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Practice Test
: Biochemistry Chapter 3
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phosphoric-carboxylic anhydrides
Why doesn't AMP hydrolyze as easily and ATP and ADP
At equilibrium, what is the relationship between free energy change and the equilibrium constant?
First law of thermodynamics
reduced enzymes and high-energy phosphate compounds
Are biological reactions similar or different from standard state conditions?
What value tells you if the reaction will proceed as written?
mixed anhydrides of phosphoric and carboxylic acids. Energy rich. Hydrolysis leads to inorganic phosphates. Large ∆Gº’ from bond strain: partial positive charges on carbonyl carbon and phosphorus atoms of these structures. Energy stored in mixed anhydride bond released upon hydrolysis. Value of ∆Gº’ depends on pKa of starting anydride and product phosphate and carboxylic acids.
Small family of universal biomolecules that mediates the flow of energy from exergonic reactions to the energy-requiring process of life.
∆Gº = -RT ln Keq
Destabilization of reactants and stabilization of products for pyrophosphate also apply to ATP or other phosphoric anhydrides ATP and ADP destabilized due to electrostatic repulsion, competing resonance and entropy. AMP (not an anhydride), does not have a large negative ∆Gº’ and is, therefore, no as favored to hydrolyze as ATP and ADP.
Different. Especially in concentrations.
Gibbs free energy, G. Any process with nonzero ∆G proceeds spontaneously to a final state of lower free energy. (Whichever writing of the equation makes ∆G negative)
Total energy of an isolated system is conserved. All forms of energy could ultimately be converted to some other form.
Short Answer
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Gibbs free energy equation
negentropy
chemotrophic organisms
closed system
three kinds of systems
Multiple Choice
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entropy
open
Portion of the universe with which we are concerned
Effects of concentration much greater than effects of protons or metal ions under physiological conditions.
Measure of disorder and randomness in the system. Organized or ordered state is low-entropy.
Experimentally determines enthalpy changes for biochemical processes.
energy dispersion
G = H - TS. At constant pressure and temperature: ∆G = ∆H - T∆S.
What entropy represents, the dispersion of energy among a large number of molecular motions relatable to quantized states (microstates)
Cannot exchange matter or energy with its surroundings
Unpaired electrons of bridging oxygen in acetic anhydride can’t participate in resonance structures.
Carbonyl groups withdraw e- density Adjacent acetyl groups destabilize each other, fighting for e- density Phosphorous also e- withdrawing, destabilize the potential for PPi or P2O7 2- from forming. In addition, if this were to happen, reformation of ATP would require the repulsion of these anions to be overcome
In real life, how do metal ions affect free energy of hydrolysis of ATP?
free energy of hydrolysis of ATP altered more by metal ions that protons
mixed anhydrides of phosphoric and carboxylic acids. Energy rich. Hydrolysis leads to inorganic phosphates. Large ∆Gº’ from bond strain: partial positive charges on carbonyl carbon and phosphorus atoms of these structures. Energy stored in mixed anhydride bond released upon hydrolysis. Value of ∆Gº’ depends on pKa of starting anydride and product phosphate and carboxylic acids.
No bearing
∆E = E2 - E1 = q + w Where q: The heat absorbed by the system from the surroundings. w: the work done on the system by the surroundings.
∆E = heat transferred in a constant volume system. ∆H = heat transferred in a constant pressure process. Often essentially equal though, because volume changes are typically quite small.
What are the 3 chemical reasons for large negative ∆Gº values in pyrophosphoryl/phosphoric acid anhydride linkages
the process is at equilibrium and there is no net flow either in the forward or reverse direction.
Destabilization of reactant due to bond strain caused by electrostatic repulsion, stabilization of the products by ionization and resonance, and entropy factors due to hydrolysis and subsequent ionization.
sum free energy changes for each reaction.
Unpaired electrons of bridging oxygen in acetic anhydride can’t participate in resonance structures.
Gibbs free energy, G. Any process with nonzero ∆G proceeds spontaneously to a final state of lower free energy. (Whichever writing of the equation makes ∆G negative)
describe the stabilization of hydrolysis products by ionization and resonance in pyrophosphoryl/phosphoric acid anhydride linkages
The free energy change that occurs upon hydrolysis, that is, upon transfer of a particular group to water. In many reactions, a functional group is transferred from a donor molecule to a specific receptor molecule or water. Explains the tendency for reactions to occur. Analogous to those of ionization potential and reduction potential. Release of free energy that occurs upon the hydrolysis of ATP and other “high-energy phosphates” treated quantitatively in terms of group transfer.
For solutes in a solution, standard state is normally unit activity (often simplified to 1 M concentration) Symbolized by “º”.
Total energy of an isolated system is conserved. All forms of energy could ultimately be converted to some other form.
By itself, pyrophosphoryl moiety has two negative charges at pH of above 7.5 Hydrolysis product, two phosphate esters, each carry two negative charges (pH above 7.2) Increased ionization stabilizes the electrophilic phosphorous nuclei
large positive
True or False
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system
Portion of the universe with which we are concerned
True
False
What is the equation for w?
w = -P∆V where P is the pressure and ∆V is the volume change and is equal to V2 - V1.
True
False
How does ATP rank as a high-energy phosphate?
the process is at equilibrium and there is no net flow either in the forward or reverse direction.
True
False
How do you find the ∆Gº when pH is involved?
(E or U) Includes all the energies that might be exchanged in physical or chemical processes. Eg. rotational, vibrational, translational energies of molecules and also energy stored in covalent and noncovalent bonds.
True
False
high-energy compound
open
True
False
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