/*! This file is auto-generated */ .wp-block-button__link{color:#fff;background-color:#32373c;border-radius:9999px;box-shadow:none;text-decoration:none;padding:calc(.667em + 2px) calc(1.333em + 2px);font-size:1.125em}.wp-block-file__button{background:#32373c;color:#fff;text-decoration:none} Problem 52 Glucose Metabolism The standard ... [FREE SOLUTION] | 91Ó°ÊÓ

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Glucose Metabolism The standard potentials for the reduction of nicotinamide adenine dinuclcotide (NAD") and oxaloacetate (reactants in the multistep metabolism of glucose) are as follows: $$ \mathrm{NAD}^{+}(a q)+2 \mathrm{H}^{+}(a q)+2 \mathrm{e}^{-} \rightarrow \mathrm{NADH}(a q)+\mathrm{H}^{+}(a q) $$ Oxaloacetate \((a q)+2 \mathrm{H}^{+}(a q)+2 \mathrm{e}^{-} \rightarrow\) malate \((a q)\) \(E^{*}=-0.166 \mathrm{V}\) a. Calculate the standard potential for the following reaction: Oxaloacetate \((a q)+\mathrm{NADH}(a q)+\mathrm{H}^{+}(a q) \rightarrow\) malate( \(a q)+\mathrm{NAD}^{+}(a q)\) b. Calculate the equilibrium constant for the reaction at \(298 \mathrm{K}.\)

Short Answer

Expert verified
Given information: - Standard potential for the reduction of oxaloacetate: -0.166 V - Standard potential for the reduction of NAD+: E* Solution: Step 1: Find the standard potential for NADH to NAD+: E*(NADH → NAD+) = -E*(NAD+ → NADH) Step 2: Calculate the standard potential for the overall reaction: E*(Overall Reaction) = E*(NADH → NAD+) + E*(Oxaloacetate → Malate) Step 3: Calculate the equilibrium constant (K) at 298 K using the Nernst equation: K = e^[(2 * 9.6485 * 10^4 * E*(Overall Reaction))/(8.314 * 298)] Once the standard potential for the overall reaction is calculated, plug that value into the equation to find the equilibrium constant, K.

Step by step solution

01

Write down all the given information

The standard potentials for the reduction of NAD+ and oxaloacetate are: $$\mathrm{NAD}^{+}(a q)+2 \mathrm{H}^{+}(a q)+2 \mathrm{e}^{-} \rightarrow \mathrm{NADH}(a q)+\mathrm{H}^{+}(a q)$$ $$Oxaloacetate(a q)+2 \mathrm{H}^{+}(a q)+2 \mathrm{e}^{-} \rightarrow Malate(a q), E^{*}=-0.166 \,V$$ The overall reaction for which we need to calculate the standard potential is: $$Oxaloacetate(a q)+\mathrm{NADH}(a q)+\mathrm{H}^{+}(a q) \rightarrow Malate(a q)+\mathrm{NAD}^{+}(a q)$$
02

Find the standard potential for NAD+ reduction

Notice that the NAD+ reduction actually occurs in the opposite direction of the given reaction. Thus, we need to find the standard potential for the reverse reaction of NAD+: $$\mathrm{NADH}(a q)+\mathrm{H}^{+}(a q) \rightarrow \mathrm{NAD}^{+}(a q)+2 \mathrm{H}^{+}(a q)+2 \mathrm{e}^{-}$$ Since the equation is reversed, we need to multiply the standard potential by -1. Thus, the reaction becomes: $$-1 \cdot E^{*}(\mathrm{NAD}^{+} \rightarrow \mathrm{NADH}) = E^{*}(\mathrm{NADH} \rightarrow \mathrm{NAD}^{+})$$
03

Calculate the standard potential for the overall reaction (part a)

Now we have both standard potentials for the reactions involved. We can calculate the standard potential for the overall reaction by adding the standard potentials of each half-reaction: $$E^{*}(\mathrm{Overall \, Reaction}) = E^{*}(\mathrm{NADH} \rightarrow \mathrm{NAD}^{+}) + E^{*}(Oxaloacetate \rightarrow Malate)$$ $$E^{*}(\mathrm{Overall \, Reaction}) = (-1 \cdot E^{*}(\mathrm{NAD}^{+} \rightarrow \mathrm{NADH})) + (-0.166 \,V)$$ Find the standard potential for the overall reaction.
04

Calculate the equilibrium constant (part b)

Use the Nernst equation to calculate the equilibrium constant for the overall reaction at 298 K: $$\Delta G^{*} = -nFE^{*}(\mathrm{Overall \, Reaction})$$ since $$K = e^{-\frac{\Delta G^{*}}{RT}}$$, combining the two equations will give us: $$K = e^{\frac{nFE^{*}(\mathrm{Overall \, Reaction})}{RT}}$$ We know that the number of electrons transferred in the overall reaction is n = 2. Plug in the values of n, R (gas constant = 8.314 J mol^{-1}K^{-1}), T (298 K), and the calculated standard potential for the overall reaction: $$K = e^{\frac{(2)(9.6485 \times 10^{4} \,\mathrm{C} \,\mathrm{mol}^{-1})(E^{*}(\mathrm{Overall \, Reaction}))}{(8.314\,\mathrm{J} \,\mathrm{mol}^{-1}\,\mathrm{K}^{-1})(298 \,\mathrm{K})}}$$ Calculate the equilibrium constant K for the overall reaction at 298 K.

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Key Concepts

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

NAD+ Reduction
In the metabolic pathways, NAD+ plays a crucial role as an electron carrier. It participates in redox reactions by accepting electrons and getting reduced to NADH. The reduction can be represented by the following reaction: \[ \mathrm{NAD}^{+} + 2 \mathrm{H}^{+} + 2 \mathrm{e}^{-} \rightarrow \mathrm{NADH} + \mathrm{H}^{+} \] This process occurs in glycolysis and the citric acid cycle, pivotal phases of glucose metabolism. During these reactions, glucose is gradually broken down to extract energy, and NAD+ is critical in shuttling electrons to the electron transport chain. In the context of standard cell potential, understanding such reactions is vital. The standard potential for the conversion of NAD+ to NADH is typically measured under standard conditions – this relates to its ability to gain electrons. Since the electron transfer in NAD+ reduction predominantly happens in reverse during energy conservation, we often talk about it in both forward and backward directions during metabolic processes.
Standard Cell Potential
The standard cell potential (\(E^*\)) is a measure of the electrode potential difference in a cell. It gauges the tendency of a chemical species to be reduced. Consider it as a force that "drives" the flow of electrons in a circuit or process. For cellular reactions involving NAD+ and metabolites like oxaloacetate and malate, useful insights can be drawn through these potentials. These reactions often form parts of larger metabolic pathways. For example, oxaloacetate is reduced to malate in the citric acid cycle, which is accompanied by an electron transfer from NADH to NAD+. To compute the standard cell potential for a full reaction:
  • Determine the half-reactions involved
  • Find individual cell potentials for these reactions
  • Combine them, factoring in the direction (often necessitating reversing and negating certain standard potential values)
This combined potential gives insights into reactant favorability and reaction spontaneity. High positive values typically indicate reactions favoring product formation under standard conditions.
Equilibrium Constant Calculation
The calculation of the equilibrium constant \(K\) is crucial as it predicts the extent of a reaction at equilibrium. The \(K\) of a reaction reflects the ratio of concentrations of products to reactants when the reaction has reached a state where their rates are equal. To calculate \(K\) for reactions in glucose metabolism, such as the reduction of oxaloacetate by NADH, the Nernst equation proves incredibly useful. First, we need the standard cell potential (\(E^*\)) for the overall reaction, which combines potentials from the involved half-reactions. Once \(E^*\) is known, the change in Gibbs free energy \(\Delta G^*\) can be computed using: \[ \Delta G^{*} = -nFE^{*} \] where \(n\) is the number of moles of electrons transferred, and \(F\) is Faraday's constant. From \(\Delta G^*\), \(K\) can be derived through: \[ K = e^{-\frac{\Delta G^*}{RT}} \]Where \(R\) is the gas constant and \(T\) is temperature in Kelvin. This approach reveals whether products or reactants dominate at equilibrium, thus framing the metabolic reaction landscape.

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Most popular questions from this chapter

Sodium-Sulfur Batteries The low cost of sodium and sulfur relative to lithium makes voltaic cells based on sodium attractive to electric vehicle manufacturers, provided the technological hurdles of managing a battery that operates at \(300^{\circ} \mathrm{C}\) can be overcome. The overall cell reaction is $$ 2 \mathrm{Na}(s)+3 \mathrm{S}(\ell) \rightarrow \mathrm{Na}_{2} \mathrm{S}_{3}(s) \quad E_{\mathrm{cell}}^{\circ}=2.076 \mathrm{V} $$ a. Which element is oxidized and which is reduced? b. How many electrons are transferred in the overall cell reaction? c. What is the value of \(\Delta G^{\circ}\) for the reaction? d. If a battery containing \(5.25 \mathrm{kg} \mathrm{Na}\) is \(50 \%\) discharged when it is connected to a charger with an output of 200 A, how long does it take to recharge the battery? e. Draw a Lewis structure for the \(\mathrm{S}_{3}^{2-}\) anion.

Using the appropriate standard potentials from Appendix 6, determine the equilibrium constant for the following reaction at \(298 \mathrm{K}:\) $$ \mathrm{Fe}^{3+}(a q)+\mathrm{Cr}^{2+}(a q) \rightarrow \mathrm{Fe}^{2+}(a q)+\mathrm{Cr}^{3+}(a q) $$

Quantitative Analysis Electrolysis can be used to determine the concentration of \(\mathrm{Cu}^{2+}\) in a given volume of solution by electrolyzing the solution in a cell equipped with a platinum cathode. If all of the \(\mathrm{Cu}^{2+}\) is reduced to \(\mathrm{Cu}\) metal at the cathode, the increase in mass of the electrode provides a measure of the concentration of \(\mathrm{Cu}^{2+}\) in the original solution. To ensure the complete (99.9996) removal of the \(\mathrm{Cu}^{2+}\) from a solution in which \(\left[\mathrm{Cu}^{2+}\right]\) is initially about \(1.0 M,\) will the potential of the cathode (versus SHE) have to be more negative or less negative than \(0.34 \mathrm{V}\) (the standard potential for \(\mathrm{Cu}^{2+}+2 \mathrm{e}^{-} \rightarrow \mathrm{Cu}\) )?

A copper penny dropped into a solution of nitric acid produces a mixture of nitrogen oxides. The following reaction describes the formation of \(\mathrm{NO},\) one of the products: \(3 \mathrm{Cu}(s)+8 \mathrm{H}^{+}(a q)+2 \mathrm{NO}_{3}^{-}(a q) \rightarrow\) \(2 \mathrm{NO}(g)+3 \mathrm{Cu}^{2+}(a q)+4 \mathrm{H}_{2} \mathrm{O}(\ell)\) a. Starting with the appropriate standard potentials from Appendix \(6,\) calculate \(E_{\text {ren }}^{\circ}\) for this reaction. b. Calculate \(E_{\text {rxn }}\) at \(298 \mathrm{K}\) when \(\left[\mathrm{H}^{+}\right]=0.100 \mathrm{M}\) \(\left[\mathrm{NO}_{3}^{-}\right]=0.0250 \mathrm{M},\left[\mathrm{Cu}^{2+}\right]=0.0375 M,\) and the partial pressure of \(\mathrm{NO}=0.00150\) atm.

To inhibit corrosion of steel structures in contact with seawater, pieces of other metals (often zinc) are attached to the structures to serve as "sacrificial anodes." Explain how these attached pieces of metal might protect the structures, and describe which properties of zinc make it a good selection.

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