Understanding Thermodynamics: Phase Diagram, Spontaneous and

Non-Spontaneous Process and its relationship to Carnot Cycle

Thermodynamics lets us predict Every single thermodynamic system exists in a particular

whether a process will occur but
gives no information about the
amount of time required for the
process. A spontaneous process is
one that occurs without outside
intervention.
state. When a system is taken through a series of different
states and finally returned to its initial state, a
thermodynamic cycle is said to have occurred. In the
process of going through this cycle, the system may
perform work on its surroundings, for example by moving
a piston, thereby acting as a heat engine. A system
undergoing a Carnot cycle is called a Carnot heat engine,
although such a "perfect" engine is only a theoretical
construct and cannot be built in practice. However, a
microscopic Carnot heat engine has been designed and
run.

Essentially, there are two "heat reservoirs" forming part of the

heat engine at temperatures Th and Tc (hot and cold respectively).
They have such large thermal capacity that their temperatures are
practically unaffected by a single cycle. Since the cycle is
theoretically reversible, there is no generation of entropy during
the cycle; entropy is conserved. During the cycle, an arbitrary
amount of entropy ΔS is extracted from the hot reservoir, and
deposited in the cold reservoir. Since there is no volume change
in either reservoir, they do no work, and during the cycle, an
amount of energy ThΔS is extracted from the hot reservoir and a
smaller amount of energy TcΔS is deposited in the cold reservoir.
The difference in the two energies (T h-Tc)ΔS is equal to the work
done by the engine.

Processes of Carnot Cycle

2. Reversible adiabatic gas

1. Isothermal expansion expansion process

3. Reversible isothermal 4. Reversible adiabatic gas

gas compression process compression process
 Heat is transferred reversibly from high
temperature reservoir at constant
temperature TH (isothermal heat addition or
absorption). During this step the gas is allowed to
. expand, doing work on the surroundings by pushing up
the piston (stage 1 figure, right). Although the pressure
drops from points 1 to 2 (figure 1) the temperature of
the gas does not change during the process because it is
in thermal contact with the hot reservoir at Th, and thus
the expansion is isothermal. Heat energy Q1 is absorbed
from the high temperature reservoir resulting in an
increase in the entropy of the gas by the amount

For this step the gas in the engine is thermally insulated

from both the hot and cold reservoirs. Thus they neither
gain nor lose heat, an 'adiabatic' process. The gas
continues to expand by reduction of pressure, doing
work on the surroundings (raising the piston; stage 2
figure, right), and losing an amount of internal energy
equal to the work done. The gas expansion without heat
input causes it to cool to the "cold" temperature, Tc.
The entropy remains unchanged.

Now the gas in the engine is in thermal contact with the

cold reservoir. The surrounding do work on the gas
pushing the piston down, causing an amount of heat
energy to leave the system to the low temperature
reservoir and the entropy of the system will be
decreased.

Once again the gas in the engine is thermally insulated

from the hot and cold reservoirs, and the engine is
assumed to be frictionless, hence reversible. During
this step, the surroundings do work on the gas, pushing
the piston down further (stage 4 figure, right),
increasing its internal energy, compressing it, and
causing its temperature to rise back to Th due solely to
the work added to the system, but the entropy remains
unchanged. At this point the gas is in the same state as
at the start of step 1.
 IDEAL CARNOT CYCLE
p-V Diagram

ISOTHERMAL EXPANSION
At constant temperature ADIABATIC EXPANSION
No exchange of Heat

ADIABATIC COMPRESSION ISOTHERMAL COMPRESSION

No exchange of Heat At constant temperature
 Carnot engine has three main parts. First, an insulated, non-conducting stand, so
that the transfer of energy is not possible. Second is the hot reservoir with infinite heat
capacity. Heat capacity is infinite so that the temperature of the reservoir remains
constant after taking any energy from it. It is also called Heat source. Third, a cold
reservoir. Its heat capacity is also infinite . So that any amount of heat is given, its
temperature does not change. This is called heat sink.
Another is a cylinder in which the working substance can be kept. Working
substance can be anything gas or liquid. Cylinder is fitted with a movable piston. The
piston and cylinder walls are made of non-conducting material. Due to which transfer
of heat is not possible. While the base of the cylinder is conducting. A carnot engine
goes through four different stages of the Carnot cycle. Which is graphically displayed
on a PV graph.
For this, first place the cylinder on the hot reservoir. Since the temperature of the
reservoir is higher than the temperature of the gas, the heat flows from the heat reservoir
to the gas. Due to which the gas starts to expand. Since due to heat transfer gas is
expanding, therefore the temperature of the gas remains constant. This process is called
Isothermal expansion. As the gas expands, the volume of the gas increases and pressure
decreases.
In next step, take off the cylinder from the hot reservoir and place it on the
insulating stand. When doing so, the gas is confined to the non-conducting wall. Now
let Piston rise slowly upward. Due to which the gas continues to expand. But this time
the gas is not getting any heat to expand. Such expansion is called adiabatic expansion.
Since this expansion is taking place without heat, the temperature of the gas starts to
decrease. Due to this expansion, the volume of the gas also increases and the pressure
decreases. Then, lift the cylinder from the stand and place it in cold reservoir. Press
the Piston downward which causes compression of the gas. The reservoir absorbs
whatever extra heat is produced due to compression of the gas. In this way the gas
compresses at the same constant temperature. This is called isothermal compression.
Due to this compression the volume of the gas decreases and the pressure increases.
In the final step, keeping the cylinder on the stand again, press Piston downward.
But now there is no cold reservoir to absorb, the heat getting produced extra. Therefore,
the temperature of the gas starts increasing. This compression is called adiabatic
compression. Press the piston until the temperature of the gas rises back to equal that
of the hot reservoir. This decreases the volume of the gas and increases the pressure.
At the end of this step, the gas returns to its initial stage. This complete cycle is
called the Carnot cycle. And the engine working on it is called the Carnot engine. The
efficiency of a Carnot engine depends on the temperature of both reservoirs. Either rise
the temperature of the hot reservoir to infinite Kelvin. or low down the temperature of
the called reservoir to zero Kelvin. In both cases, the engine efficiency will be 100%.
 Heat Engine Efficiency: How is Spontaneous & Non-
Spontaneous Process and Carnot Cycle Related

Carnot Cycle is a hypothetical process. It’s the most ideal cycle of changing pressure and temperatures
in a fluid. In case of a heat engine, 100 % efficiency would not be possible but improving the
efficiency can, if we try to model it to Carnot Cycle design. This idea shows that the efficiency of a
heat engine is only dependent on the temperature of the heat reservoirs rather thanthe type of fluid
that it uses. As such, the maximum attainable efficiency of a heat engine is equal to the formula shown
below:
Limitation of efficiency was also discovered based
on the idea of Carnot Cycle and this is one of the
foundation toward understanding waste and energy.
Rudolf Julius Emanuel Clausius who was a German
physicist and mathematician was considered one of
the central founders of the science of
thermodynamics.
thermodynamics. By his restatement of Sadi Carnot's principle known as the Carnot cycle, he
introduced the idea of entropy. Entropy is the loss of energy available to do work. It’s also the measure
of the disorder, or randomness of a system. As another form of the second law of thermodynamics, it
states that the total entropy of a system either increases or remains constant; it never decreases.
Entropy is zero in a reversible process; it increases in an irreversible process. Generally a reaction
will occur spontaneously if the entropy increases, but the enthalpy is also negative, or small and
positive, according to Gibbs free energy equation.

Entropy (S) is a measure of the disorder in a system.

In a closed system, entropy always increases over time. In an open system,
energy can be added to a system to cause a decrease in entropy, but this is not
necessarily a spontaneous reaction.
If entropy (disorder) increases, and the reaction enthalpy is exothermic (ΔH<0)
or weakly endothermic (ΔH>0 & small), the reaction is generally spontaneous.
The Gibbs free energy equation is:
ΔG=ΔH−TΔS
A reaction will be spontaneous if the change in G, ΔG, is negative.
For the product of temperature times ΔS, where ΔS is the change in entropy, if
the change in entropy is positive (disorder increases), then TΔS, when
subtracted, becomes negative.
Since the cosmos (observable universe) is essentially a closed system, entropy
will continue to increase until the universe essentially ceases to exist.
 This novelty toy, known as the drinking bird, is an example of Carnot’s engine. It contains methylene
chloride (mixed with a dye) in the abdomen, which boils at a very low temperature—about 100ºF. To
operate, one gets the bird’s head wet. As the water evaporates, fluid moves up into the head, causing
the bird to become top-heavy and dip forward back into the water. This cools down the methylene
chloride in the head, and it moves back into the abdomen, causing the bird to become bottom heavy and
tip up. Except for a very small input of energy—the original head-wetting—the bird becomes a
perpetual motion machine of sorts. (credit: Arabesk.nl, Wikimedia Commons)

We know from the second law of thermodynamics that a heat

engine cannot be 100% efficient, since there must always be some
heat transfer Qc to the environment, which is often called waste
heat. How efficient, then, can a heat engine be? This question was
answered at a theoretical level in 1824 by a young French engineer,
Sadi Carnot (1796–1832), in his study of the then-emerging heat
engine technology crucial to the Industrial Revolution. He devised
a theoretical cycle, now called the Carnot cycle, which is the most
efficient cyclical process possible. The second law of
thermodynamics can be restated in terms of the Carnot cycle, and
so what Carnot actually discovered was this fundamental law. Any
heat engine employing the Carnot cycle is called a Carnot engine.
What is crucial to the Carnot cycle—and, in fact, defines it—is that
only reversible processes are used. Irreversible processes involve
dissipative factors, such as friction and turbulence. This increases
heat transfer Qc to the environment and reduces the efficiency of
the engine. Obviously, then, reversible processes are superior

CARNOT ENGINE
Stated in terms of reversible processes, the second law of thermodynamics has a third form:

A Carnot engine operating between two given temperatures has the greatest possible
efficiency of any heat engine operating between these two temperatures. Furthermore, all
engines employing only reversible processes have this same maximum efficiency when
operating between the same given temperatures.
A pressure–volume diagram (or PV diagram, or volume–pressure loop) is
used to describe corresponding changes in volume and pressure in a
system. They are commonly used in thermodynamics, cardiovascular
physiology, and respiratory physiology.
http://www.wright.edu/~guy.vandegrift/openstaxphysics/chaps/15%20Thermodynamics.pdf
https://youtu.be/2B81W6nNds0
https://chem.libretexts.org/Bookshelves/General_Chemistry/Map%3A_Principles_of_Modern_C
hemistry_(Oxtoby_et_al.)/Unit_4%3A_Equilibrium_in_Chemical_Reactions/13%3A_Spontaneo
us_Processes_and_Thermodynamic_Equilibrium/13.8%3A_Carnot_Cycle_Efficiency_and_Entr
opy?fbclid=IwAR3pHqt_5yuTRPFNHASmfWBrLGkBZGP285T9XDSvOUKWh7nICvFqavFB
tjE
https://youtu.be/NasmLQOf30s
https://www.google.com/search?q=carnot+cycle&hl=fil&authuser=0&source=lnms&tbm=isch&
sa=X&ved=2ahUKEwiQgO3Sp5HyAhUEL6YKHXuDAEIQ_AUoAXoECAEQAw&biw=1821
&bih=833#imgrc=YTaMMhWPNpPPGM

Prepared by:

RICHELLE B. AMGAO

KRISTEL MARICON H. CAJALA

JANE ARA S. MARASIGAN

CYLLIZ KAESSA M. MERILLES

JONNA MAE F. TAYTAY

 QUANTIFYING HUMAN STRESS RESPONSE USING ENTROPHY CHANGE

The paper presents the results providing an entropy change to model human stress response. Finger skin
temperature was used as an indicator of stress response to a stressor (or stressful event) followed by a
recovery. The entropy change (Δ𝑆) is calculated using heat transfer (𝛿𝑄) from the peripheral skin and finger
skin temperature (𝑇𝑓). It was hypothesized that the human stress response, as evidenced by finger skin
temperature change, is a quasi-static process. The researchers used data collection method using published
article related to this study. From the data collected, the entropy approach is demonstrated using data from
a medical school experimental study. The finger skin temperature was measured under three conditions
(relaxation, stressor task, and recovery) during the physiological test profile. The entropy change (Δ𝑆) is
postulated as entropy damage (Δ𝑆D), which is a metric for measuring the aging or system degradation. The
aging-ratio, 𝐴aging-ratio, that is, the ratio of entropy change due to stressor to that of recovery, is presented
for both male and female subjects. The statistical 𝑡-tests demonstrate statistical significance in human stress
response to stressor and recovery states within and between male and female subjects. This novel approach
could be valuable to medical researchers, particularly in the field of occupational health to evaluate human
exposure to stressful environments.

Introduction

The stress response, or “fight or flight” response is the emergency reaction system of the body. It is there
to keep you safe in emergencies. The stress response includes physical and thought responses to your
perception of various situations. When the stress response is turned on, your body may release substances
like adrenaline and cortisol. Your organs are programmed to respond in certain ways to situations that are
viewed as challenging or threatening. The stress response can work against you. You can turn it on when
you don’t really need it and, as a result, perceive something as an emergency when it’s really not. It can
turn on when you are just thinking about past or future events. Harmless, chronic conditions can be
intensified by the stress response activating too often, with too much intensity, or for too long. Stress
responses can be different for different individuals. The parasympathetic nervous system in your body is
designed to turn on your body’s relaxation response. Your behaviors and thinking can keep your body’s
natural relaxation response from operating at its best. (The Stress Response and How it Affects You Ver3.0
– July 2013).

Numerous researchers have been studying human stress physiology to better understand the complexity of
stress response to stressful events in different environments. The human physiological system maintains
internal core temperature (98.6∘F) at a normal level by enhancing or inhibiting heat production and heat
loss. The state of maintaining constant internal temperature is called homeothermic state and the
phenomenon is called homeostasis. The finger skin temperature, which is considered to be representative
of the sympathetic nervous system (SNS), is a strong indicator of human stress response . Thermoreceptors
located underneath the skin respond to both local temperature and its changes. Signals from the
thermoreceptors are transmitted by the central nervous system on the hypothalamus which in turn
determines the overall thermal state of the body and issues the appropriate effector commands, which cause
changes in the body temperature via blood flow changes and metabolic heat production. The leading stress
researcher Hans Selye defined stress as the nonspecific response of the body to any demand. In other
words, he established the fact that stress response to a stressor is wear and tear of the body. Karwowski has
clearly elucidated the importance of using psychophysiological measures to quantify mental stress, fatigue,
and performance in the field of human factors and ergonomics. Mental stresses cause a wide range of effects
on worker performance. As discussed by A. Mital and C. Mital , these could be physiological (elevated
heart rate, blood pressure, etc.), performance related (decreased output, increased errors, etc.), or behavioral
(lack of attention, anxiety, etc.). Several researchers have investigated the effects of mental and physical
stresses. Increase in heart rates, changes in blood pressure, and body temperature are some of the human
stress responses used in the past. Another study by Boregowda et al. investigated the use of
thermodynamics-based Maxwell relations to quantify stress response in terms of multiple physiological
variables (blood pressure, heart rate, skin temperature, electromyogram, and skin conductance level).
(Journal of ThermodynamicsVolume 2017)

However, none of these studies use an easily measurable physiological indicator and a straightforward
thermodynamics based methodology. The present study overcomes the past limitations to quantify stress
response using an easily measurable finger skin temperature in a straightforward thermodynamic expression
for entropy change. This study, which used specific event data, is unique in that it examines entropy change
as a measure of reliability.

Methodology

In response to our objective which is to quantify human stress using entropy change, the researchers made
use of the published article of the Journal of Thermodynamics Volume 2017. In order to attain the given
goal, the researchers formulated three (3) equations based on the following aspects. The first one is the
formulation of entropy change equation. The researchers considered a quasi static process of heat transfer
taking place between the human physiological system and the physical environment as a result of stressful
event. The entropy change is given by:

Next is the entropy damage. The entropy damage is the disorder in the human physiological system caused
by heat transfer due to imbalance in the internal physiology as a result of imposed psychological stress.

This equation of the entropy damage shall be used to compute the aging ratio. The aging ratio provides a
quantitative measure of human physiological aging or system degradation. The researchers used this
formula for the aging ratio:

Where:

Tf1- finger skin temperature at the end of relaxation period.

Tf2 – finger skin temperature at the end of stressor period.

Tf3 – finger skin temperature at the end of recovery period.

The data is collected at three different states: relaxation, stressor task, and recovery. The relaxation state is
considered as the reference state and any deviation from it is measured in terms of entropy damage. The
participants in this study are the 48 medical residents aged 22-40 years weighing 57-106 kg and 36 female
medical residents age 23-41 years and weighing 48-114 kg. All the eight-four (84) subjects completed a
standard physiological stress profile procedure routinely used for clinical assessment in the Primary Care
Medicine Department at Eastern Virginia Medical School.( Journal of Thermodynamics Volume 2017).
The physiological data were collected by a ProComp+ biofeedback system connected to a Dell 166MHz
PC computer running a MultiTrace biofeedback software for data processing and analysis, as well as a
standalone Dinamap 1846 Vital Signs Monitor (Critikon Inc.,Tampa, FL). The stress profile (Stroop test)
is a 20-minute standard testing sequence, during which skin temperature from the palmar surface of the left
hand little finger is collected continually during the three states identified previously, specifically in the
three states. State 1 (relaxation period). It includes relaxing in a semireclining position with eyes open for
three minutes followed by relaxing with eyes closed for three minutes (total time = 6 minutes). Next is State
2 (stressor period). This includes solving a series of forty (40) six-second long cognitive tasks presented on
a computer screen, that is, Stroops-type color-naming tasks and arithmetic problems, which are alternated.
The sequence of tasks is the same for all subjects (total time = 8 minutes). And the final state is the State 3
(recovery period). This includes relaxing again with eyes open for three minutes followed by relaxing with
the eyes closed for three minutes (total time = 6 minutes). 𝑡-tests, at the level of significance, 𝛼 = 0.05, are
conducted. Two 𝑡-tests were used in this study. The 𝑡-tests which include tests with two paired samples for
means. A single-tailed 𝑡-test with paired two samples is conducted to determine if there is a difference in
mean physiological stress response (finger skin temperature and entropy damage) for both male and female
subjects at stressor and recovery states relative to the relaxation (reference) state. And the 𝑡-tests which
include tests with two samples assuming unequal variances. A single-tailed 𝑡-test with two independent
samples is conducted to determine if there is any significant difference between male and female mean
stress responses (finger skin temperature, entropy damage, and aging-ratio) for both stressor and recovery
states relative to the relaxation (reference) state.

RESULTS AND ANALYSIS

This study aimed to present the results providing an entropy change to model human stress response. Finger
skin temperature was used as an indicator of stress response to a stressor (or stressful event) followed by a
recovery. The entropy change (Δ𝑆) is calculated using heat transfer (𝛿𝑄) from the peripheral skin and finger
skin temperature (𝑇𝑓). It was hypothesized that the human stress response, as evidenced by finger skin
temperature change, is a quasi-static process. The researchers used data collection method using published
article related to this study. From the data collected, the entropy approach is demonstrated using data from
a medical school experimental study. The finger skin temperature was measured under three conditions
(relaxation, stressor task, and recovery) during the physiological test profile. The entropy change (Δ𝑆) is
postulated as entropy damage (Δ𝑆D), which is a metric for measuring the aging or system degradation. The
aging-ratio, 𝐴aging-ratio, that is, the ratio of entropy change due to stressor to that of recovery, is presented
for both male and female subjects. The statistical 𝑡-tests demonstrate statistical significance in human stress
response to stressor and recovery states within and between male and female subjects. This novel approach
could be valuable to medical researchers, particularly in the field of occupational health to evaluate human
exposure to stressful environments. These aspects were described in the previous chapter that presented the
methodology used in the study.

The mean change in finger skin temperature from relaxation State 1 to stressor State 2 and recovery
State 3 for both male and female subjects is provided in Figure 1. The -test on paired samples for male and
female subjects is provided in Table 1. It is clear from Table 1 that there is a significant statistical difference
in the mean finger skin temperature change from relaxed (reference) State 1 to that of stressor (State 2) and
recovery (State 3) for male subjects. However, in female subjects it is observed that there is statistical
significance in the mean finger skin temperature change from relaxed State 1 to stressor State 2 while there
is no statistical difference between relaxed and recovery states. The entropy damage occurs when there is a
change from relaxation State 1 to stressor State 2 and recovery State 3. This takes us to the next step to
quantitatively demonstrate entropy damage for both males and females at stressor and recovery states.

Figure 2 shows the entropy damage for both male and female subjects. Relaxation State 1 is the reference
state and has a zero value of entropy damage. Any change from this reference state is shown in Figure 2
and statistical differences are indicated in Table 2 for both male and female subjects. It is clear from Table
2 that there is a significant difference Male Female Aging-ratio 0 0.2 0.4 0.6 0.8 1 1.2 Figure 3: Aging-ratio
for male and female subjects. between entropy damage values at the stressor and recovery states for male
subjects. At level of significance, 𝛼 = 0.05, the entropy damage for female subjects is not that significant
as indicated by a 𝑝 value of 0.09 in Table 2. The negative values of entropy damage indicate that the heat
is lost from the body with decrease in finger skin temperature during the stressor task [1]. The ratio of
entropy damage at the stressor state (Δ𝑆DS) relative to the recovery state (Δ𝑆DR) is termed as aging-ratio
(𝐴Aging-Ratio) [15]. The statistical𝑡-tests for two independent samples of male (𝑛 = 48) and female (𝑛 =
36) subjects assuming unequal variances are presented in Table 3. At level of significance, 𝛼 = 0.05, there
is significant statistical difference between male and female subjects in terms of finger skin temperature (at
stressor State 2) and entropy damage (at stressor State 2 and recovery State 3). However, with a 𝑝 value of
0.07, there is no evidence to indicate that there is significant difference in the values of finger skin
temperature (at stressor State 2) between male and female subjects.

The difference in aging-ratio for male and female subjects is shown in Figure 3. Further from Table 3, it is
clear that there is no significant difference between the male and female aging-ratio. The aging-ratio is an
indication of wear and tear over a period of time. The 𝑡-test results presented in Table 3 serve to evaluate
if there are any significant differences Journal of Thermodynamics 5 between male and female subjects
pertaining to the values of finger skin temperature, entropy damage, and aging-ratio.

Discussion

The present study come up with presented results providing an entropy change to model human stress
response where finger skin temperature was used as an indicator of stress response to a stressor or stressful
event followed by a recovery. The entropy change (ΔS) is calculated using heat transfer (𝛿Q) from the
peripheral skin and finger skin temperature (Tf). The finger skin temperature was measured under three
conditions (relaxation, stressor task, and recovery) during the physiological test profile. The entropy change
(ΔS) is postulated as entropy damage (ΔSD), which is a metric for measuring the aging or system
degradation. The aging-ratio, 𝐴aging-ratio, that is, the ratio of entropy change due to stressor to that of
recovery, is presented for both male and female subjects. The statistical 𝑡-tests demonstrate statistical
significance in human stress response to stressor and recovery states within and between male and female
subjects.

Nevertheless, none of these studies use an easily measurable physiological indicator and a straightforward
thermodynamics-based methodology. The present study got the better of the past limitations to quantify
stress response using an easily measurable finger skin temperature in a straightforward thermodynamic
expression for entropy change. This study, which used specific event data, is unique in that it examines
entropy change as a measure of reliability.
Conclusion

This study embroiled the use of entropy change expression quantify human stress response on the
underlying structure of thermodynamic degradation methodology. It was hypothesized that entropy change
is simply entropy damage demonstrated in terms of finger skin temperature. The aging-ratio is acquired
from the ratio of entropy damage during a stressful task relative to that of a recovery period. Comprehensive
statistical results involving data from an experimental study using eighty-four (84) subjects are presented.
The t-tests indicate that the entropy damage and aging-ratio provide valuable metrics with which to evaluate
human stress response. Specifically, the result of entropy change could be used in occupational settings
where workers are exposed to various environmental stressors.

References
https://pdfs.semanticscholar.org/d683/bcd345c0727ac244be9de1d242f865c51662.pdf?_ga=2.118617673.
1757726235.1627657715-1688242384.1627657715

https://www.semanticscholar.org/paper/Using-Thermodynamic-Degradation-Approach-to-Human-
Boregowda-Handy/9b3e51afe065ace6aa2fa41bd04bbd67beaa60d4

https://www.researchgate.net/publication/319639209_Using_Thermodynamic_Degradation_Approach_to
_Quantify_Human_Stress_Response