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cause higher entropy increase?

up vote12down votefa vorite

4

Entropy is defined in my book as Δ S=QTΔ S=QT. To derive the formula it says that entropy

should be directly proportional to the heat energy as with more energy the particles would be

flying all over the place more rapidly. This makes sense. But then it says that entropy must be

inversely proportional to the temperature at which it is added. To be precise

Heat added to a system at a lower temperature causes higher entropy increase than heat added

to the same system at a higher temperature.

How does this make intuitive sense?

EDIT 1:

I found an answer here. I think this makes sense. Can anyone read it and tell me if it's correct or

not?

Rough intuitive answer:

Adding heat to a system increases the system's total energy. This gives more kinetic energy to

distribute among the particles in the system, increasing the size of the system's phase space

and hence its entropy. However, since momentum is proportional to the square root of kinetic

energy, it is clear that the total momentum phase space cannot grow exponentially as you add

more kinetic energy; so the rate of growth of its logarithm must taper off. Since entropy is

proportional to the log of the size of the phase space, we see that each additional unit of heat

must increase the entropy by less and less.

precisely dS=δq/TdS=δq/T rather than some more complicated relationship that depends on

the nature of the system is that temperature is defined such that this is true. We know that

during first-order phase transitions, the temperature actually stays constant as you add heat!

This corresponds to a region where adding heat actually does cause an exponential increase in

phase space. Finally, note that some systems actually have negative temperature, and adding

more heat to them actually makes the temperature even more negative; so adding heat actually

decreases the phase space. So the intuitive answer in the previous paragraph shouldn't be

taken too seriously.

EDIT 2: Moreover, this answer explains why there needs to be an additional factor of

temperature along with heat in the definition of entropy so as to be consistent with the second

law.

This is why heat flows from hot objects to cold objects: the entropy change of the hot object is

negative, while that of the cold object is positive. The magnitude of entropy change for the cold

object is greater. ΔS=QTc−QTh>0ΔS=QTc−QTh>0 as Th>TcTh>Tc

Keep in mind that entropy increases with temperature. This can be understood intuitively in

the classical picture, as you mention. However, at higher temperatures, a certain amount of

heat added to the system causes a smaller change in entropy than the same amount of heat at a

lower temperature.

The formula is ΔS=QTΔS=QT. The change in entropy is related to heat. Remember that heat is a

form of energy transfer, not energy; we can talk about heat only when some change takes place.

Please do point out if there is anything wrong with the answers above.

thermodynamics temperature entropy

edited Feb 10 '15 at 17:04

glS

4,91431543

asked Dec 15 '14 at 17:11

Yashbhatt

70841032

show 1 more comment

8 Answers

activeoldestvotes

up vote8down vote

The formula is actually better written

ΔS=QT.ΔS=QT.

That is, the change in entropy associated with the flow of heat is inversely proportional to the

temperature at which the heat flow occurs. Note that QQ is already a change itself: it is not a

state variable, but rather something more like ΔWΔW. Physically, this is because adding heat to

a hot system doesn't disorder it as much as adding the same heat to a cold system.

If TT is changing, you would need to integrate

ΔS=∫dS=∫δQT.ΔS=∫dS=∫δQT.

For an ideal gas at constant volume and particle number, it turns out

ΔS∝log(TfinalTinitial).ΔS∝log(TfinalTinitial).

Thus doubling the temperature does lead to the exponential of SS doubling, as you would

expect.

shareciteimprove this answer

answered Dec 15 '14 at 17:26

user10851

add a comment

up vote7down vote

+25

You asked for intuitive sense and I'll try to provide it. The formula is:

ΔS=ΔQTΔS=ΔQT

So, you can have ΔS1=ΔQTlowerΔS1=ΔQTlower and ΔS2=ΔQThigherΔS2=ΔQThigher

Assume the ΔQΔQ is the same in each case. The denominator controls the "largeness" of

the ΔSΔS.

Therefore, ΔS1>ΔS2ΔS1>ΔS2

In each case, let's say you had X number of hydrogen atoms in each container. The only

difference was the temperature of the atoms. The lower temperature group is at a less frenzied

state than the higher temperature group. If you increase the "frenziedness" of each group by

the same amount, the less frenzied group will notice the difference more easily than the more

frenzied group.

Turning a calm crowd into a riot will be much more noticeable than turning a riot into a more

frenzied riot. Try to think of the change in entropy as the noticeably of changes in riotous

behavior.

edited Feb 8 '15 at 17:49

answered Feb 8 '15 at 17:34

Inquisitive

1,352412

add a comment

up vote3down vote

Heat added to a system at a lower temperature causes higher entropy increase than heat added

to the same system at a higher temperature.

The formula defines entropy change. Since it defines new word not conceived before and thus

devoid of sense, it is hard to imagine as having "intuitive sense".

If your question really is why people use this definition and not other, here is one possible view:

Carnot came to conclusion that all reversible cycles operating between two

temperatures T1<T2T1<T2(acquiring heat Q1Q1 and Q2Q2) have the same efficiency (work

divided by heat consumed)

∑WQ2=1−T1T2.∑WQ2=1−T1T2.

Today, this is being derived from 1st and 2nd law of thermodynamics in most textbooks on

thermodynamics. It is done most easily for ideal gas, but the result is generally valid for any

substance. It is at this point where the division by temperatures enters the discussion.

Q1T1+Q2T2=0.Q1T1+Q2T2=0.

(sum of reduced heats equals zero).

General cyclic process has the same effect on the surroundings of the system as many Carnot

cycles tesselating the original cycle in the work diagram, each operating with very small

amount of heat.

Writing Carnot's equation for all of them and summing the terms, adjacent terms cancel each

other and we are left with sum over terms that correspond to boundary elements of the curve

representing the general cycle only:

∑sQsTs∑sQsTs

with both isothermic and adiabatic elements ss.

We pass from this sum to loop integral in the thermodynamic space of states XX:

∮ΓJT⋅dX=0∮ΓJT⋅dX=0

where JJ is such function of XX and ΓΓ that integral over segment of ΓΓ (let's call

it ΔΓΔΓ) ∫ΔΓJ⋅dX∫ΔΓJ⋅dX is the heat accepted by the system when it changes state along the

curve ΔΓΔΓ.

The last equation can be expressed in words this way: the line integral of J/TJ/T along closed

curve ΓΓin space of thermodynamic equilibrium states XX is always zero.

It follows that the integral

∫XfXiJ⋅dX∫XiXfJ⋅dX

(equal to heat accepted by the system) depends on the path chosen to connect thermodynamic

equilibrium states XiXi and XfXf, but the integral

∫XfXiJT⋅dX∫XiXfJT⋅dX

does not depend on it; it only depends on those two states. This enables us to define function in

the space of equilibrium states

S(Xf)=S(Xi)+∫XfXiJ⋅dXT,S(Xf)=S(Xi)+∫XiXfJ⋅dXT,

where S(Xi)S(Xi) is value of the function for reference state XiXi, chosen by convention. It does

not matter which path is chosen to connect XiXi and XfXf; value of SS only depends on the

endpoint XfXf.

This function is called entropy. Unfortunately, there is nothing intuitive about it in

thermodynamics; it's just a useful definition.

edited Feb 8 '15 at 14:10

answered Feb 8 '15 at 11:23

Ján Lalinský

11.6k1030

add a comment

up vote2down vote

I find that the question here relates directly to the definition of temperature, and I'll give a

short version of it. For simplicity let us consider a system generated by two sub-systems, A and

B, in thermal contact (meaning they only exchange energy in the form of heat).

Let me state that, for AA and BB in thermal equilibrium, the entropy SASA and SBSB for each

respective sub-system depend upon the energy in precisely the same way. This statement only

reflects the thermal equilibrium condition. Further, consider this statement in more

mathematical terms

dSAdE=dSBdEdSAdE=dSBdE

that is, that when an infinitesimal energy quantity dEdE is traded between sub-

system AA and BB such that SASA changes, then the corresponding change in SBSB exactly

compensates for this. The observation to be made is that the quantity dS/dEdS/dE gives us a

measure of how benign a system is to accept a change in energy by thermal means. From this

we define temperature as

dSdE≡1TdSdE≡1T

and we can see that for temperatures T1<T2T1<T2, the change in entropy is greater when

trading energy at T1T1 as compared to T2T2.

Edit: The intuition is in understanding the definition. Although, I will admit that it is still rather

abstract, since it contain two abstract concepts like energy and entropy. This may be stated

somewhat differently if we look more closely at the definition of entropy. For a given system,

the entropy is defined as the logarithm of the number of accessible microstates gg at some

energy EE

S∝ln(g(E))S∝ln(g(E))

that is, g(E)g(E) counts the number of accessible microstates for a given energy E. This gg may

depend on several factors of course (volume for instance). Considering the definition again and

not talking explicitly in terms of entropy; let us give a system some energy δEδE through

thermal contact and we realize that for a low system temperature the number of accessible

quantum states g(E)g(E) increase to a greater extent than compared to when the system has a

higher temperature. As such, the intuition is that we ''unlock'' more microstates for a system at

low temperature than at a higher temperature with some quantity of energy δEδE. This is

relatively speaking, since at low temperatures the system has a low energy and thus few

accessible microstates to be in, such that an energy δEδE for the system will increase the

number of accessible states to a greater extent than when at high temperatures, that is, the

impact of δEδE it on g(E)g(E) depends on the number of new states it makes available

compared to the number which was already available.

shareciteimprove this answer

edited Feb 10 '15 at 9:22

answered Feb 8 '15 at 12:54

Invoker

15516

add a comment

up vote2down vote

The question is based on the reasoning that "S rises when Q is added, and T rises when Q is

added, so S must rise if T rises." The problem is that T is kinetic energy per particle while Q is

internal energy added to the entire system minus the work done. T is an intensive property

while S and Q are extensive properties. It's true that for every particle in a given system S ~

ln(T) + c and that S ~ ln(Q) + c (which I show below). I think the core problem is that the

question mixes system-wide Q with a per particle T.

To be precise in explaining how T and Q are different when considering an entire system: to

raise T without raising Q you would have to reduce the number of particles carrying the

energy. The energy from the removed particles would be added to the remaining ones. This

would result in lower entropy because although the number of states per particle is increased,

the number of particles is decreased (the reduced N dominates in gases: S ~ N [a ln(T) + b - c

ln(N) ]. But to raise Q without raising T you would have to add particles which raises entropy.

BTW, the original formula should have dQ instead of Q so that you should have dS=dQ/T. But in

either case, it is obvious from the equation that at a higher T there will be less of an dS increase

for a given amount of Q added.

In the following I'll detail the relationship between Q and S, and then T and S, for a given

system, showing they have the same effect on S for a given fixed system but only if you do not

mix T and Q. "~ "will mean proportional, not approximately. My statements should be exact

exact, but a lot is hidden in the proportionalities because it takes advantage of log(x^c) = c

log(x).

In looking at the Sackur-Tetrode equation for an ideal gas of N particles in a given box I see:

S ~ ln(states per particle) + constant

note: the "states per particle" does not change in a simple way if N changes.

states per particle ~ momentum p per particle

momentum per particle ~ SQRT(2m (K.E.) per particle)

K.E. per particle ~ Temperature, internal energy, and heat per particle (above absolute zero)

but approximating an unrealistic ideal that heat capacity is not changing with temperature.

ln(x^0.5) ~ ln(x)

S ~ ln(T) + constant

or

S ~ ln(Q) + constant

S ~ ln(Q0 + Q1) + constant

verses

S ~ ln(2Q0 + Q1) + constant

Example: Q0 = Q1 = 2

low T has fractional S increase with Q1 added of (1.38+c)/(0.69+c)

2x T has fractional S increase with Q1 added of (1.79+c)/(1.38+c)

I could replace the Q's with T's, so the original question has some reason, but I can't mix and

match the T and Q like the question does.

edited May 1 '17 at 23:01

answered Jul 25 '15 at 2:49

zawy

717

add a comment

up vote1down vote

In my statistical mechanics course last year, we derived that S∝1TS∝1T from the following

considerations:

Consider two boxes (each with NiNi particles, ViVi volume, UiUi internal energy,

and TiTi temperature, where i=1,2i=1,2) separated by a wall through which they can exchange

energy (heat).

Clearly Ωi∝UiΩi∝Ui and Ωi∝U−13−iΩi∝U3−i−1 when the total energy, U0=U1+U2U0=U1+U2, is

fixed, where ΩiΩi is the number of states of system ii.

The first law of thermodynamics says that, at equilibrium, T1=T2T1=T2. The second law says

that, if T1<T2T1<T2, then heat goes from system 2 to system 1, meaning

that U1<Ueq1U1<U1eq, where UeqiUieq is the internal energy of system ii when the two

systems are in equilibrium with each other.

In equilibrium, entropy (S=kblnΩS=kblnΩ) is maximized.

Let's now expand the total entropy of the two systems, STST:

ST(U1)≈S1(Ueq1)+∂S1∂U1∣∣∣Ueq1(U1−Ueq1)+S2(U0−Ueq1)+∂S2∂U1∣∣∣Ueq1(U1−Ueq1)ST(U1)≈S1(U

1eq)+∂S1∂U1|U1eq(U1−U1eq)+S2(U0−U1eq)+∂S2∂U1|U1eq(U1−U1eq)

≈ST(Ueq1)+(∂S1(U1)∂U1+∂S2(U0−U1)∂U1)∣∣∣Ueq1(U1−Ueq1)≈ST(U1eq)+(∂S1(U1)∂U1+∂S2(U0−

U1)∂U1)|U1eq(U1−U1eq)

From the above statement about equilibrium maximizing entropy,

∂ST∂U1∣∣∣Ueq1=0=(∂S1(U1)∂U1+∂S2(U0−U1)∂U1)∣∣∣Ueq1∂ST∂U1|U1eq=0=(∂S1(U1)∂U1+∂S2(U0

−U1)∂U1)|U1eq

Consider that

U0=U1+U2 ⇒ 0=dU1+dU2 ⇒ dU1=−dU2U0=U1+U2 ⇒ 0=dU1+dU2 ⇒ dU1=−dU2

So

0=dS1(U1)dU1∣∣∣Ueq1−dS2(U2)dU2∣∣∣U0−Ueq10=dS1(U1)dU1|U1eq−dS2(U2)dU2|U0−U1eq

At this point, it might seem reasonable to suppose that T=dSdUT=dSdU (which it is not). As a

check, let's expand about U~1<Ueq1U~1<U1eq:

ST(U1)≈ST(U~1)+(∂S1∂U1+∂S2∂U1)∣∣∣U~1(U1−U~1)ST(U1)≈ST(U~1)+(∂S1∂U1+∂S2∂U1)|U~

1(U1−U~1)

⇒ dSTdU1=dS1dU1∣∣∣U~1−dS2dU2∣∣∣U0−U~1>0⇒ dSTdU1=dS1dU1|U~1−dS2dU2|U0−U~1>0

But this implies that T1−T2>0T1−T2>0, and that heat is flowing from cold to hot, in violation of

the second law. To make our definition of temperature mesh with the second law, we therefore

need

1T=dSdU ⇒ dU=TdS1T=dSdU ⇒ dU=TdS

shareciteimprove this answer

edited Feb 8 '15 at 19:42

answered Feb 8 '15 at 19:24

CactusHouse

1113

add a comment

up vote1down vote

Entropy is defined in my book as ΔS=Q/T.

Already, this is not correct. In general,

δS≥δQ/T.δS≥δQ/T.

In the specific case where the system being heated is at always in thermal equilibrium, then

δS=δQ/TδS=δQ/T

So, clearly, δS=δQ/TδS=δQ/T can not be taken as the definition of entropy.

The definition of entropy is [See Landau and Lifshitz "Statistical Physics" (2nd edition)

Equation 7.7]:

S=log(ΔΓ),S=log(ΔΓ),

where ΔΓΔΓ is the statistical weight of the subsystem, which is defined as follows:

If wn=w(En)wn=w(En) is the probability of finding the system in quantum

state nn then w(E¯)ΔΓ≡1w(E¯)ΔΓ≡1, where E¯E¯ is the most probable energy of the system

(which is the same as the macroscopic internal energy of thermodynamics since fluctuations

are negligible). To put it another way, ΔΓΔΓ is the number of states

within ΔEΔE of E¯E¯ (where ΔEΔE is defined as: ΔEΔE times the energy-probability-distribution

at E¯E¯ equals 1).

We can rewrite the Entropy more explicitly as a function of E¯E¯ as:

S=−log(w(E¯)).S=−log(w(E¯)).

(As an aside, it turns out that the log of ww has to be linear in EE so that

S=−log(w(E¯))=−∑nwnlog(wn),S=−log(w(E¯))=−∑nwnlog(wn),

which is another often-encountered definition of entropy.)

But, anyways, since SS is a function of E¯E¯, we can take the derivative of SS with respect

to E¯E¯. This derivative is defined to be the inverse temperature:

dSdE¯≡1TdSdE¯≡1T

The derivative above is taken at fixed system volume, so this says that δS=δQ/TδS=δQ/T... I

can explain that a little bit more below:

One way to change the energy of system is to perform work on the system. Typically in

thermodynamics this happens by compressing or expanding the volume of the system

(although it doesn't have to happen this way). If the system is not thermally isolated there is

another way to change the energy of the system, which is called heat. Heat is a direct transfer of

energy to/from other systems in thermal contact with the system. Heat and work. Work and

heat. This is how we change the energy of the system. I.e.,

δE=δW+δQδE=δW+δQ

If, the system of interest is always in thermal equilibrium throughout the process over which

the energy is changed by heat and work, then from the definition of temperature we know that

δE=δW+TδSδE=δW+TδS

I.e., δQ=TδSδQ=TδS holds.

So, anyways, we've arrived at ΔS=Q/TΔS=Q/T by defining TT as

dSdE¯≡1T,dSdE¯≡1T,

but why define the right hand side as the inverse of the temperature, why not define it as the

inverse of the square of the temperature? One answer is that if you make any other definition

you will not end up with the usual known thermodynamic laws, such as PV=NkTPV=NkT and

whatnot. But does this definition jive with my intuitive sense of temperature?! I'm sure you are

asking... Well, no, it does not. In order to make it jive with your intuitive sense you need

Boltzmann's constant kk and make the substitutions T→kTT→kT and S→S/kS→S/k. So now

does it jive?! Well, that depends on what your intuitive sense of temperature was to begin with.

If you think about this you will probably realize that we humans probably start off with an

intuitive sense of hot and cold and the sense that heat flows from hot to cold (but not an

intuitive sense of temperature). Later on we associate temperature with the expansion of

mercury in thermometers and whatnot. And the above definition of temperature appropriately

describes the expansion of mercury in thermometers just as it appropriately describes the ideal

gas law and so on... So, yes, this definition does jive with that simple intuitive sense of

temperature, only it is much sharper and more useful.

P.S. Most of the equations use the notation from Landau and Lifshitz. For more info along these

lines read chapters one and two of their "Statistical Physics".

edited Feb 12 '15 at 5:54

answered Feb 12 '15 at 5:41

hft

3,5321821

add a comment

up vote0down vote

A simple explanation: We know that heat travels from a body or system which has higher

temperature to a colder body or system which has lower temperature. Also the entropy is

directly proportional to heat. Therefore the entropy decreases in the former body (higher

temperature body) and increases in the latter body (lower temperature body). This explains

the following notion, "Heat added to a system at a lower temperature causes higher entropy

increase than heat added to the same system at a higher temperature."

answered Jan 14 at 16:41

Neil Paliwal

1

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