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Entropy
  • 00:05Overview
  • 01:17Principles Behind a Cooling Experiment
  • 03:33The Cooling Experiment
  • 04:29Calculation and Results
  • 06:06Applications
  • 07:07Summary

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Overview

资料来源: Ketron 米切尔韦恩博士, Asantha 库雷博士,物理系 & 天文,物理科学学院,加利福尼亚大学,加利福尼亚州欧文市

热力学第二定律是自然界的基本定律。它表示系统的熵总是增加随着时间的推移,或保持恒定在理想情况下,当系统处于稳定状态或正在进行”可逆过程”。如果系统正在经历一个不可逆转的过程,系统的熵总是会增加。这意味着出发,熵的变化总是大于或等于零。系统的熵是微观配置系统可以达到的数目。例如,与已知的体积、 压力和温度的容器中的气体可以有极大可能的配置数的单个气体分子。如果打开的容器,气体分子逃脱和配置数目的增加显著,基本上接近无穷大。当容器被打开时,熵是说增加。因此,熵可以看作”障碍”的一种系统的一项措施。

Principles

Procedure

1.安装程序。 获得加热元件和站、 温度计、 秒表、 几个纸巾,水和一个大烧杯。 充满的足够的水的烧杯,使样品,不会太迅速降温 (即至少 500 毫升)。 装满水的烧杯放下面加热元件的立场,并将它打开。 一旦把烧杯中的水沸腾,插入温度计和关闭加热元件。 小心拆卸烧杯从加热站,并将它放在桌子上,在纸巾上。这些将充当从表绝缘。 …

Results

Representative results for 680 mL of water are shown in Table 1. The cooling constant k was found using the data points in the table and solving Equation 7. After 35 min, T(35) = 50.6. The initial temperature was 100 °C, and data collection ceased at 28.5 °C. Using these variables gives the following equation to obtain k:

50.6 = 28.5 + (100 – 28.5) e-k 35. (Equation 8)

Solving for k gives a value k = 0.034. The curve with this cooling constant is shown as a dashed gray line in Figure 1, along with the data points from the experiment. The functional form of Equation 6 matches the experimental results very closely.

As the water cools, the entropy decreases, since the number of states available to the water molecules decreases. The entropy of the ambient air in the room increases because the water beaker transfers heat to the air molecules surrounding it; the overall entropy of the water + air system increases. The number of states that the now-hotter air molecules can occupy is much higher than before the hot water was introduced to the room.

In differential form, the heat dQ added to or removed from the water can be calculated using the relationship between mass, specific heat c, and temperature change:

dQ = mc dT, (Equation 9)

where c is known to be 4.18 J/(gK) for water. The change in entropy of the water is then:

ΔSwater = Equation 1

= mwater cwater ln(Tfinal / Tinitial). (Equation 10)

Using the conversion to Kelvin as K = °C + 273.15, the change in the entropy of the water is calculated as:

ΔSwater = 680 g * 4.18 J/(g K) * ln[(28.5 + 273.15)/(100 + 273.15)]

= -604 J/K.

The ambient air temperature is constant at 20.4 °C, so this is an isothermal process. The entropy change of the air is then:

ΔSairEquation 2,

where Q is the heat released by the water, which is given by Equation 9. The change in entropy of the air is then calculated as:

ΔSair = Equation 3

= 3337 J/K.

The total change in the entropy of the water + air system, ΔStot, is the sum of the individual changes in entropy of the water and ambient air:

ΔStot = ΔSwater +ΔSair (Equation 11)

= -604 J/k + 3337 J/K

= 2733 J/K.

Table 1. Temperatures recorded during the experiment.

Time (min s) Water Temperature (°C)
0 0 99.6
1 10 97.1
1 50 94.2
2 30 91.8
3 22 89
4 05 87.2
5 08 82.7
6 05 82.4
8 25 78
9 15 76.5
10 15 74.6
11 38 72.7
12 58 70.7
13 58 69.2
15 15 67.7
16 55 65.8
18 38 64
20 25 62.3
24 02 58.8
25 45 57.3
34 45 50.6
40 50 47.4
44 30 45.9
49 59 43.6
53 42 42.4
60 01 40.2
64 20 39.5
76 37 37
103 50 32.1
116 41 30.3
122 46 29.6
134 11 28.5

Figure 1
Figure 1. Plot of temperature versus time. The blue dots indicate the experimental data, and the dashed line represents theoretical data based on Newton's law of cooling.

Applications and Summary

A pair of headphones kept in a bag always tends to become knotted-this is an increase in entropy caused by carrying the bag around. It is necessary to do work on the headphones to un-knot them and decrease the entropy (this can be thought of as a “reversible process”). The most efficient heat engine cycle allowed by physical laws is the Carnot cycle. The second law states that not all heat supplied to a heat engine can be used to do work. The Carnot efficiency sets the limiting value on the fraction of heat that can be used. The cycle consists of two isothermal processes followed by two adiabatic processes. A refrigerator, which is essentially just a heat pump, is also a classic example of the second law. Refrigerators move heat from one location at a lower temperature (the “source”) to another location at a higher temperature (the “heat sink”) using mechanical work. According to the second law, heat cannot spontaneously flow from a colder location to a hotter one; thus, work (energy) is required for refrigeration.

Newton’s law of cooling was demonstrated by a beaker full of water at 100 °C cooling down to room temperature, which led to an increase in the entropy of the water-air system. By measuring the temperature of the water as a function of time over a period of 135 min, it was possible to confirm that the cooling of the water was exponential in form. The cooling constant of the water sample was found by solving the cooling equation using collected data.

Transcript

Entropy is a fundamental thermodynamic principle used to describe heat transfer in a system.

The term Entropy is often considered a measure of the “disorder” of a system and the second law of thermodynamics states that if the system is undergoing an irreversible process, then the entropy of the system will always increase.

Think about gas trapped in a container with known volume, pressure and temperature. The gas molecules can have an enormous number of possible configurations. If the container is opened, the gas molecules escape and the number of configurations increases dramatically, essentially approaching infinity. Therefore S, which denotes entropy, definitely increased after opening the container. Thus, ΔS, or the change in entropy,is greater than zero.

Similarly, entropy also increases when hot water is left at room temperature and allowed to cool down. In this video, we will illustrate how to measure the change in entropy of a system during such cooling experiments.

Before learning how to do the experiment and gather data, let’s learn some laws and equations that allow us to calculate rate of temperature change and increase in entropy during cooling experiments.

Newton’s Law of Cooling states that the rate of temperature change of an object is proportional to the difference between its own temperature and the temperature of the surroundings. Using calculus, this relationship can be converted into this equation, where lower case t represents time, Ts denotes temperature of the surroundings, T0 is the initial temperature, and k is a constant that depends on the characteristics of the object and its surroundings.

Using this equation, one can calculate the temperature of a cooling system at any time if all the other variables are known. This equation also shows that temperature is an exponential function of time. Thus, when a hot object, like a glass of hot water, is placed in a cooler environment, its temperature will decrease at an exponential rate until it reaches the temperature of the surroundings.

Now, let’s see how to calculate the change in entropy, or ΔS. Let’s rewind to when the water was hot.

When talking about entropy, we must first define the system. Here, the system is the glass of water plus the air in the room. So the change in entropy of the system, or ΔStotal is a sum of the change in entropies of these individual components. Mathematically, the change in entropy is defined as heat gained or lost, denoted by Q, divided by the temperature.

In this scenario, we know that heat leaves water, thus ΔS for water decreases. On the contrary, the surrounding air gains heat. Therefore, ΔSair increases. From the second law of the thermodynamics, we know the change in entropy of the total system must be positive.

Now let’s see how to conduct an experiment to test these theoretical predictions of Newton’s Law of Cooling and the second law of thermodynamics.

To begin, fill a large beaker with between 500 mL to one L of water. Place the beaker on a hot plate, and heat the water to boiling. Once the water boils, turn off the heating element.

Then, carefully remove the beaker from the hot plate, and place it on the table on top of paper towels. The paper towels will act as insulation between the water and the cool table. Measure the temperature of the water using the thermometer.

Start the stopwatch, and record the temperature of the water every minute for the first 20 minutes.

For the next 20 minutes, record the temperature every 5 minutes.

Stop taking measurements when the water has come close to room temperature. Then, plot the data points in a graph of temperature of the water versus time.

Now let’s analyze the data obtained. The initial temperature of the water was 100 degrees, at 35 minutes the temperature dropped to 50.6, and the surrounding temperature was 28.5 degrees. Plug in these values into Newton’s Law of Cooling, and solve for the cooling constant k.

Now using the calculated value for k, plot the equation as a continuous function. If we lay our measured data points on this chart, we can see that the theoretical and experimental functions follow an almost identical path.

Now let’s talk about entropy. As we know, the total change in entropy, or delta S, is equal to the entropy change for the water plus the room.

The change in entropy equals Q, or the amount of heat transferred from the hot water to the air, divided by T, so the change in entropy can be calculated if Q is known.

Q can be calculated using the relationship between mass, m, specific heat, c, and the change in temperature in Kelvin, delta T. Using the values for water the amount of heat released by the water, Q can be calculated and used to solve for delta S.

Thus, the experimental data shows that the entropy of the total system has increased since heat was transferred from the water to the air molecules in the room. This validates the second law of thermodynamics.

Entropy and the Second Law of Thermodynamics describe a wide range of occurrences in nature and engineering.

A refrigerator is essentially a heat pump, and removes heat from one location at a lower temperature, the heat source, and transfers it to another location, the heat sink, at a higher temperature.

According to the second law, heat cannot spontaneously flow from a colder location to a hotter one. Thus, work, or energy, is required for refrigeration.

A campfire is another example of entropy changes in real life. The solid wood used as fuel burns and turns into a disordered pile of ash. In addition, water molecules and carbon dioxide gas are released.

The atoms in the vapors spread out in an expanding cloud, with infinite disordered arrangements. Thus, the entropy change from burning wood is always positive.

You’ve just watched JoVE’s introduction to entropy and the second law of thermodynamics. You should now understand the basic concept of entropy, Newton’s Law of Cooling, and examples of entropy changes in everyday life. Thanks for watching!

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JoVE Science Education Database. JoVE Science Education. Entropy. JoVE, Cambridge, MA, (2023).