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Q&A for lecture on the first lesson

Dear Folks
To be an effective learner, you will have to be more critical in the understanding
and usage of scientific terms. Please remember that very often the scientific
meaning of a word can be different from its meaning in English.
Also, pleaseplease, read through the Q&A and give yourself ample time to
think deeply about the subject matter. Do not wait until the exam time to do so.
The number of Q&As involved can be overwhelming.
Do not hastily formulate questions and raise them. It is important for you to learn
to raise high order questions, but it is even more important for you to learn to
construct answers to your (and others) questions. You should then, through
discussion, compare and contrast your answers with those of your peers (or with
mine in the Q&A) to check on the correctness of your understanding on the subject
matter.
Below, please see the questions raised by your senior and my answers to them.
To facilitate you learning, I have also uploaded a 16 min video clip to ivle as extra
lesson or tutorial on Thermodynamics. Please view them at your leisure.
Also, although it would be hard on you, please glance through the article in this
website, and pay special attention to the very last section on \ "Is Entropy a
Measure of "Disorder"?"
http://www.tim-thompson.com/entropy1.html
From there, you can have an idea on whether your concept on entropy being
regarded as orderness/disorderness is right or wrong. You can easily unlearn and
relearn.
Best wishes
Prof Ip
Coverage:
A. Vital characteristics, page 2
B. Thermodynamic systems, page 6
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C.
D.
E.
F.
G.
H.

Enthalpy, entropy and heat, page 7


Gibbs free energy and thermodynamic reversibility, page 14
Spontaneity, equilibrium and thermodynamic reversibility, page 21
Melting of ice and delta G, page 26
Energy in general, page 28
Biological useful work, page 31

A. Vital Characteristics
1. What are the 7 vital signs of life you mentioned in the lecture?
The 7 vital characteristics of living organism are: (1) nutrient intake, (2)
respiration, (3) excretion, (4) locomotion/movement, (5) irritability/sensibility, (6)
growth, and (7) reproduction.
2. I refer to what you mentioned during the lecture about what defines life. I
understand that at the moment, cessation of brain activity is would confirm death.
But is it possible to resuscitate the brain after it stops functioning, just like how the
heart can be revived by a defibrilator?
I'm also a little confused. Shouldn't cessation of brain activity AND organs define
death? But then again, organ transplant may not be possible this way. Why is it that
when someone meets with an accident and falls into a coma (becomes a
'vegetable') up till the point where the doctor declares him brain dead (or can pull
off the plugs), he can still wake up miraculously some day and recover to being a
perfect man/woman?
Please take note that brain death and organ donation is not purely a
biological/medical issue, but also involves philosophy, ethics and religion. And, to
date, there are still people who do not support the idea of organ donation after a
person is declared brain death. Here, the important thing to understand is the
current definition of and procedure involved in identifying brain death.
Brain death can occur from a severe injury to the head, brain hemorrhage, stroke,
drowning or gunshot wound to the head. When the brain does not receive a steady
blood supply of oxygen and nutrients it needs to function, the brain cells die.
Brain death is the complete and irreversible end of all brain function. Brain death is
declared when medical tests confirm a complete loss of brain function, including
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the brain stem. Only a very small percentage (e.g. 1% in the U.S.) of death results
in brain death.
Brain death is not the same as a coma. A person can recover from a coma, but
brain death is death (base on the current medical definition).
If you are interested in this subject, please do some quick reading on these three
websites on brain death and organ donation (the second one brings in various
perspectives and is a good one to read):
http://www.organtransplants.org/understanding/death/
http://www.americamagazine.org/content/article.cfm?article_id=11369
http://www.cuhk.edu.hk/med/ans/Trainee%20Manual/Neurological%20Problems/Brain%20Deat
h%20and%20Organ.pdf

3. I would like to ask you about the definition of death. In lecture, you mentioned
that a person who is brain dead can be considered death. But if the person is still
sustained on oxygen supplies, and still 'breathing', do we consider him really dead
because physically we can still feel the heart beat, the breathing of the person. In
addition, is being brain dead the same as being a vegetable? According to what i
know, there are some miracles in which the people declared to be vegetables came
back to consciousness. If brain dead = vegetable, and brain dead= death, would the
definition e wrong since there is a chance of the person being 'alive'?
I would also like to ask if the definition of death can be said that a person do not
show the 7 signs of vitality/ life. Would it be acceptable?
I hope you have already gone through the three website that I have recommended
in my last email to all of you. If you have done so, you would notice that (1) brain
death is a clinical definition of the death of an individual, (2) the definition of brain
death is used as a criterion to transplant organs from a severely injured person
(which is a social reason to save life), and (3) the judgment of brain death depend
completely on doctors. Being officially diagnosed as Brain Dead is a complicated
and very detailed process in a hospital. An EEG needs to be done twice and in
some countries even preformed by two different neurologists. A French transplant
surgeon, Dr. Didier Houssin, acknowledged the difficulties that arise because of
the discrepancies between the different criteria for brain death. He observed that
"death is a medical fact, a biological process, and a philosophical question, but it is
also a social fact. It would be difficult for a society to admit that a man could be
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said alive in one place and dead in another place. However, as a proponent of
transplants, he said that it is important for society to trust doctors.
The definition of "brain dead" is used in different contexts, but generally means
that the part of the brain that controls essential brain functions such as breathing
and circulation is literally dead. There are people classified wrongly as brain dead
who still have activity going in the brain stem--those are the ones who could have a
chance at recovery---and that also depends on the injury sustained to the brain.
Those who show no activity in the brain stem are literally brain dead without any
hope of recovery. Dead brain cells cannot be replaced, so it is irreversible. The
chances of recovery from a "brain dead" state are virtually zero unless a person is
misdiagnosed in the first place and is not actually brain dead.
If someone has officially been diagnosed as brain dead there is basically no chance
of recovery. People are miss lead by media stories of people coming out of comas,
this very rarely happens and a coma is something completely different to being
brain dead.
However, I also want you to understand several important points: (1) The concept
of brain death is purely a clinical one and there are still people who do not agree to
it base on religious or philosophical reasons. (you can visit this website to gain a
opposite view
http://www.chninternational.com/brain_death_is_not_death_byrne_paul_md.html
Brain Death Is Not Death. You should be aware of all the information and make a
judgment based on analysis, reasoning and logical thinking. (2)'Brain death' is not
equivalent to 'death' if 'death' also includes the status of the cells, tissues and
organs in the individual. (3) With advances in science and medicine, the criteria of
brain death are highly likely to change or modified with time. (4) With advances in
technology, the accuracy of monitoring and executing those criteria will also
improve with time.
The seven signs of vital characteristics and the criteria set for 'brain death' are not
the same. To complicate the issue, let's examine a real case of a pregnant woman
who was diagnosed as brain-dead. She continued her pregnancy while on lifesupport system, even producing breast milk for her unborn child. The mother
produced milk, but scientist and doctors regarded that production as an inhibited
mechanical reflex rather than a sign of enduring human life. The production of
breast milk resulted from the signal sent from the anterior lobe of the pituitary that
stimulated the secretion of milk and possibly breast growth because of some
minimal hormonal production in the brain. While the brain might still be able to
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have some minor function, it could not support the body's functions to live which
are the current criteria of brain death.
Please do not be frustrated with all these confusion and controversies. You are now
in the university. Only through thinking deeply on them can you then develop as a
thinker and being able to hold your own view based on balanced judgment. Please
remember that 'to question (like what you have done) is to learn' and 'to provide
yourself with an answer to your own question is to construct knowledge'.
4. I have is actually a question concerning life and death. Frankly speaking, I find
it quite hard to accept that brain dead is used as a parameter to determine a person
is alive or dead as some parts of the brain may still be alive but perhaps they are
not significant enough to be detected. Also, there are instances where brain dead
patients come back to life so can professor tell me any logical reasons why brain
dead can actually be assumed as 'dead'?
As for the "definition" of death, it is a highly debatable issue, as it touches on
philosophy, religion, biology and medicine, and law. Even within the
medical/biological field, there was no major consensus until 1968-1972, when
Harvard Medical School defined the death of a person by "brain death". However,
it does not mean that every individual would accept this, and for instance, there
were people who refused to take their love one as dead although doctors declared
he/she being in a condition of brain death. It is really an important and interesting
topic and hence I strongly encourage you to going through the following websites
when you have some free time to do so.
You can find much information in Wikipedia. It is easy to read, and perhaps you
should focus on the section on "Problems with definition"
http://en.wikipedia.org/wiki/Death
This is a good website for you to know the history and definition of death
according to biology/medicine. It is a bit longer than the first one but worth
reading.
http://www.deathreference.com/Da-Em/Definitions-of-Death.html
This is a Stanford U website dealing with the philosophical issues of death. You
should know the differences on view arising from animalism, personalism and
mindism. It is not easy to read, but you may be interested by the arguments stated
within this article.
http://plato.stanford.edu/entries/death/
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I am glad that you asked these questions, and sincerely hope that you will know
more about these topics after going through "independent" learning.
B. Thermodynamic systems
1. How to define an isolated system?
Isolated systems can exchange neither energy nor matter with an outside system.
While they may be portions of larger systems, they do not communicate with the
outside in any way. The physical universe is an isolated system; a closed thermos
bottle is essentially an isolated system (though its insulation is not perfect). Living
systems are open systems; they are NOT isolated.
2a. Isolated system cannot exchange heat, energy and matter.
Closed system can exchange heat and energy but not matter.
Open system can exchange anything with its surrounding.
Now, I want to raise some questions: Since heat is a kind of energy, why we have
to separate it to the other types of energy when defining these terms?
This is because scientist has defined one more type of system: the adiabatic
system, which deals with heat specifically. An adiabatic system is one in which
processes occur without gaining or loosing heat from the surrounding.
2b. And what does energy means in these particular concept? Does energy
imply all the other types of energy?
Yes, energy here implies all other types of energy except heat.
2c. About isolated system, when we consider a system as isolated one, it implies
that such system is isolated from the surrounding and other system. The universe
alone is also defined to be isolated but from what surrounding or systems is it
isolated? Is it likely that we just assume the physical universe is isolated system
because there is only one universe that we have known?
Yes. Also, we do not know what is outside the physical universe at present.
2d. You said that the second law of thermodynamics states that The total entropy
of any isolated thermodynamic system always increases over time, i.e. the
occurrence of thermodynamic processes would increase the entropy of the
universe. This is because the physical universe is an isolated system. The second
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law of thermodynamic deals with the universe, i.e. the system and its surrounding,
and it does not deal with the system alone. I was a bit confused when I read this
part. I dont see any cause and effect relationship between the fact that the universe
is an isolated system and the increasing in its entropy over time. Can you explain
more about this?
It is essential to understand the physical universe as an isolated system; only then
the first law of thermodynamic would hold, i.e. the amount of energy present in the
universe is constant. Based on this, we can understand that thermodynamic
processes occurring in any system in the universe would involve the transformation
of energy from one type to another with more and more energy being turned into
the more disordered type, i.e. heat, and that the proceed of an exergonic reaction
would lead to an increase in the entropy of the universe.
3. Am I right to say that entropy, enthalpy and Gibbs free energy do not apply to
any isolated system inside another isolated system as no energy transfer takes
place?
No, that is incorrect. The concept of S, H and G can be applied to an isolated
system. However, the concepts of changes (delta) in S, H, and G do not apply
because there is no energy transfer between the system and the outside system. In
the sense, an isolates system does not have a valid surrounding.
C. Entropy, enthalpy and heat
1. What are heat energy, heat content/enthalpy and heat? I'm confused with these
terms.
Heat content/enthalpy is not the same as heat. Enthalpy is the type of energy
(stored within the system) that would be released as heat after the process of
combustion. Heat is a type of energy and there is no need to describe it as heat
energy.
2. Does energy/heat content refers to the energy available in the system?
No, energy is not heat content. "A white horse is not a horse", because "horse" is
the big set, and "white horse" is only a sub-set of the big set. When you say "a
horse" you havent specify the color and it can be a horse of any color. In this
sense, the term "white horse" and the term "horse" are not equivalent. The same
applies to "energy" and "heat content". Heat content of enthalpy is a type of
energy. During a thermodynamic process, enthalpy can be released from the
system to the surrounding (exothermic) or gained from the surrounding by the
system (endothermic). For an exothermic process, enthalpy can be released
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completely as heat, or part of it can be used to do work and part of it released as


heat.
3. Energy, as we express is the potential to work. While delta G is the maximum
amount of Gibb's free energy (you have to specify the type of energy being
referred to) available for a system to do biological work. So, does this amount of
energy refer to energy content (no, it is the amount of Gibb's free energy released
as a summation of changes in enthalpy and entropy)? If so, why is it not the same
as energy? Energy is the big set and there are many subsets, e.g. light, heat,
entropy and etc.
4. What is the difference between "enthalpy" and "entropy"?
Energy is an expression of the potential of doing work. In order to define it better,
scientists have categorized it into many different types. Just like describing human
beings; you can categorize people into British, Chinese, American, and etc. You
should be quite familiar with certain types of energy, like gravitational energy,
sound energy and heat energy. Enthalpy (heat content) and entropy are two types
of energy which you may not be familiar with. Both are involved in calculating for
the Gibbs free energy for chemical reactions. Enthalpy is the heat content of the
system which is under your observation. Under certain conditions, this specific
amount of energy can be released as heat (note: heat content is not heat). Entropy
is the dispersed energy of the system which you are observing. Under most
situations, a system would prefer to go towards a state of greater dispersal of
energy within the system and from the system to the surrounding. Energy that is
dispersed is less available to do work compare with energy that is concentrated.
5. How should we understand entropy in terms of thermodynamics? Why did my
teacher tell me that entropy is disorderness?
I know some of you still have difficulties of dissociating entropy (in classical
thermodynamics) with disorderness. However, please understand that entropy
should not be explained as disorderness in classical thermodynamics. If you want
to know more about this, please go through this website:
http://entropysite.oxy.edu/cracked_crutch.html
The term "entropy" is generally interpreted in three distinct but semi-related ways;
from a macroscopic viewpoint (classical thermodynamics and non-equilibrium
thermodyanmics, microscopic viewpoint (statistical thermodynamics), and
information viewpoint (information theory).Please take note that we are studying
physiology and I am dealing with bioenergetics which concerns mainly chemical
reactions. Please consult this website for details in different meanings of entropy
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Please take note that in this website the link between entropy and disorderness is
regarded as only a "common sense", but you should get an understanding that is
better than common sense at the university level!
http://www.scholarpedia.org/article/Entropy
Previously, in information science, entropy has been associated with disorderness,
but now we understand that:
a. Entropy measures lack of information; it also measures information. These
two concepts are complementary.
b. Entropy measures freedom, and this allows a coherent interpretation of
entropy formulas and of experimental facts.
To associate entropy and disorder implies defining order as absence of freedom,
but disorder or agitation is shown to be more appropriately linked with
temperature.
It is important to take note that although "Entropy is disorder" is a common
assertion, commonality does not make it right. Entropy is not "disorder", although
the two can be related to one another. Daniel Styer (American Journal of Physics
68(12): 1090-1096, 2000) uses liquid crystals to illustrate examples of increased
entropy accompanying increased "order", quite impossible in the entropy is
disorder worldview.
In classical thermodynamics, entropy S is defined as Q/T or delta S = Delta Q/T.
When you apply this to physical chemistry, that is to understand how energy
transfer take place in spontaneous and nonspontaneous reactions, you will have to
extend your understanding on entropy to a deeper level ( S = ( H - G)/T). With
your background, perhaps you will be able to get something out of this article,
although you may still find in difficult to read. Anyway, please remember learning
through difficulties would sharpen your thinking skills and strategies and there will
lead to changes in your knowledge, which is what an university education is about.
http://www.tim-thompson.com/entropy1.html
To conclude, please unlearn "entropy is related to disorderness" and learn that
"entropy has multiply meanings in different science disciplines" and that "entropy
represents the dispersal of energy in a system or the universe in classical
thermodynamics.
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6. When we say 'there is an increase in entropy', we mean that there is an increase


in energy possessed and stored by the molecules as there is an increase in
disorderness? The disorder results during the transition from an initial unstable
state to the final stable state?
No, that is not correct. When a system increases in entropy, energy is released from
the system to the surrounding, resulting in a greater dispersal of energy in the
universe (i.e. system + surrounding). However, I realize that your teacher might
have taught you entropy=disorderness in the past. I do not think that is correct. But,
if, and only if, you still want to view it that way, then it is important for you to
imagine that energy is stored within orderness, not disorderness. A system with
high degrees of orderness has low entropy by value. A system with low degrees of
orderness has high entropy by value. When a system goes from a state of orderness
(low entropy) to a state of disorderness (high entropy) you have to take the final
state value to subtract away the initial value. Therefore the sign of change would
be opposite to that of enthalpy. In order to correct this problem of convention/sign,
a "negative" has to be added in front of change in entropy in the equation for the
calculation of delta G.
So, when you look at the equation delta G =delta H - Tdelta S, it should actually be
understood arithmetically as change is G being the summation of change in H and
change in S, that is delta G =delta H + (- Tdelta S).
7. Does high entropy mean that the molecules in the system are more chaotic eg.
the molecules have more energy. Doesn't this mean that energy is taken in by the
system?
No. I am afraid you misunderstood the whole concept of entropy. Entropy as
dispersal of energy is distinctly different in concept (although related to a certain
extent) from the kinetic energy of molecules (referred by you as more chaotic)
which is a manifestation of temperature. Please visit the website that I have
suggested on thermodynamics and see whether the information there can facilitate
your understanding on this.
8. Am I right to say that ice has low entropy and liquid water has high entropy?
And for ice to melt to become liquid water, energy should be taken in?
Yes, you ice has low entropy and water has high entropy. So for delta S for melting
of ice, it is positive based on final entropy minus initial entropy.

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For the second questions, it depends on whether you are talking about energy as
delta G, delta H or delta S. For ice melting at room temperature, delta H is positive
meaning that heat is absorbed with an increase in enthalpy, delta S is also positive
meaning that there is an increase in entropy and hence dispersal of energy, and the
overall Gibb's free energy is negative meaning that energy is released from the
system to the surrounding during the melting process.
9. I understand that a system will prefer to go from a state of orderness to
disorderness (No, this is NOT what the Second Law of Thermodynamics said.
Entropy represents the dispersal of energy in a system and/or surrounding; in
classical thermodynamics, entropy is a type of energy, has the unit of energy, and
is NOT disorderness.), which results in an increase in its entropy (which is the
amount of energy that is dispersed and unavailable to do work). (Yes, that is
correct.) But the second law of thermodynamics also state that "there is always a
certain amount of energy which changes into a lower quality form such as heat"
during this process. So is it true to say that whenever a system goes from a state of
orderness to disorderness (NO, this is the part where understanding gets wrong.) ,
it will always be accompanied by an increase in its entropy AND transformation of
some of its energy stored in its orderness to heat? If so, why is the equation for
delta S, S=Q/T and not simply S is proportional to Q?
S is the dispersal of energy, NOT disorderness! The dispersal (S1) of a fixed
quantity of Q (heat) at T1 (say 20oC) is not the same as the dispersal (S2) of the
same quantity of Q at T2 (say 30oC). Please take note that Q is not T. So, S1 is
greater than S2 although Q were the same in quantity.)
This is not dissimilar from the concept of density where D=M/V. You can have the
same mass, but if the mass is distributed in two different volume, V1 and V2 where
V2>V1, then D2<D1 meaning that the density would be different although the
mass is the same.)
When you learn something, you must not take it as totally new or as isolated facts,
but you should try to associate it with something that you have already learned: in
this case, density.
You must practice unlearn and relearn. In this case, what prevented you from
achieving a deep understanding of entropy is due to your prior knowledge which
associate entropy with disorderness. This is NOT correct. You have apparently
understood the "dispersal of energy" concept but then you did not want to unlearn
and "forsake" the idea on disorderness. That would make a deep understanding of
entropy difficult, if not impossible.
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10. My concern is that looking at the equation of Entropy: Q/T, does it mean a
higher temperature will cause a lower dispersal of energy since the entropy of S2 is
lower than S1? (assuming that the Q used is of the same value) If so, what is the
reasoning behind this observation?
Your observation that you made on the S=Q/T relationship is correct, and there is
nothing wrong with it. However, strictly speaking, the understanding should be
that the entropy change S of a thermodynamic system absorbing a quantity of
heat Q at absolute temperature T is simply the ratio between the two: S = Q/T.
Also, the understanding here depends on the spreading of heat in a range of energy
states. If you really want to understand it you should try to read up at this website:
http://www.chem1.com/acad/webtut/thermo/entropy.html. You should focus on the
section on "Why heat flows from hot to cold" and try to understand this paragraph
"If the body receiving the heat is initially at a very low temperature, relatively few
thermal energy states are initially occupied, so the amount of energy spreading into
vacant states can be very great. Conversely, if the temperature is initially large,
more thermal energy is already spread around within it, and absorption of the
additional energy will have a relatively small effect on the degree of thermal
disorder within the body." Here, you will have to understand S as S and Q as Q.
It would mean that when Q is added to a system at high T, the S would be
smaller than when Q is added to a system at low T.
10. The 2nd law states that "There is always a certain amount of energy which
changes into a 'lower quality' form of such as heat and becomes less available to do
work.' And the 1st law also states that "The amount of energy in this Universe is
constant".
I am not sure if this is very relevant to what we are learning right now, but I was
wondering if that's the case, then would there eventually be a day where there will
be no energy available to do work? Since my understanding is that "lower quality"
energy cannot be converted to higher quality energy, so if the energy is lost as heat
and remains unavailable to do work, and the amount of energy in the Universe is
constant, then eventually all the energy that is available for work will be converted
to heat (or some other lower quality energy)? Or is there some conceptual error
that I have that led me to this conclusion?
I am glad to know that you have being thinking about this. Thousands and
thousands of scientists has also been doing the same. This question that you have
raised is important, profound, and cross the boundary of science into philosophy. I
am not teaching you physics but will try to explain it in a way that I think you will
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be able to understand. Well, I hope you will gain the foundation from my
explanation and do some further reading AT LEISURE (this understanding has no
bearing for the 1104 exam!), and to develop as an independent learner.
I want to point out that the statement "... Since my understanding is that "lower
quality" energy cannot be converted to higher quality energy,..." is flawed. Lower
quality energy is "less available" to do work is not the same as "cannot be used" to
do work. Heat can be used to do mechanical work through a heat engine, but the
maximal theoretical efficiency is only 40% (most of the time, only ~25%). That
means you can turn the Gibbs free energy from gas/coal 100% into heat but from
heat you can only take 40% to do work. That indeed will lead to more and more
heat, and heat will increase of heat will result in increase of entropy in our
universe, and your analysis is correct.
In fact, your analysis is in agreement with what has been proposed as "heat-death"
of our universe. The currently accepted view of cosmology is that our universe will
expand forever until it's ultimate "heat death". It's exactly what you just described
it's a state of maximum entropy where there is no more potential for work to be
done. This would be for all practical purposes the end of time, because the universe
would now be indistinguishable from moment to the next. You may want to do
some quick reading here:
http://en.wikipedia.org/wiki/Heat_death_of_the_universe
Heat death of the universe is related somehow to the expansion of our universe.
Dark energy is a hypothetical form of energy that permeates all of space and tends
to accelerate the expansion of the universe. Dark energy is the most accepted
hypothesis to explain observations since the 1990s that indicate that the universe is
expanding at an accelerating rate. In the standard model of cosmology, dark energy
currently accounts for 73% of the total massenergy of the universe. You may read
up on dark energy and the end of the universe here:
http://www.mso.anu.edu.au/~charley/papers/LineweaverEganParisv2.pdf
As the stars, galaxies and black holes decay, entropy will keep on increasing. (A
Super massive black hole decays emitting hawking radiation roughly in the order
of 10 to the power 100 years. So 'at least' we should keep increasing entropy till
then). As the universe goes on expanding, its temperature (as measured in the
cosmic microwave background) goes on decreasing. However, there is a lower
limit to the minimum temperature possible in the universe. This temperature is
around the order of 10 to the power -30 degree Kelvin (which is not zero degree
Kelvin). This puts an upper limit to the maximum entropy possible too. That stage
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of maximum entropy can be regarded as the black hole era (Where black holes
remain the only celestial objects) ends and universe enters dark era while
everything decays into sub atomic particles. The high estimate for this phase is 10
to the power 1200 years from now. Through this and after this part, things get even
more controversial and I cannot explain that to you here. You may want to read up
on the time line of these events.
http://en.wikipedia.org/wiki/Timeline_of_the_far_future
Having said all these, I wish to point out the scientists at CERN has recently
discovered a particle that can travel VERY fast (faster than the light constant!).
This may change our prediction of the fate of our universe.
11. Base on the 2nd Law of Thermodynamics, can I say that the entropy of our
physical universe (an isolated system) always increases as there are always some
spontaneous thermodynamic processes taking place in the universe?
Yes, that is correct.
12. It is mentioned in the lecture notes that the movement of individual molecules
at a certain temperature is due to heat - kinetic theory. Can I propose that the
mechanism behind it is that the temperature provides heat and the heat is
transformed into kinetic energy that is responsible for the movement of the
individual molecules?
The usage of the word "transformed in your statement is inappropriate. The
understanding should be that "The average molecular kinetic energy is proportional
to the absolute temperature." If temperature is measured in Kelvin degrees, then its
value is directly proportional to the average kinetic energy of the molecules of a
substance. Note that temperature is not energy; it is a number proportional to a type
of energy. Heat, on the other hand, is actual energy measured in Joules or other
energy units. Heat is a measurement of some of the energy in a substance. When
you add heat to a substance, you are adding energy to the substance. This added
heat (energy) is usually expressed as an increase in the kinetic energies of the
molecules of the substance. When heat (energy) goes into a substance one of two
things can happen: 1. The substance can experience a rise in temperature. The heat
(the added energy) can be realized as an increase in the average kinetic energy of
the molecules. The molecules now, on average, have more kinetic energy. This
increase in average kinetic energy is registered as a number called temperature that
changes proportionally with it. Note that this increase in the average kinetic energy
of the molecules means that they will now, on average, be traveling faster than
before the heat arrived. 2. The substance can change state. For example, if the
14

substance is ice, it can melt into water. Perhaps surprisingly, this change does not
cause a rise in temperature. At the exact moment before melting, the average
kinetic energy of the ice molecules is the same as the average kinetic energy of the
water molecules at the exact moment after melting. That is, the melting ice and the
just melted water are at the same temperature. Although heat (energy) is absorbed
by this change of state, the absorbed energy is not used to change the average
kinetic energy of the molecules, and thus proportionally change the temperature.
The energy is used to change the bonding between the molecules. Changing the
manner in which the molecules bond to one another can require an absorption of
energy (heat) as in the case of melting, or require a release of energy (heat) as in
the case of freezing.)
D. Gibbs free energy and thermodynamic reversibility
1. I still do not understand the delta G = delta H + -T delta S equation. Could you
explain it again?
There are several things that must be straightened out first.
(1) The second law of thermodynamics states that The total entropy of any
isolated thermodynamic system always increases over time, i.e. the
occurrence of thermodynamic processes would increase the entropy of the
universe. This is because the physical universe is an isolated system. The
second law of thermodynamic deals with the universe, i.e. the system and its
surrounding, and not the system alone. Hence, one cannot argue that there is
an isolated system and therefore there is no surrounding. If that is the
argument, thermodynamics no longer applies.
(2) There are many types of energy (as defined by our human concept of the
external world, e.g. gravitational energy, electrical energy, magnetic
energy..), and the types of energy that specifically deal with a chemical
reaction are enthalpy and entropy.
(3) Entropy is a type of energy, and enthalpy is another type of energy. Entropy
is primarily a concept of dispersal of energy and not simply the orderness or
disorderness of matter. For instance, heat (which is not a matter like
water/ice) would have a higher entropy than gravitational energy.

15

(4) The summation of changes in these two types of energy, i.e. enthalpy (H)
and entropy (S) in a system is regarded as the change in Gibbs free energy
(G).
(5) The entropy of all systems and of all states of a system is zero at absolute
zero, but it is impossible to reach the absolute zero of temperature by any
finite number of processes.
(6) The theoretical changes of enthalpy and entropy in a system, with energy
released to or supplied by the surroundings, during a thermodynamic process
define if that process would occur spontaneously in that direction, will
proceed only if a specific amount of energy is supplied from the surrounding
to the system, or will state in this thermodynamic state for a long period of
time (i.e. at equilibrium).
(7) Since biochemistry deals with chemical reactions, the concept of H, S and G
are essential to the understanding of not only physics but also bioenergetics
and physical biochemistry.
Change in G of the system is the summation of change in H and change in S in the
system after the occurrence of a thermodynamic process. The convention accepted
in science is that delta here refers to the change from initial state to final state and
is calculated as "final-initial". If a system loses enthalpy and entropy going from
an initial state to a final state, then delta G equal to -delta H + (-delta S), meaning
that delat G is a big negative value, and hence the process is highly spontaneous in
that direction. If a system gains in enthalpy and loses entropy, then whether the
reaction will proceed depend on the quantum of +delta H and the quantum of -delta
S. For instant, when ice melts at 25oC, there is a gain in enthalpy, so delta H is
positive. However, the system achieves a greater dispersal of energy, so delta S is
positive. When you multiply the -delta S with (25 +273oK), the quantum is bigger
than that for delta H. Thus, the summation of the two gives a negative delta G
value, meaning that ice will spontaneously change to water at 25oC. However,
when the temperature of the system and its surrounding is -1oC (or -1+273oK), then
-Tdelta S becomes a much smaller value, and because the quantum is smaller than
the value of +delta H, so delta G is positive in value, and the process is nonspontaneous at -1oC meaning that it would not occur spontaneously.
2a. Im unsure how "T" functions in the equation for the calculation of changes in
Gibbs free energy.
16

T here represents the absolute temperature of the system under observation. The
product of T multiplied by delta S expresses the effect of T on the change in
entropy of the system. The number of microstates for energy dispersal in a system
would be greater at higher temperature.
2b. If T represents the absolute temperature of the system under observation, is this
the temperature of the initial state only, since in spontaneous reaction, there is heat
released and the heat can increase the temperature of the system and surroundings?
The assumption is that T did not change during the process. This is a valid
assumption because any heat produced or absorbed by the system should be
transmitted to or originated from the surrounding, which is large enough as a sink
that relatively nothing has changed. Hence T is constant and there is no delta T in
the equation.
3. What is a thermodynamically reversible process?
A thermodynamically reversible process is regarded as a process which can be
brought from the initial state to the final state, and then from the final state to the
initial state again without causing any change in the universe. All processes on
earth are thermodynamically irreversible, meaning that it would cause an increase
in the entropy of the universe. Hence, according to the Second Law of
Thermodynamics, we can never produce a perpetuating motion machine on earth.
Here, you have to be clear in your concept. If you have a chemical reaction (the
system you are observing) in equilibrium with 50 A and 50 B. For every moment,
1 A changes into B and 1 B changes into A. The system is described as kinetically
reversible, but not thermodynamically reversible. In this example, you have two
velocities going equal in magnitude but opposite in direction. This is described by
"kinetics". For such a system in equilibrium, you cannot differentiate the initial
state and final state (because there is only one state), therefore, actually no
thermodynamic process has occurred.
4. In the slide on (Whats the meaning of G?), in the definition of -G, if
the process is reversible is mentioned. Why is it necessary for the process to be
reversible?
A thermodynamically reversible process is one that can go from the initial state to
the final state and then from the final state back to the initial state without
producing any change in the universe, that is, it defy the second law of
thermodynamics and no energy has been converted to a less useful type (more
disordered type) of energy, e.g. heat. Hence, the statement means that delta G
represents theoretically the maximum amount of energy that can be used to do
biological work if no heat is produced. However, this would occur only in theory
17

because the portion of delta G that turns into heat cannot be used to do biological
useful work in real life situation.
5. Do the concepts of enthalpy and Gibbs free energy apply to our physical
universe?
Yes, it applies to process taking place on Earth, and Earth is part of our physical
universe.
6. Why is it impossible to achieve 100% efficiency in energy transfer between
exergonic and endergonic reactions?
Based on our understanding of thermodynamics, for any thermodynamic process to
proceed, it must be exergonic, meaning that delta G must be negative in value.
Imagine that you have two reactions. One is an endergonic reaction having delta G
=+1000 kcal/mol. Another is an exergonic reaction having a delta G=-1000
kcal/mol. Now, you have made a coupling agent (e.g. enzyme) to try to couple
these two reactions together, and you are aiming for 100% transfer of energy
between these two processes when they take place. So, you sum it up and the
results is delta G=0, meaning that there is no energy released to the
surrounding.That means you will not achieve coupling at all and there would not
be any coupled process taking place. It is because whatever ingredients you added
in to the system, they will maintain at equilibrium.
7. Suppose a spontaneous process takes place, a certain amount of free energy will
be released. In what form is the free energy released? Is it possible to
experimentally measure the free energy released?
The form of energy is what we called it as Gibbs free energy, which is the energy
that can be used to do work. It can also be understood as the energy released from
the change in the internal energy of the system minus the energy not available to
do work. For chemical reactions that concern biology, the Gibbs free energy
release (or absorbed for an endergonic reaction) from an exergonic reaction can be
calculated from the standard Gibbs free energy if the concentrations of the
reactants and products and temperature are known. The standard Gibbs free energy
equals to RTlnKeq, at standard molar concentration of reactants and substrates.
The values of standard Gibbs free energy for ATP hydrolysis, for example, is well
established (and many other reactions occurring in the cell) and amounts to ~7 kcal
per mol. However, the Gibbs free energy of ATP hydrolysis at physiological
concentrations of ATP, ADP and Pi would be ~11 kcal per mole.

18

Please spend some time to go through this article and look out for answers to your
questions. You will learn better that way.
http://ccnmtl.columbia.edu/projects/biology/lecture8/index.htm
8. Is it true that if there is no transducer present, then the delta G will all be
released as heat? If the statement is true, then, when we use a calorimeter to
measure the heat emitted when a chemical reaction happens, is it a measurement of
delta H or delta G? Because you said that delta H is not heat, it is enthalpy or heat
content. Then why can we get the value of delta H by measuring the heat emitted?
In retrospect, I think I have not elaborated enough on this topic in the Q&A. Also,
it is possible that you might have raised this question because you still have
difficult in accepting the concept of entropy (q/T), or you may not be able to see
the differences between G, H, S, Q and T. They are all conceptually different.
In the Gibbs equation, G = H TS, each term describes an aspect of the
energy that is dispersed because of a chemical reaction occurring in a system:
G is the total energy that is spread out in the universe (system plus surroundings)
due to the reaction that has taken place in the system.
H is the energy from the reaction that is dispersed from the system to the
surroundings.
TS is the energy that is dispersed in the system in the products of the reaction
as compared to the reactants.
If each term is divided by T, the Gibbs can be seen as an all entropy equation: G/T(system) = - H/T(system) + S(system)
If there is no work done, delta G is not released as heat (which is q) but as entropy
(Q/T) in the surrounding. Q/T cannot be measure simply as Q, and Q/T is not Q.
Put it another way, Gibbs free energy change, G, is only considered entropy
change (after being divided by T) when no useful work of any kind is done by the
heat transfer in the system or in the surroundings.
The measurement based on calorimeter will give you the change in delta H of the
reaction which is measured as heat released since there is no work done. The heat
can be used to do work (e.g. in a steam engine). However, a systems enthalpy
becomes entropy change (after H is divided by T) if it is transferred to the
19

surroundings and no work of any sort is done there in the surroundings. Equally, a
surroundings enthalpy would become entropy change (after H being divided by
T) when it is transferred to the system and no work is then performed in the
system.
That means energy would become entropy if not work is done and entropy of the
universe (system + surrounding) will always increase. In other words, G, H and S
are different types of energy, but H and G can be transformed into S.
Entropy (S) is not heat (Q). The calorimeter measures T in relations to Q (T is not
Q) but does not measure Q/T (which is S).
9. Regarding the 2nd law of thermodynamics, is it possible to say that the electric
heater which converts electrical energy to heat energy is 100% efficient? Even
though there are light and sound energy given off, it will eventually become heat
energy. Hence, is it correct to say that there is a energy conversion process that is
100% efficient in the case of the electric heater?
a. Electric energy can be turned into heat 100%, but that is not what the second law
of thermodynamic says.
b. The second law says that for a thermodynamic process to take place, some
energy necessarily become less available to do work, or put it another way, the
entropy (S) of the universe (system + surrounding) increases.
c. In the case of the water heater, electrical energy is used to heat up water, but this
process is not 100% efficient because some heat is dissipated to the surrounding
and not stored in water as enthalpy.
d. Finally, the specific amount of energy (Q) used to heat up water would all
dissipate to the surrounding (without work done) and becomes entropy (S) which is
Q/T.
10a. I would like to ask if delta G=0 for a particular reaction means that the
reaction is reversible while the reaction is not reversible when delta G is not equal
to 0.
No, your understanding here is incorrect. When G=0, the system is in equilibrium
with the surrounding meaning that no thermodynamic process takes place. There is
only one state as defined by the functions of state, i.e. P, V, T, C. Since there is no
20

change in these parameters over a long period of time, there is no reaction from an
initial state to a final state. Positive delta G means the reaction would run
spontaneously in the opposite direction, or it would run in the specified direction if
an amount of energy greater than the delta G value is supplied from the
surrounding to the system. It has to be a greater amount because no reaction in our
universe is thermodynamically reversible. The excess energy is to be turned into
entropy in the universe (system + surrounding) as stated by the second law of
thermodynamics. Negative delta G means the reaction would run spontaneously in
that direction with release of an amount of energy equivalent to the delta G value
to do work on the surroundings. However, the work done would be smaller than
this amount because a certain amount of energy necessarily becomes entropy in the
universe.
10b. for example, you are provided with some amount of A, B and AB. The
reaction goes like this: A + B --> AB So when delta G<0, reaction is spontaneous
but not reversible so reaction goes forward and only AB will be present when
reaction is complete? When delta G>0, reaction is non-spontaneous and nonreversible so reaction would go backwards and eventually only A and B will be
present. Is that right?
No. When the reaction is complete there would still be A and B present together
with AB, the ratio of which is defined by the equilibrium constant AB/A.B or
indirectly by the standard Gibbs free energy which equals -RTlnKeq. Even when
the Keq is as large as 1000000, there would still be 1 A and 1 B present together
with 1000000 AB based on the equation AB/A.B. The same go for the reverse
reaction, i.e. AB would always be present with A and B at equilibrium. Here, when
you say irreversible, it should refer to thermodynamic irreversibility which I have
explained above based on the concept of entropy of the universe. I think you have
wrongly taken that as kinetic irreversibility which is not correct. When the system
is in equilibrium with the surrounding, some A and B would turn into AB, and an
equal amount of AB would turn back into A and B, and this is regarded as
kinetically reversible. However, there is no thermodynamic process taking place
because in effect there is no change in the concentration of A, B and AB at
equilibrium and therefore the system is in one state, which is the equilibrium state.
E. Spontaneity, equilibrium and thermodynamic reversibility
1. What is "spontaneity"?
Spontaneity deals with the tendency of the process which one is observing. For
example, we say ATP hydrolysis to ADP and Pi is an exergonic reaction, hence
21

spontaneous in that direction. Conversely, the reaction of ADP and Pi to produce


ATP is endergonic and hence nonspontaneous in that direction. Although a bigger
negative change in Gibbs free energy indicates that there is higher tendency for
the reaction to proceed in that direction, it tells you nothing about the rate. In the
presence of ATPase (the enzyme which catalyze the hydrolysis of ATP) the
velocity of the reaction can be enhanced many fold. But, remember, enzyme as a
catalyst, cannot change the direction of the tendency of the reaction, unless its
capable of coupling an endergonic reaction to an exergonic reaction.
2. I still have some doubts on the 'spontananeity' concept. A positive Gibbs Free
energy indicates the reaction is endergonic while a negative Gibbs Free Energy
indicates that the reaction is exergonic. (Yes, that is correct.) The spontaneity of
reaction is based on the Gibbs Free enrgy. (Yes, that is correct.) Since this is the
case, why we cannot relate endergonic and exergonic to 'spontaneity' since they are
commonly based on the concept of 'Gibbs Free Energy'? (Yes, you can. But, you
cannot link it with endo- or exo-thermic.) Also, regarding the example of 'melting
of ice cream' that you mentioned in the lecture: Melting of ice-cream is an
endergonic reaction (No. It is an exergonic process in room temperature), and is
spontaneous. How does this relate to the delta G? (delta G is negative. ) Will delta
G be positive since it is an endothermic reaction? (No. While there is an increase in
enthalpy, there is also an increase in entropy, i.e. water molecules in a fluid that are
more disordered than those in a solid state. Hence, there is an overall release of
energy from to the environment because (-Tdelta S gives a value bigger than +delta
H). As a result, delta G is negative and the process occurs spontaneously at room
temperature.)
Your obstacle in understanding this can perhaps be solved by critically evaluate
two sets of terms: (a) exergonic and (b) endergonic versus (c) exothermic and (d)
endothermic.
(a) Exergonic refers to a thermodynamic process that releases Gibbs free energy
(hence -delta G) to the environment. It is a spontaneous process.
(b) Endergonic refers to a thermodynamic process that absorbs energy (hence
+delta G) from the environment. It is a non-spontaneous process, but would go in
that direction if energy is supply to the system from the surroundings.
In the above definitions, Gibbs free energy refers to the energy free from both
enthalpy and entropy and is available to do work.
(c) Exothermic refers to a thermodynamic process that releases heat to the
environment with a decrease in enthalpy. It does not tell you whether the process is
spontaneous.
22

(d) Endothermic refers to a thermodynamic process that absorbs heat from the
environment with an increase in enthalpy (hence +delta H). It does not tell you
whether the process is spontaneous.
3. Why an endergoic process does not occur spontaneously?
Thermodynamics depends on simple observation. We observed on earth that
systems would like to go to more stable states with lower energy level. For an
endergonic process to occur, delta G is positive, meaning that energy supply to the
system is required. If energy supply is not available, it cannot go, hence, nonspontaneous. In indeed energy is supplied to the system and the endergonic process
proceeds, this specific process is described as "active" under such a condition.
4. Is exergonic process spontaneous? Is endergonic process non-spontaneous?
Yes, you got it right. Please remember that the spontaneity of a reaction is not
governed by whether it is exothermic or endothermic.
5. What is the difference between endergonic and endothermic, exothermic and
exergonic?
Exothermic (give out heat) or endothermic (takes in heat) are terms which describe
the change of enthalpy (heat content) of the process which takes place. Exergonic
(negative delta G) or endergonic (positive delta G) are terms which describe the
change in Gibbs free energy of the process. Its a summation of changes in
enthalpy and entropy. Exergonic or endergonic tells you something about the
spontaneity of the reaction. Exothermic or endothermic tells you nothing about the
spontaneity of the reaction. For example, melting of ice is endothermic but
exergonic, hence spontaneous.
A system possessing high energy content is relatively unstable, and it tends to go to
a state of lower energy content. Since the convention is to subtract the parameter of
the initial state from that of the final state, delta G would be negative for such a
spontaneously reaction.
6. How can you explain the hydrolysis of ATP based on the Laws of
Thermodynamics?
ATP hydrolysis is spontaneous because it is unstable and would like to go towards
a more stable state of ADP and Pi. You can imagine that the ATP molecule is
unstable due to the 3 phosphate groups being "squeezed" together, and they repel
each other. After hydrolysis, ADP is more stable and contains less energy. Energy
is evolved during ATP hydrolysis. According to the First Law of Thermodynamics,
this amount of energy released cannot be destroyed and can be converted into other
forms, for example, into light in a special organ in the firefly, or into chemical
23

potential energy like the sodium and potassium gradient. But, remember, according
to the Second Law of Thermodynamics, the energy transfer can never be 100%
efficient, and some necessary become heat.
7. When we said G=0, which mean the system is in the equilibrium with the
surrounding. But, is there any reactions still occur? If got reaction occurs, then
which mean that there is still energy being produce or used? Please correct me if I
was wrong.
I am glad that you raised this question which is a critical one. You must try hard to
apply critical thinking skills here to better understand thermodynamics. Here, the
most important thing to do is to understand every term critically because each term
has its own meaning. Please note the following:
a. Thermodynamics and kinetics are two different sectors of physics, both trying to
understand different facets of a phenomenon (or phenomena) occurring in
nature.
b. A thermodynamic process is defined as a process that occurs within a system
from an initial state to a final state. Here a thermodynamic state refers to the
energy level of the system as defined by the various functions of states (i.e. n, p,
v and t).
c. There are two types of thermodynamics (Classical and Onsager). Classical
thermodynamics does not deal with velocity. When a process is spontaneous
occurring as define with a negative delta G value, you know nothing about how
fast the process is taken place; nor does classical thermodynamics deal with the
path through which the process occurs.
d. A system would go from an initial high energy state spontaneously to a low final
energy state, and energy is being released which can be used to do work if a
transducer (coupling agent) is available. At the final state, the system will
remain unchanged over a long period of time with reference to various function
of states (including the concentrations of substrate and product), and is referred
to as in equilibrium with the surroundings.
e. When the system is at equilibrium with the surroundings, no thermodynamic
process occurs because the system remain to be at one single state, i.e. the
equilibrium state.
f. "Reaction" as a term is NOT equivalent to "thermodynamic process".
Specifically, when you refer to "reaction rate", you are referring to kinetics and
not thermodynamics.
g. Kinetics deals with velocity and velocity is linked to the specific path
(mechanisms) through which the reaction occurs. For example, a reaction can
occur in the absence of presence of enzymes (catalysts) and there would be
differences in the reaction rate (velocity). However, it would not change the
24

equilibrium constant of the reaction which is defined by the standard Gibbs free
energy of the reaction. Thus, the equilibrium constant is link to thermodynamics
but not to the reaction itself in terms of velocity. Also, catalysts by themselves
cannot change the direction of spontaneity of a thermodynamic process, and
catalysts cannot change the equilibrium constant of a reaction.
h. Concerning chemical reactions, there are still reactions taking place in the
system when the system is in equilibrium with the surroundings. In essence,
substrate turns into product at the same rate as product turns into substrate, i.e.
forward reaction rate is identical to backward reaction rate. There are no
changes in the concentration of the substrate and product after these reactions
have occurred. Thus, these are not thermodynamic processes. They are kinetic
processes which take place within the system, and the overall changes in kinetic
processes (both forward and backward together) involves no change in the
energy state of the system.
i. The "thermodynamic process" that has occurred which brings the system from in
the initial state to the final state is "thermodynamically irreversible".
j. By contrast, the "reaction" occurring within the system in which a chemical
reaction occurred is regarded as "kinetically reversible".
k. I know these can be difficult for you to digest all at once. However, please try to
persevere and think hard about it. If you can go through this hurdle and develop
a correct concept about bioenergetics, you will appreciate and understand
physiology (and biochemistry) much better. More importantly, through this
valuable exercise, you will sharpen your thinking skills and develop as a
thinker.
8. My teacher said when a chemical reaction is in equilibrium, one A turns into B
and one B turns into A. Yet, you said no process takes place when a system is in
equilibrium with the surrounding. So, why is this contradiction?
Scientific terms have specific meanings. A thermodynamic process is a process
which takes place between two thermodynamic states: the initial state and the final
state. A thermodynamic state can be described by various functions of states (e.g.,
pressure, temperature and volume). When a system is in equilibrium with its
surrounding, nothing happens through a long period of observation, and no initial
and final states can be differentiated. Hence, no thermodynamic process has
occurred. What your teacher has described as the phenomenon of one A to one B
and one B to one A is a kinetic process and not a thermodynamic one. Such a
phenomenon should be described as "kinetically reversibility" and not
"equilibrium", the latter being a thermodynamic term. Thermodynamic and
kinetics are two different sectors of Physics, and we should not mix up their
terminology.
25

9. For a reaction in equilibrium with the surrounding, initial stage and final stages
cannot be differentiated and that there is no defined direction. Is that correct?
Yes its correct, and the statement can be made even clearer. For a reaction in
equilibrium with the surrounding, there are "no initial or final stages (not just
because they cannot be differentiated). Since there are no initial or final stages,
there is no thermodynamic process. If there is no process, there is no direction,
isnt it? However, for a thermodynamically reversible process, you can identify
initial and final states. And, you can bring the state through 2 processes, from
initial to final and from final to initial without producing any energy of lower form.
Here, it defies the second law of thermodynamics.
F. Melting of ice and delta G
1a. I have a query. During your lecture you mentioned that melting of ice-cream is
a spontaneous process, even though it is an endothermic reaction. Is it because the
reaction is exergonic, where the energy level of the products is lower than the
reactants?
Yes, that is correct. The system gains energy in the form of heat content (enthalpy),
but loses energy in the form of entropy. Overall (delta G = delta H -Tdelta S), the
delta G for the system at room temperature (T=273 + 25) is negative in value.
Therefore, the reaction is spontaneous and would like to go towards a state of
lower internal energy.
For changes in enthalpy (H) and entropy (S) of some of the common reactions,
they have been determined and you can get the information from the Handbook of
Physics and Chemistry.
For instance:
delta H of ice melting at 25oC = 1440 cal/mol
delta S of ice melting at 25oC = 5.3 cal/mol/oK
Hence, delta G = delta H + (-Tdelta S) = 1440-(298 x 5.3) =1440-1580 = -140
cal/mol.
Please take note that delta H is positive while although delta S is positive, a
negative sign was included in the equation to accommodate the contention of
increase in entropy means an increase in the dispersal of energy (or less energy
available to do work). Since 1580 is greater than 1440, the overall delta G is
negative in value, meaning that the process is exergonic and would occur
26

spontaneously at 25oC. Also please take note that the degree of spontaneity, the
delta H value and the delta S value would change as T changes.
In the example given above, ice and water together constitute the system. Within
this system, energy is given out as Gibbs free energy (from the summation of
changes in H and S) from the initial state to the final state. The delta G of -140
cal/mol in the above calculation implies that this among of energy would be
released from a system containing 1 mole of melting ice at 25oC, and this amount
of energy can be used to do work by the system on the surrounding if a transducer
(or coupling mechanism) is available, but it does not mean that for sure there will
be work done (i.e. in the absence of a transducer).
1b. But the ice-cream molecules had gained kinetic energy during the melting
process. Why is this so?
If you examine the equation again (delta G = delta H -Tdelta S), you will find that
there is a factor "T" there, which is the temperature of the surrounding at which the
process take place. The initial state of the ice would have a temperature of zero
degree, but the melting occurs at room temperature which is 25oC (but T should be
in degree Kelvin). So, molecules during and after melting at room temperature
would have greater kinetic energy, because the temperature of the system will
finally be in equilibrium with that of the surrounding (i.e. 25oC).
From this equation, you can learn about another important concept. If the reaction
is occurring in Alaska at -10 degree C then you can immediate see that the process
(melting) would not be spontaneous (because of the contribution of T into -Tdelta
S), and there would not be an increase in kinetic energy of the molecules.
2. I am not very clear with the concept of Gibbs free energy on the example of ice
melting. For the process of ice melting at room temperature at 25 C, it occurs
spontaneously because delta G is negative in value, i.e. exergonic. However, the
process is endothermic so there is a positive change in delta H meaning that the
system gains in heat content (endothermic) and For an endergonic process to
occur, delta G is positive, meaning that energy supply to the system is required
Similarly, on the notes, it also indicates that positive delta G equals to endergonic
reaction and negative delta G is exothermic reaction. Is the example of ice melting
an exception of endergonic reaction? Does negative delta G value always indicate
an exergonic reaction?
Ice melting at room temperatures is an exergonic reaction (not endergonic as you
have subsequently stated). Yes, negative delta G always indicates an exergonic
reaction.
27

It is important for students of science to critically understand the meaning of terms


and use them critically. Please take note of the following:
a. Negative delta G = exergonic, spontaneously occurs in that direction
b. Positive delta G = endergonic, non-spontaneous in that direction (but
spontaneous in the opposite direction)
c. Negative delta H = exothermic
d. Positive delta H = endothermic
It is therefore incorrect to state that negative delta G is exothermic. Delta H does
not govern the spontaneity of the reaction, but delta G does. For a reaction that has
a positive delta G, it would not occur spontaneously in that direction, but if the
system is supplied with an amount of free energy larger than the required delta G
value (for any thermodynamically irreversible process), the reaction would take
place. For ice melting at 25oC, delta G is negative, despite delta H being positive,
because of a large + delta S value. Substitute those into the equation G =H + (TS) and you can understand a better.
3. The melting of ice is an exergonic process, therefore a spontaneous process. If
that is the case, is it correct to say that freezing of water is an endergonic process
and not spontaneous? What then about freezing water in winter conditions? From
observation, it is a spontaneous process, therefore is it correct to say that it depends
on the conditions involved if we want to say that a process is spontaneous or not?
You must state clearly the temperature of the system and the surrounding. Yes,
melting of ice is an exergonic process at room temperature (25C). And, formation
of ice at room temperature is an endergonic process. Thats why you need to make
ice by putting water into the freezer, and you need to supply electricity (energy) to
the freezer to make ice!
Formation of ice in Alaska during winter is different because you have to take
temperature into consideration. Temperature is a function of state and involve in
the equation delat G=delta H-Tdelta S. At that temperature, melting of ice is an
endergonic process, but formation of ice is an exergonic process.
G. Energy in general
1. While I agree with the fact that energy cannot be created or destroyed, how did
energy come about in the first place? And if that phenomenom that created all the
energy happened once, is it possible to recreate that event?
I am happy that you've gone through the Q&A and are thinking about "energy". To
tell you the true, I do not think I can answer your question, nor I think anybody
can. The theory that has received the greatest support on the beginning of the
universe is the big bang theory. According to this theory, that was a very big
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explosion presumably from a highly dense mass of material, which resulted in a lot
a lot of energy. The energy then created space (the universe) which is still
expanding today, and some of the energy became mass again. I do not know if that
event can be recreated; physicists all over the world continue to think about and
work on new theories and that is the beauty and value of science. Because you are
now thinking about it, and if you continue with you effort, without realizing it, you
are developing yourself as a scientist and get involved in the exciting and
challenging process of hypothesizing, testing, and proving what you have thought
of in your mind.
2. In the slide on Different forms of energy, are all different forms of energy
listed here arranged in such an order that the forms of energy higher in the list is of
higher quality (more available to do work; more ordered) and the forms of energy
lower in the list is of lower quality. For example, energy of rotation is of higher
quality/more ordered compared to energy of orbital motion.
Yes, that is correct in general. However, please take note that some of the items in
the list share the same rank of orderness.
3.Could you give some examples for energy of rotation?
Examples include the rotation of earth along its axis and the rotation of twin
(binary) stars. For instance, the Earth has a rotational kinetic energy of 2.141029 J.
4. Mechanical energy is just a generic term for work being done right?
No. You can have energy but there can be no work done. Energy and Work are
two different concepts in physics. Energy can be viewed as the potential (as an
English, and not a scientific, term) to do work. Mechanical energy is a concept that
encompasses the sum of potential energy and kinetic energy within a mechanical
system.
5. Chemical engines convert chemical energy to mechanical energy.
No. Chemical engines convert energy released from chemical reactions to work
done. Mechanical work is a type of works. Chemical engines in your body, for
example, can convert chemical energy to chemical potential energy. Others in the
animal world can convert chemical energy into light (Practical one).
6. Why can't we substitute mechanical energy for kinetic energy? Are they the
same thing? Or is the term "mechanical' of greater significance?

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They are not the same. Mechanical energy exists as both kinetic and potential
energy in a system. Kinetic energy, the energy of motion, exists whenever an
object is in motion. Potential energy is based on the position of an object. It can not
cause any change on its own, but it can be converted to other forms of energy. A
bowling ball suspended ten feet above the ground, for example, would possess no
kinetic energy. It would, however, possess a large amount of potential energy that
would be converted to kinetic energy if the ball were allowed to fall. The
summation of kinetic and potential energies gives the mechanical energy of the
system.
7. I understand that high order energy can be transform into low level of energy but
not the other way round. However, this does not seem to apply to heat engine. Is
my concept wrong?
It's good that you raised this question. If you change your statement to this "high
order energy can be transformed 100% into low order energy but low order energy
can never be changed 100% to high order energy", you should be able to
understand it better. The 100% concept here is the most important. A heat engine
can turn at most 38-40% of heat to mechanical work. If you apply this concept to
biology, it would mean that chemical energy released from glucose oxidation can
be turned into heat 100%, but you cannot take the released energy (as heat) and
turn it completely back to the chemical energy as stored in glucose. Thus, the
amount of low order energy (heat) on earth and the Universe will increase with
time.
8. Is "transform" a more appropriate word to use than "convert". What is the
difference between the two words? Does transform means that not all of the energy
is being changed to another form of energy (which means heat is released) while
convert means that all of the energy is being changed into another form of energy
with no heat loss?
If that is the case, whenever one form of energy is being changed to another, we
have to use the word "transform" instead of "convert"? Eg. Electrical energy is
being transformed into kinetic energy instead of electrical energy is being
converted into kinetic energy?
It is a combination of English and scientific usage that I believe 'transform' is a
better word than 'convert' to describe the transformation/conversion of energy from
one type to the other.

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In terms of English, 'Marriage transforms his character', is more appropriate than


'marriage convert his character'. The word convert implies the involvement of
some sort of physical devices.
In term of scientific usage, it is correct to say 'Gravitation energy is transformed
into mechanical energy', but it may not be appropriate to say 'based on E=mc2,
mass can be transformed into energy'. Rather, it is more appropriate to say that
'based on E=mc2, mass can be converted into energy' because mass is not (a form
of) energy.
For both 'transform' and 'convert', there is no implication on the efficiency of the
process.
I am happy that you start asking this type of question which superficially may
appear as confusing and un-meaningful. However, this is the beginning of critical
thinking which involve the critical usage of terms. You are learning to be critical
and that is a very good start!
9 If energy can neither be created nor destroyed due to the law of thermodynamics,
but can only be transformed from one form to another through the help of a
transducer, eg chemical potential energy to electrical energy, is there a possibility
that our body has a hidden magical potential energy that can actually be transform
into other form of energy, such as electrical magical energy or heat energy in the
form of fire which we have seen in books and movie? The only thing that is
lacking now may be the presence of a transducer that has yet to be discovered to
actually transform this energy. Do you think that there is a possibility or an aspect
in science worth discovering?
The word "energy" has different meaning to different people, but to scientist it has
only one meaning, that is the potential to do work. In scientific terms, energy
represents the work that can be performed by a forced, which implies that energy
can be measured by work done. However, people outside the scientific arena also
use the word energy to describe other phenomena, and under those circumstances
the meaning of energy is not the same as what I have described above. Personally,
I would not mix them up. My mind is open and I am tolerant of unexplained
phenomena, but at present, I am afraid scientific data does not support a "hidden
type of potential energy" that can be transformed into other forms of energy. If the
other forms of energy have already been established by scientists then there is no
reason why we cannot trace back to the hidden type. I am not trying to argue that
non-scientists cannot define some unexplained phenomena using the word
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"energy", but my point is that this "energy" is not the same as the type of energy
that govern by the laws of thermodynamics in science.
H. Biological useful work
1. In the sentence "the system to do biological useful work on its surrounding",
what does "biological useful work" mean?
There are three types of biological useful work: (1) formation and/or maintenance
of electrochemical gradients, (2) synthesis of biomolecules and (3) mechanical
movements.
2. For the synthesis of biomolecules as biologically useful work, do we do this
work to the environment or ourselves? I think we do this for ourselves but not the
environment right?
In science, it is of utmost importance to know the exact scientific meaning of the
words, which can be different from the common English meaning, so that
communication would be clear and exact.
In thermodynamics, system and surrounding has their own scientific meaning
although they are English words. Surrounding as a thermodynamic term is not
the same as environment. System can be defined as a chemical reaction taking
place in a small compartment with a cell, a protein or a group of protein, an
organelle, a cell, a tissue, a organ, an organism, a population, and etc, and anything
outside that system is defined thermodynamically as the surrounding. The
system and the surrounding equal to the universe.
You have apparently taken my explanation in thermodynamics e.g. surrounding, as
the environment. Perhaps, you can understand it better if you can critically
evaluate the meaning of these terms to you (how did you learn thermodynamic
previously?) so that you can use them correctly. It is important to unlearn and
relearn.
3. You said that humans did not defy the 2nd law of thermodynamics even though
they have a high degree of maintained order. may I know why is that so?
a. The second law of thermodynamics deals with entropy of the universe, NOT the
orderness of a system (or living system). Entropy is NOT disorderness but a form
of energy.

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b. For any thermodynamic process that take place within the living system, there
would be an increase in the entropy of the system + surrounding (=the universe)
which is in agreement with the second law of thermodynamics.
c. For any living system, the overall delta G of the living process is negative. Since
no work would be done, this free energy would increase the entropy of the
surrounding as delta G/T.
4. I do understand that ATP is unstable, as it is at a high energy level, and it has a
tendency to form more stable products like ADP, Pi through hydrolysis. The
reaction does release Energy, and it is exergonic. Does it mean that ATP is a low
energy bond, and it has a tendancy to form higher energy bonds like in the case of
ADP, Pi. So I suppose high energy bonds are the same as a strong bonds, which
also means that they are at a low energy level, as an exothermic process( E
released) creates stronger bonds.
Please unlearn the relationship between energy released from ATP hydrolysis
(which is delta G) and high energy phosphate bond. By the way, please
remember that you need to supply energy to break a bond.
ATP is not a store of energy - it is the immediate donor of free energy that is
continually being regenerated from ADP (40kg/day is turned over in humans). We
store energy in the form of glycogen and fat (or phosphagens like creatine
phosphate).
The large amount of free energy released from ATP hydrolysis has got nothing to
do with the breaking of the phosphoanhydride bond attaching to the terminal
phosphate group (breaking this bond uses energy). Some books call this bond a
high energy bond but this is misleading.
Why is G' so high for ATP hydrolysis?
a) Hydrolysis reduces electrostatic repulsion between negative charged oxygen
atoms on the phosphorus atoms.
b) ADP and Pi are stabilised by resonance.
c) Entropy (disorder) is higher after the reaction

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These 3 factors make ATP hydrolysis favourable and are responsible for the large
amount of energy released during hydrolysis.
The free energy released from ATP during hydrolysis is derived from enthalpy and
entropy, which are concepts totally different from bond energy.
If you are interested, please visit this website
http://web.virginia.edu/Heidi/chapter3/chp3.htm and directly do for the subheading
'Phosphoric Acid Anhydrides' and the following three subheading.

END

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