E n E r g y a n d L i f E in Visual Studio .NET

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chapter 4 E n E r g y a n d L i f E
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of the final state is always less than that of the initial state That is, for a process that happens spontaneously (ie, on its own, with no outside push), Gibbs energy always decreases; DG is negative This was in fact what Gibbs was striving for when he proposed a way to measure the available energy Gibbs knew well, from the branch of physics called mechanics, that a force is what moves a physical object He also knew that there is a simple mathematical relation between force and movement (F 5 ma) Physical chemists at that time were looking for a property analogous to force which could be measured and which could be shown to be the force that drives chemical reactions Gibbs found it Just as the force of gravity causes a ball to roll down hill, so too, for any process that takes a system from state A to state B, if state B has less Gibbs energy than state A, then the process will proceed spontaneously, rolling down the Gibbs energy hill from A to B
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The Second Law of Thermodynamics
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No review of thermodynamics would be complete without some discussion of the second law of thermodynamics In all likelihood you ve heard of the second law and learned something about it And you probably know that it has something to do with entropy increasing Perhaps you even know there are many ways to state the second law of thermodynamics, and as different as they all may sound, they are all various views of the same thing For example,
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The universe is winding down Heat spontaneously flows from a place of higher temperature to a place
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of lower temperature
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When converting energy into work, some of the energy is always lost to
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heat
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In any process, the entropy of a closed system will either increase or
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remain constant
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In any process, the entropy of the open system and its surroundings, taken
together, will either increase or remain constant
In any process, a system taken together with its surroundings will always
go from a more ordered state to a less ordered state Some statements of the second law are very precise Others, such as The universe is winding down, can be ambiguous Care must be taken not to misinterpret
B i o p h y s i c s D e mys tifie D
their meaning For example, it is not scientifically correct to make statements like His dorm room is proof of the second law of thermodynamics When a living thing develops from an undifferentiated mass of cells to a fully grown plant or animal, it is clear that it has gone from a less ordered state to a more ordered state Because of this fact and the fact that living things continue to propagate their order by having offspring, scientists have speculated that living things may somehow violate the second law Or, at least, they considered it a possibility there are physical laws we have yet to discover that are apparent only in the case of living matter But living things are open systems When taken together with their surroundings, the impact of the living is to increase the disorder of the environment to a greater extent than they increase their own order Overall the result is an increase in disorder and the second law of thermodynamics is not violated
The gibbs Function as the Driver of Biophysical Processes
For the most part (and this may strike you as odd) biophysics is not concerned with the second law of thermodynamics, at least not as stated What concerns us more is the Gibbs function The Gibbs function effectively has the second law of thermodynamics built into it, so by focusing on the Gibbs function alone, everything is taken care of In this context we can make the following statement, which is akin to other statements of the second law: All else being equal, in any process, an increase in entropy makes a favorable contribution to the Gibbs energy change, whereas a decrease in entropy makes an unfavorable contribution to the Gibbs energy change By favorable and unfavorable we mean whether or not the process is driven forward So forget about the second law of thermodynamics Well, don t actually forget about it, but focus on biophysical processes in terms of the Gibbs function being the force that drives the process DG 5 DH 2 T DS We can see from the Gibbs function that there are three things that contribute to negative DG and thus to rolling down the Gibbs energy hill and to driving a process forward 1 Releasing energy When a system goes from a higher-energy state to a lowerenergy state, it releases energy; its enthalpy decreases DH is negative, and a negative DH contributes toward a decrease in Gibbs energy
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