Energy-Entropy Dynamics LO26967

From: AM de Lange (
Date: 07/09/01

Replying to LO26947 --

Dear Oganlearners,

Greetings to all of you. Akthough I am replying to myself, I do it to
finish off some untold business.

I have described in "Energy-Entropy Dynamics LO26947"
with an associated complex graph in
< >
how the total energy E, the entropy S and the free energy F change
during a chemical reaction. In each chemical reaction there is always
the change in (molecular) structure from that in the reagents A, B, C, ...
to that in the products D, E, F, ...

The total energy E(sy) of the system and the entropy S(sy) of the
compounds change with /_\E(sy) and /_\S(sy) in a linear manner as is
indicated by straight lines. The reason why the free energy /_\F(sy) of
the system does not change in a linear, is that it F does not drive only
the conversion in structure from reagents A, B, C, ... to products D, E,
F, ..., but also ALL other changes in the system. Should it have been
possible to use the free energy F for only the change in structure, the
graph of /_\F(sy) would also have changed linearly like /_\E(sy) and

However, it is not possible in any chemical reaction to suppress ALL other
emergences except those for the intended change in structures. This means
that it is not possible to have 100% efficiency for only the intended
change in structure (even if it is an emergence). These unintended changes
(even emergences or immergences) also have to be driven. They occur as a
result of the 7Es. The chemical reaction cannot decide which of the 7Es it
has to give up so as to prevent other changes (flow of heat, phase change)
than the intended structural changes on molecular level.

The free energy F drives the production (creation) of entropy S in the
system. Thus the SYSTEM'S free energy decreases in a curve like manner
bent to the bottom. Some of this entropy stays in the system SY while the
rest goes into the surroundings SU. The total entropy change /_\S(un) for
the universe UN (i.e. system AND surroundings) will thus be nonlinear like
the change /_\F(sy) in free energy of the system. However, the UNIVERSE'S
entropy increases in a curve like manner bent to the top. These two
graphs (note the asymmetry, F for SY and S for UN) are inverted images of
each other, almost as if the one negates the other.

When such extra entropy goes into the surroundings, it does so as "form"
by means of pure energy E as its "content" ("carrier"). In other words, we
may think of energy E and entropy S together as the two sides of a "coin".
These whole "coins" (or quanta) are exchanged with the surroundings and
not merely the "one side of the coins", whether such a side is energy E or
entropy S. We may have various kinds of "coins" such as thermal,
electrical and magnetical, almost like having various currencies like US$,
DM and YEN.

Have any of you spotted in LO26947 the tacit assumption that there
is no transfer of compounds (molecular structures) between the system
and the surroundings for the chemical reaction
aA + bB + cC + ... => dD + eE + fF + ...
In other words, "coins" may be exchanged, but "goods" not. Such a
chemical system, somewhere between fully isolated (neither "coins"
nor "goods") and fully open (both "coins" and "goods"), is called a
closed system. In a fully isolated system neither pure energy&entropy
nor compounds (molecular structures) can be transferred between the
system and its surrounding. In a fully open system anything can be
transferred between the system and its surroundings. But in a closed
system there is a restriction on the transfer of some parts of the system.

In the example of the sales office of the factory producing pipes,
4.forms + 5.sellers + nr.customers + nr.items + ... => ...@#$%&*.
the system is closed for sales personnel and two of the forms (store,
manager), but open for customers, the other two forms (invoice, delivery)
and items (pipes) taken from the premises. In other words, thinking of
humans as organised structures, have a system more open than the
chemical system considered in LO26947.

To understand what now happens with its energy-entropy dynamics,
let us go back to the general chemical system
aA + bB + cC + ... => dD + eE + fF + ...
and allow one of the compounds A, B, C, ... or even products D, E, F, ...
to enter or leave the system, unlike in LO26947. Let us then explore
what will happen.

Let us first look at the reagents A, B, C, ... Assume the system becomes
open for only compound A. There are two possibilities: some of compound A
either enters or leaves the system. Firstly, assume some extra compound A
enters the system. By doing so it also brings with it additional energy E,
entropy S and free energy F into the system. Although the total number of
entities of A increase, it is still only an amount a of A which will react
with b of B and c of C ... Thus the graphs of /_\E(sy) and /_\S(sy) stay
the same for they indicate what happens during the reaction and not what
are available before reaction.

However, because the total amount of A has increased, its total free
energy has also increased. Thus all entropic forces in which compound A is
involved, increase. The effect of this increase is to shift the
equilibrium point (at 70% conversion) of /_\F(sy) to the right, say 80%.
If A keeps on coming in, the equilibrium A will keep on shifting to the
right. It is as if the system wants to remove some of the additional A by
converting some of it (together with some of the remaining B, C, ...) into
products. This is known as Le Chatelier's principle. Put a stress on the
system and the system will react (using its entropic forces and fluxes) in
such a manner as to relieve some of this applied stress.

Just as the minimum (at 70%) of the graph /_\F(sy) moves to the right, the
maximum (at 70%) of the graph /_\S(un) will also move to the right to keep
pace with it. Hence we see that relieving the stress on the system is
associated with an increase in entropy production /_\S(un) for the
universe. It means that Le Chatelier's principle is one of many ways in
which LEP becomes manifested.

Secondly, in the opposite manner, assume that some of the available
compound A leaves the system before having had the opportunity to react.
What now happens is the reverse of the former case. The equilibrium point
(at 70%) for the graph of /_\F(sy) moves to the left (say 50%). By taking
more and more of A out, thus forcing it into a limiting reagent (tragedy
of the commons, spareness), even less and less of the other reagents B, C,
... will become converted into products. Try to draw you own graph on
which the bottom graph /_\F(sy) is grabbed by its equilibrium point and
then pulled to the left. The graph ust be pulled in such a manner that
there is always a minimum (dip) in its curve.

Likewise the maximum of the graph /_\S(un) will move in pace with it to
the left. Hence, although entropy still gets produced, less of it becomes
produced. Again Le Chatelier's principle can be seen operating here. By
taking some of the compound A out before it reacted, the reverse reaction
begins to produce some additional A by reconverting some of the products
into reagents. Hence the system tries to relieve the deficiency stress in
A by trying to refurnish some of it by the backward reaction.

Should we do to anyone of B, C, ... what we did to A, the same will
happen. Adding a reagent will push the equilibrium point to the right
while removing a reagent will pull it to the left.

Assume that all of A, B, C, ... are added in the precise ratio of numbers
a, b, c, ... when say 40% conversion has been reached. What now happens is
that the system will move only slower to the equilibrium point at 70%
while all the graphs stay otherwise the same. Should we, at the moment
when A, B, C, are added, remove D, E, F, ... in the precise ratio of
numbers d, e, f, .. the system will remain at 40% conversion and not even
move slowly to the 70% conversion point. The system is now at a labile
equilibrium rather than a stabile equilibrium. Since there are flows of
extensive parameters in out of the system while the intensive parameters
stay the same, a homeostasis has been reached.

Let us go back to the factory selling pipes. Its management tried to
increase sales (shift equilibrium to the right) by adding another form
which sales office had to fill in for each transaction. But what
management accomplished, was merely to slow down the rate of sales
(conversion). Should the delivery and security departments manage to get
the few served customers fast enough away, then the sales office would
soon (perhaps even before noon) get stuck in a labile equilibrium (local

Let us go back to the general chemical reaction and its complex graph to
see what happens when it opens up for one of the products rather than the
reagents. Say for example only product D is added to the system. Then the
graph for /_\F(sy) will be pushed to the left at its equilibrium point
(from 70% to say 50%) just like the case when less of A also pulls it to
the left. On the other hand, when product D is removed from the system,
the graph for /_\F(sy) will be pulled to the right at its equilibrium
point (from 70% to say 80%) just like the case when more of A also pushes
it to the right. In each case the graph of /_\S(un) will follow suite to
keep pace as the inversion of /_\F(sy).

Let us go back to the factory selling pipes. Assume its management becomes
worried because of the decrease in sales (as a result of the over
burdening of its sales department which they are oblivious to). Assume
they suspect the delivery (store) to ship illegally pipes from the
factory. Using their modus operandi once again, they would then force
delivery to fill in extra forms too, sending one back to the sales
department to check up on their deliveries. This would be like increasing
a product like F (served customer). Hence the equilibrium point will be
pushed to the left so that the rate of transactions will decrease. The
sales office might become saturated long before noon.

Such a possibility seems to be like a nightmare.

I observed the nice lady carefully. She waited some five minutes after she
had completed all forms. I asked her innocently (not demanding) why she is
waiting. She said cheerfully that management ordered delivery to phone
sales office back, telling them that they have removed the item from stock
and how much would be left over. So management was indeed following the
modus operandi. I smiled at her, saying: "So you sales people have to even
check that nothing gets stolen." She said: "Yes Mr De Lange, you know how
easily anything gets stolen in South Africa nowadays."

It is clear that the management of that factory thinks it is its duty to
stress the system to perform better. It is also clear that management does
not know Le Chatelier's principle -- stress a system with a certain action
and it will try to relieve that stress by counteracting the action made by
management. Those cheerful people at the sales department are taking the
brunt of the stress, but for how long will they cope with it? I also
wonder how long that factory will still be in business?

Is it not high time for Learning Organisations to incorporate Le
Chatelier's principle in their Systems Thinking?

With care and best wishes


At de Lange <> Snailmail: A M de Lange Gold Fields Computer Centre Faculty of Science - University of Pretoria Pretoria 0001 - Rep of South Africa

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