - (-0.76) = 1.10 V. This potential indicates a spontaneous redox reaction.
  5. Gibbs Free Energy Relationship: The section leads to a connection with Gibbs Free Energy via the formula:

ฮ”Gยฐ = -nF Eยฐcell which determines the spontaneity of the reaction based on cell potential.

  1. Nernst Equation: It discusses the Nernst equation to calculate Ecell under non-standard conditions, incorporating reaction quotient Q, thus aiding in predicting how changes in concentration affect the potential of the cell.
  2. Concentration Cells: Lastly, concentration cells are highlighted as special galvanic cells where both compartments contain the same metal but differ in ion concentrations, thus demonstrating the basis for the generated cell potential relying solely on concentration gradients.

Audio Book

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Cell Potential Calculation

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A galvanic cell built from two halfโ€cells will have a cell potential (voltage) under standard conditions equal to the difference between the standard reduction potentials of the two halfโ€cells:

Eยฐcell = Eยฐ(cathode) โ€“ Eยฐ(anode)

where both Eยฐ values are taken as standard reduction potentials. The cathode is the halfโ€cell where reduction occurs (the one with the higher Eยฐ), and the anode is where oxidation occurs (the halfโ€cell with the lower Eยฐ).

Detailed Explanation

In a galvanic cell, we can measure a voltage called the cell potential. This potential tells us how much energy can be drawn from the cell as it operates. The formula we use to calculate this potential is: Eยฐcell = Eยฐ(cathode) โ€“ Eยฐ(anode). This means that the cell potential is determined by subtracting the standard reduction potential of the anode (where oxidation occurs) from the standard reduction potential of the cathode (where reduction occurs). A higher electrode potential indicates that the reaction can happen more easily.

Examples & Analogies

Imagine a water slide where the height difference between the starting point and the end point determines how fast you can slide down. Similarly, in a galvanic cell, the difference in potential energy (voltage) between the cathode and anode determines how much electricity can be produced.

Example: Daniell Cell Standard Potential

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Example: Daniell Cell Standard Potential

Halfโ€reactions and standard potentials:
โ— Zinc half (written as reduction): Zn^2+ + 2 eโˆ’ โ†’ Zn(s) Eยฐ = โ€“0.76 V
โ— Copper half (reduction): Cu^2+ + 2 eโˆ’ โ†’ Cu(s) Eยฐ = +0.34 V

In the Daniell cell, zinc metal is oxidized (written as the reverse of the reduction halfโ€reaction above):
Zn(s) โ†’ Zn^2+ + 2 eโˆ’ Eยฐ (as oxidation) = +0.76 V (the negative of โ€“0.76 V)
Copper(II) is reduced:
Cu^2+ + 2 eโˆ’ โ†’ Cu(s) Eยฐ = +0.34 V (as reduction)

Cell potential (standard) = Eยฐ(cathode) โ€“ Eยฐ(anode). Because copper halfโ€cell has the higher reduction potential (+0.34 V) it is the cathode. Zinc halfโ€cellโ€™s reduction potential (โ€“0.76 V) is lower, so it is the anode if written as reduction. Therefore:

Eยฐcell = 0.34 V โ€“ (โ€“0.76 V) = 1.10 V

Alternatively, thinking in terms of oxidation potential for zinc (+0.76 V) plus reduction potential for copper (+0.34 V) gives 1.10 V.
This 1.10โ€volt cell potential is what would be measured with a voltmeter under standard conditions (1 M Zn2+, 1 M Cu2+, 25 ยฐC, 1 atm H2 in SHE reference).

Detailed Explanation

In the Daniell cell, we examine two half-reactions: one involving zinc and the other involving copper. The standard potentials of these reactions tell us how readily each species will gain or lose electrons. For zinc, which has a more negative standard potential, it will oxidize and lose electrons, while copper gains electrons and is reduced. When calculating the total cell potential, we subtract the anodeโ€™s potential from the cathodeโ€™s. In our example, this results in a cell potential of +1.10 V, indicating that this galvanic cell can generate electrical energy efficiently under standard conditions.

Examples & Analogies

Think of a race where two athletes are competing. One athlete is faster (the copper), and the other is not (the zinc). By measuring the time difference or the potential between them, we can tell who will win. In our galvanic cell, the copper is the faster athlete (cathode), and by subtracting the slower time (anode, zinc), we find out how much faster the copper can complete the raceโ€”this is like finding the cell potential.

Spontaneity and Gibbs Free Energy Relationship

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A positive cell potential (Ecell > 0) under standard conditions indicates that the overall redox reaction is spontaneous as written. The relationship between the standard cell potential and the change in Gibbs free energy under standard conditions (ฮ”Gยฐ) is:

ฮ”Gยฐ = โˆ’n F Eยฐcell

where
โ— n is the number of electrons transferred in the balanced overall redox reaction,
โ— F is the Faraday constant (approximately 96,500 coulombs per mole of electrons),
โ— Eยฐcell is the standard cell potential in volts,
โ— ฮ”Gยฐ is in joules per mole.

Hence, if Eยฐcell is positive, ฮ”Gยฐ is negative, indicating a spontaneous reaction under standard conditions. If Eยฐcell is negative, ฮ”Gยฐ is positive, indicating a nonspontaneous reaction under standard conditions (but which can proceed if an external voltage greater than |Eยฐcell| is applied, as in electrolysis).

Detailed Explanation

Here, we connect cell potential to the concept of spontaneity using Gibbs free energy (ฮ”Gยฐ). When we have a positive Eยฐcell value, it signifies that the reaction can occur naturally (spontaneously). The equation ฮ”Gยฐ = โˆ’n F Eยฐcell reveals this relationship, where n represents the number of electrons transferred. A positive standard cell potential leads to a negative Gibbs free energy, reinforcing that the reaction is favorable. Conversely, if the cell potential is negative, it means energy is needed to drive the reaction, making it nonspontaneous under standard conditions.

Examples & Analogies

Consider a ball at the top of a hill. If it starts rolling down, that's like a spontaneous process where energy is released (positive Eยฐcell). But if you want to roll it back up, you need to do work against gravity (nonspontaneous process)โ€”related to a negative Eยฐcell. Just like itโ€™s easy for the ball to roll down but hard to push it back up, reactions with positive cell potentials favor 'falling down' to completion spontaneously.

Definitions & Key Concepts

Learn essential terms and foundational ideas that form the basis of the topic.

Key Concepts

  • Standard Cell Potential: The voltage difference between the reduction potential of the cathode and anode.

  • Nernst Equation: Used for calculating cell potentials under non-standard conditions.

  • Gibbs Free Energy: Related to the spontaneity of a reaction and is calculated through standard cell potential.

Examples & Real-Life Applications

See how the concepts apply in real-world scenarios to understand their practical implications.

Examples

  • Example 1: For a Daniell Cell, Zn^2+ + 2 eโˆ’ โ†’ Zn(s) (Eยฐ = -0.76 V) and Cu^2+ + 2 eโˆ’ โ†’ Cu(s) (Eยฐ = +0.34 V). Thus, Eยฐcell = 1.10 V.

  • Example 2: A concentration cell where Zn is at 0.10 M and Cu is at 0.010 M will show how relative concentration impacts the Ecell.

Memory Aids

Use mnemonics, acronyms, or visual cues to help remember key information more easily.

๐ŸŽต Rhymes Time

  • When E is positive, reactions will thrive, spontaneous steps make them come alive.

๐Ÿ“– Fascinating Stories

  • In the tale of the Daniell cell, Zinc and Copper played their roles well. With zinc losing its shine, the spontaneity was fine.

๐Ÿง  Other Memory Gems

  • Remember 'COR' - Cathode for Oxidation, Reduction at the anode!

๐ŸŽฏ Super Acronyms

Use 'FINE' for recognizing Gibbs Free Energy

  • F: = Free
  • I: = Indicator
  • N: = Negative
  • E: = Energy.

Flash Cards

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Glossary of Terms

Review the Definitions for terms.

  • Term: Cell Potential

    Definition:

    The electromotive force, or voltage, generated by an electrochemical cell.

  • Term: Standard Electrode Potential

    Definition:

    The measure of the voltage (Eยฐ) of a half-reaction under standard conditions.

  • Term: Galvanic Cell

    Definition:

    A type of electrochemical cell that converts chemical energy into electrical energy spontaneously.

  • Term: Nernst Equation

    Definition:

    An equation that relates the cell potential to the concentrations of the reactants and products.

  • Term: Reaction Quotient (Q)

    Definition:

    A ratio of the concentrations of products over reactants for a reversible reaction at any point in time.