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Molecular Biology of the Cell by Bruce Alberts, Alexander Johnson, Julian Lewis, David Morgan, Martin Raff, Keith Roberts, Peter Walter by by Bruce Alberts, Alexander Johnson, Julian Lewis, David Morg

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62 Chapter 2: Cell Chemistry and Bioenergetics

FOR THE ENERGETICALLY FAVORABLE REACTION Y → X,

Figure 2–30 Chemical equilibrium. When

a reaction reaches equilibrium, the forward

and backward fluxes of reacting molecules

are equal and opposite.

Y

when X and Y are at equal concentrations, [Y] = [X], the formation of X

is energetically favored. In other words, the ΔG of Y → X is negative and

the ΔG of X → Y is positive. But because of thermal bombardments,

there will always be some X converting to Y.

THUS, FOR EACH INDIVIDUAL MOLECULE,

X

Y

X

Therefore the ratio of X to Y

molecules will increase with time

X

Y

conversion of

Y to X will

occur often.

Conversion of X to Y

will occur less often

than the transition

Y → X, because it

requires a more

energetic collision.

EVENTUALLY, there will be a large enough excess of X over Y to just

compensate for the slow rate of X → Y, such that the number of Y molecules

being converted to X molecules each second is exactly equal to the number

of X molecules being converted to Y molecules each second. At this point,

the reaction will be at equilibrium.

Y

X

AT EQUILIBRIUM, there is no net change in the ratio of Y to X, and the

ΔG for both forward and backward reactions is zero.

The Equilibrium Constant and ∆G° Are Readily Derived from

Each Other

Inspection of the above equation reveals that the ∆G equals the value of ∆G°

when the concentrations of Y and X are equal. But as any favorable reaction proceeds,

the concentrations of the products will increase as the concentration of the

substrates decreases. This change in relative concentrations will cause [X]/[Y] to

MBoC6 e3.18/2.30

become increasingly large, making the initially favorable ∆G less and less negative

(the logarithm of a number x is positive for x > 1, negative for x < 1, and zero for x

=1). Eventually, when ∆G = 0, a chemical equilibrium will be attained; here there

is no net change in free energy to drive the reaction in either direction, inasmuch

as the concentration effect just balances the push given to the reaction by ∆G°.

As a result, the ratio of product to substrate reaches a constant value at chemical

equilibrium (Figure 2–30).

We can define the equilibrium constant, K, for the reaction Y → X as

K = [X]

[Y]

where [X] is the concentration of the product and [Y] is the concentration of the

reactant at equilibrium. Remembering that ∆G = ∆G° + RT ln [X]/[Y], and that

∆G = 0 at equilibrium, we see that

∆G° = –RT ln [X] = –RT ln K

[Y]

At 37°C, where RT = 2.58, the equilibrium equation is therefore:

∆G° = –2.58 ln K

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