Entropy

Entropy is in some sense a measure of disorderness.

The symbol for entropy is S, and the units are J/K.

Second Law of Thermodynamics A container of ideal gas has an entropy value, just as it has a
pressure, a volume, and a temperature. Unlike P, V, and T,
which are quite easy to measure, the entropy of a system is
difficult to calculate.

On the other, a change in entropy is easy to determine.

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Change in Entropy in Non-Isothermal

Change in Entropy in Isothermal Process Processes
If the heat transfer Q occurs with the temperature of the
system changing from T1 to T2, ΔS is:
Entropy changes whenever there is a transfer of heat. The
change in entropy is the heat added divided by the ⎛T ⎞
ΔS = mc ln⎜⎜ 2 ⎟⎟ (non-isothermal process)
temperature at which the transfer took place. ⎝ T1 ⎠

If the heat transfer Q takes place at a single temperature, the where m is mass of the system and c is the specific heat
change in entropy is simply: capacity. Note that if T2 > T1, ΔS > 0; if T2 < T1, ΔS < 0.

If T1 and T2 are not very different (differ by a few %), the

Q
ΔS = (isothermal process) following approximation holds:
T
Q Q
ΔS ≈ =
(T1 + T2 ) / 2 Tav

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where Tav denotes the average of T1 and T2. 4

Entropy: time’s arrow

The Second Law of Thermodynamics Consider two gases A and B in two chambers, separated by a
movable partition. Suppose you open the partition and let the
The entropy of a closed system is constant for reversible
two gases mix. In this process, both energy and momentum
processes and increases for irreversible processes. Entropy are conserved. However, the entropy is increased The
never decreases (for a closed system). direction of time is the direction of increasing entropy.
A B
For a closed system, ΔS ≥ 0 Both gases are at the
same temperature and
the chambers are
thermally isolated from
the surroundings.
Partition

Reversible and irreversible processes

In an irreversible process, the entropy of a closed system
increases.
5 In a reversible process, the entropy stays the same. 6

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 Example 1: Reversible or not? Example 1: Reversible or not? (cont’d)
⎛ T2 ⎞
Question: You have two styrofoam containers of water. Each Use the change in entropy equation, ΔS = mc ln⎜ ⎟⎟
⎜
holds 1 kg of water. In one the water temperature is 17°C, ⎝ T1 ⎠
while in the other it is 37°C. The colder water is then poured For the cooler water,
into the warmer water, and the system is allowed to come to J ⎛ (27 + 273)K ⎞
ΔS 1 = (1kg )(4186 ) ln⎜ ⎟ = +141.9J/K
kg o C ⎜⎝ (17 + 273) K ⎟⎠
equilibrium. Find the change in entropy of the system. Hence
determine if this process reversible or irreversible.
Solution: For the warmer water,

The container of water will not spontaneously separate into J ⎛ (27 + 273)K ⎞
ΔS 2 = (1kg )(4186 ) ln⎜ ⎟ = −137.3J/K
two parts that differ in temperature by 20°, so this process kg o C ⎜⎝ (37 + 273) K ⎟⎠
must be irreversible. Let’s calculate the change in entropy.
ΔS = ΔS1 + ΔS2 = +4.6 J/K > 0 ⇒ Irreversible.

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Example 1: Reversible or not? (cont’d)

Alternative Method A Heat Engine
The change in temperature for either the cooler or warmer water A heat engine is a device that uses heat to do work. A gasoline-
is only a few percent. To see this, we calculate the final powered car engine is a good example.
temperature, Tf, by using ΣQ = 0: To be useful, the engine must go through cycles, with work
cm17C(Tf – 17 oC) + cm37C(Tf – 37 oC) = 0 being done every cycle. Two temperatures are required. The
⇒ Tf = (17 + 37) oC/2 = 27 oC higher temperature causes the system to expand and do work,
and the lower temperature re-sets the engine so another cycle
This shows that ΔT = +10 K (-10 K) for the cooler (warmer) water. can begin. In a full cycle, three things happen:
Since 10K is only a few % of Ti or Tf in K, we can use the
approximation, ΔS = Q/Tav. First find Q: Heat |QH| is added at a relatively high temperature TH.
Some of this energy is used to do work |W|.
Q = mcΔT = (1 kg)[4186 J/(kgoC)](±10 oC)= ±41860 J The rest is removed as heat |QL| at a lower e.g. Atmosphere
temperature TL. |QL|
For the cooler water, the average temperature, Tcool = (17 +
Heat
27)/2 oC = 22°C = 295 K. For the warmer water, the average For the cycle: |QH| = |W| +|QL| engine
|W|
temperature, Twarm = (37 + 27)/2 oC =32 °C = 305 K.
|QH|
Qcool Qwarm +41860 J −41860 J (In one cycle, 0 = ΔEint = |QH| – |W| – |QL|) e.g. Combustion
ΔS = + = + = +4.65 J/K 9 Chamber 10
Tcool Twarm 295 K 305 K

Efficiency Carnot’s Principle

Sadi Carnot (1796 – 1832), a French engineer, discovered an
In general, efficiency is the ratio of the work done divided by interesting result that is a consequence of the Second Law of
the heat needed to do the work. Thermodynamics.
Even in an ideal situation, the efficiency of a heat engine is
W QH − QL Q
e= = = 1− L limited by the temperatures between which the engine
QH QH QH operates. 100% efficiency is not possible, and most engines,
even in ideal cases, achieve much less than 100% efficiency.
The net work done in one cycle Q Q Q T
ΔS = H − L ≥ 0 ⇒ L ≤ L
is the area enclosed by the cycle TH TL QH TH
T
on the P-V diagram. Maximum (Carnot) efficiency: eC = 1 − L
TH
QL TL
Carnot Principle for the maximum efficiency: =
11 QH TH 12

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 Refrigerators or Heat Pumps -- Heat Example 2: A Heat Pump

Engines Running Backwards Question: If you heat your home using electric heat, 1000 J
of electrical energy can be transformed into 1000 J of heat.
(a) e.g. Atmosphere
Refrigerators and air conditioners An alternative way of heating is to use a heat pump, which
are heat engines that run backward. |QL| extracts heat from a lower-temperature region (outside the
Work is done on the system to pump Heat
|W| house) and transfers it to the higher-temperature region
some heat QL into the system from a engine
(inside the house). Let's say the work done in the process
low temperature region TL. An |QH| is 1000 J, and the temperatures are TH = 27°C = 300 K and
amount of heat QH = QL + W is then e.g. Combustion
removed from the system at a higher TL = -13 °C = 260 K. What is the maximum amount of heat
Chamber that can be transferred into the house?
temperature TH.
(b) e.g. Cold Chamber Cold outdoor
(a) Represents a heat engine e.g. |QL| |QL|
the cylinder in a car engine while (b)
Refri- Heat
represents a refrigerator or a heat gerator |W| Pump |W| |QH| = |QL| + |W|
pump. In both cases, |QH| = |QL| + |W|.
Can you run a refrigerator such that |QH| |QH|
|QL| = |QH| + |W|? e.g. Vent at ambience
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Warm indoor 14

Example 2: A Heat Pump (cont’d)

Solution:
The maximum efficiency is determined by the Carnot principle:
QL TL T
= ⇒ QL = L × QH
QH TH TH
Using this in the energy equation gives:
TL
QH = QL + W = × QH + W ⇒ THQH = TLQH + THW
TH
For our numerical example this gives:
THW (300 K)(1000 J)
QH = = = 7500 J
TH − TL 300 K − 260 K
This shows that heat pumps running at the Carnot efficiency
can convert 1000 J of work to 7500 J of heat. This capability
makes heat pumps an attractive alternative to electric or hot15
water heating systems.