For the following redox reaction, \\[ \mathrm{NAD}^{+}+2 \mathrm{H}^{+}+2 e^{-} \longrightarrow \mathrm{NADH}+\mathrm{H}^{+} \\] suggest an equation (analogous to Equation 20.12 ) that predicts the pH dependence of this reaction, and calculate the reduction potential for this reaction at \(\mathrm{pH} 8\)

Short Answer

Expert verified
-0.32V - 0.0296V ln([NAD+]/[NADH]) + 0.0592V pH - This equation predicts the pH dependence of the reaction. Actual reduction potential at pH 8 will depend on concentrations of NAD+ and NADH.

Step by step solution

01

Understand The Problem Statement

The reaction given is a redox reaction where NAD+ is reduced to NADH while gaining 2 electrons. We are asked to derive an equation that predicts the pH dependence of this reaction, and then use that equation to determine the reduction potential at pH 8.
02

Derive The pH dependent Nernst Equation

The Nernst equation for a redox reaction is given by \[E=E^{o}-\frac{RT}{nF} lnQ\]where \(E^{o}\) is the standard reduction potential, \(R\) is the universal gas constant, \(T\) is the temperature, \(n\) is the number of electrons transferred, \(F\) is the Faraday's Constant, and \(Q\) is the reaction quotient.Considering that in our reaction \(Q = [NAD+]/([NADH][H+])\) we can derive the pH dependent form of the Nernst Equation. By substituting \(Q\) into the Nernst Equation we get \[E = E^{0} - \frac{RT}{nF} ln\left(\frac{[NAD+]}{[NADH][H+]}\right)\]We also know that \(pH = -log[H+]\). So we rewrite the equation by substitifying \(-pH\) for \(log[H+]\). We now have \[E = E^{0} - \frac{RT}{nF} ln\left(\frac{[NAD+]}{[NADH]}\right) + \frac{2.303RT}{F} \cdot pH\]
03

Calculate Reduction Potential

Given that \(E^{0}\) is -0.32V (NAD+/NADH reduction potential), \(n\) is 2 (number of electrons transferred), \(T\) is 298K (room temperature), \(R\) is 8.3145 J/(mol·K), \(F\) is 96485 C/mol (Faraday's constant), and \(pH\) is 8, we plug these values into the pH-dependent Nernst equation to calculate the reduction potential at pH 8.\[E = -0.32V - \frac{(8.3145 J/(K·mol))(298K)}{2(96485 J/V·mol)} ln\frac{[NAD+]}{[NADH]} + \frac{2.303 * (8.3145 J/(K·mol))(298K)}{(96485 J/V·mol)} \cdot 8\]Since we are looking for a general equation, we won't set any specific values for \([NAD+]\) and \([NADH]\). Notice that the term \(2.303RT/F\) can be simplified to \(0.0592V\), simplifying our equation to:\[E = -0.32V -\frac{0.0592V}{2} ln\frac{[NAD+]}{[NADH]} + 0.0592V pH\]This is the equation that predicts the pH dependence of this reaction.

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Key Concepts

These are the key concepts you need to understand to accurately answer the question.

Understanding Redox Reactions
At the heart of many biochemical processes lies a redox reaction, or reduction-oxidation reaction. This type of chemical reaction involves the transfer of electrons between two substances. It consists of two half-reactions: reduction, where a molecule gains electrons, and oxidation, where a molecule loses electrons.

A classic example is the conversion of NAD+ to NADH, where NAD+ is reduced by gaining two electrons (hence, it is the oxidizing agent) and the reducing agent loses electrons. Understanding redox reactions is crucial because they are involved in energy production, metabolic pathways, and cellular respiration.

Redox reactions are also essential for the function of batteries, where chemical energy is converted into electrical energy. In biochemistry, redox reactions are vital for the functioning of enzymes and the production of ATP, the energy currency of the cell. Thus, mastering the concepts of redox reactions enables students to better grasp complex biological systems and energy transfer mechanisms.
Exploring Reduction Potential
Reduction potential, often symbolized as E0, is a measure of the tendency of a chemical species to acquire electrons and thereby be reduced. It is a fundamental property that is used to predict the direction of redox reactions. The reduction potential is measured in volts and each half-reaction has an associated standard reduction potential.

The standard reduction potential for the half-reaction involving NAD+/NADH is -0.32 volts. This value implies that NAD+ has a relatively high tendency to accept electrons and be reduced to NADH. In a comparison of different redox couples, the one with the higher reduction potential will typically act as the oxidizing agent.

By understanding the concept of reduction potential, students can predict which substances in a redox reaction will be oxidized and which will be reduced. This understanding is essential for analyzing metabolic pathways and energy flow in biochemical systems.
The pH Dependence of Redox Reactions
In biochemistry, the pH level of a solution can significantly affect the behavior of redox reactions. The Nernst equation presents this relationship by integrating the pH into the calculation of reduction potentials.

The pH is a logarithmic scale used to measure the acidity of a solution, defined as the negative logarithm of the hydrogen ion concentration, pH = -log[H+]. The Nernst equation is crucial as it allows the calculation of the actual reduction potential of a redox couple in a solution that may not be at standard conditions, particularly regarding the concentrations of reactants/products and pH levels.

Considering the NAD+/NADH reaction, the equation that accounts for pH reveals how the reduction potential increases as the pH increases. In other words, at higher pH levels—which correspond to lower concentrations of hydrogen ions (less acidic conditions)—NAD+ has a stronger drive to be reduced to NADH. This pH dependence is a vital consideration for understanding the function of redox reactions in biological systems, where slight changes in pH can lead to significant shifts in metabolic pathways. It helps explain the biochemical phenomena in which the intracellular or extracellular pH regulates enzyme activity and energy production in cells.

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Most popular questions from this chapter

Based on your reading on the \(\mathrm{F}_{1} \mathrm{F}_{0}\) -ATPase, what would you conclude about the mechanism of ATP synthesis: a. The reaction proceeds by nucleophilic substitution via the \(S_{N} 2\) mechanism. b. The reaction proceeds by nucleophilic substitution via the \(\mathrm{S}_{\mathrm{N}} 1\) mechanism. c. The reaction proceeds by electrophilic substitution via the \(\mathrm{E} 1\) mechanism. d. The reaction proceeds by electrophilic substitution via the \(\mathrm{E} 2\) mechanism.

Consider the oxidation of NADH by molecular oxygen as carried out via the electron-transport pathway \\[ \mathrm{NADH}+\mathrm{H}^{+}+\frac{1}{2} \mathrm{O}_{2} \longrightarrow \mathrm{NAD}^{+}+\mathrm{H}_{2} \mathrm{O} \\] a. What is the standard free energy change \(\left(\Delta G^{\circ}\right)\) for this reaction if \(\mathscr{E}_{\mathrm{o}}^{\prime}\left(\mathrm{NAD}^{+} / \mathrm{NADH}\right)=-0.320 \mathrm{V}\) and \(\mathscr{E}_{\mathrm{o}}^{\prime}\left(\mathrm{O}_{2} / \mathrm{H}_{2} \mathrm{O}\right)=\) \\[ +0.816 \mathrm{V} \\] b. What is the equilibrium constant \(\left(K_{\mathrm{cq}}\right)\) for this reaction? c. Assume that (1) the actual free energy release accompanying NADH oxidation by the electron-transport pathway is equal to the amount released under standard conditions (as calculated in part \(a),(2)\) this energy can be converted into the synthesis of ATP with an efficiency \(=0.75\) (that is, \(75 \%\) of the energy released upon NADH oxidation is captured in ATP synthesis), and (3) the oxidation of 1 NADH leads to the phosphorylation of 3 equivalents of ATP. Under these conditions, what is the maximum ratio of [ATP]/ \([\mathrm{ADP}]\) attainable by oxidative phosphorylation when \(\left[\mathrm{P}_{\mathrm{i}}\right]=2 \mathrm{m} M ?\) (Assume \(\Delta G^{\circ \prime}\) for ATP synthesis \(=+30.5 \mathrm{kJ} / \mathrm{mol}\).)

Describe in your own words the path of electrons through the \(\mathrm{Q}\) cycle of Complex III.

Considering that all other dehydrogenases of glycolysis and the TCA cycle use NADH as the electron donor, why does succinate dehydrogenase, a component of the TCA cycle and the electron transfer chain, use FAD as the electron acceptor from succinate, rather than \(\mathrm{NAD}^{+}\) ? Note that there are two justifications for the choice of FAD here-one based on energetics and one based on the mechanism of electron transfer for FAD versus \(\mathrm{NAD}^{+}\).

A wealthy investor has come to you for advice. She has been approached by a biochemist who seeks financial backing for a company that would market dinitrophenol and dicumarol as weight-loss medications. The biochemist has explained to her that these agents are uncouplers and that they would dissipate metabolic energy as heat. The investor wants to know if you think she should invest in the biochemist's company. How do you respond?

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