The Nature of Spontaneous Processes | Chemistry Optional Notes for UPSC PDF Download

Spontaneous and Nonspontaneous Processes

• Processes have a natural tendency to occur in one direction under a given set of conditions. Water will naturally flow downhill, but uphill flow requires outside intervention such as the use of a pump. A spontaneous process is one that occurs naturally under certain conditions. A nonspontaneous process, on the other hand, will not take place unless it is “driven” by the continual input of energy from an external source. A process that is spontaneous in one direction under a particular set of conditions is nonspontaneous in the reverse direction. At room temperature and typical atmospheric pressure, for example, ice will spontaneously melt, but water will not spontaneously freeze.
• The spontaneity of a process is not correlated to the speed of the process. A spontaneous change may be so rapid that it is essentially instantaneous or so slow that it cannot be observed over any practical period of time. To illustrate this concept, consider the decay of radioactive isotopes, a topic more thoroughly treated in the chapter on nuclear chemistry. Radioactive decay is by definition a spontaneous process in which the nuclei of unstable isotopes emit radiation as they are converted to more stable nuclei.
• All the decay processes occur spontaneously, but the rates at which different isotopes decay vary widely. Technetium-99m is a popular radioisotope for medical imaging studies that undergoes relatively rapid decay and exhibits a half-life of about six hours. Uranium-238 is the most abundant isotope of uranium, and its decay occurs much more slowly, exhibiting a half-life of more than four billion years (Figure  13.1.1).

Figure  13.1.1: Both U-238 and Tc-99m undergo spontaneous radioactive decay, but at drastically different rates. Over one week, essentially all of a Tc-99m sample and none of a U-238 sample will have decayed.

• Two curves are shown to represent U-238 and Tc-99m respectively. The vertical axes represents the percentage of isotope remaining and the horizontal axes is the time that has elapsed in days. As another example, consider the conversion of diamond into graphite (Figure  13.1.2).
  C(s,diamond) ⟶ C(s,graphite) (13.1.1)
• The phase diagram for carbon indicates that graphite is the stable form of this element under ambient atmospheric pressure, while diamond is the stable allotrope at very high pressures, such as those present during its geologic formation. Thermodynamic calculations of the sort described in the last section of this chapter indicate that the conversion of diamond to graphite at ambient pressure occurs spontaneously, yet diamonds are observed to exist, and persist, under these conditions.
• Though the process is spontaneous under typical ambient conditions, its rate is extremely slow, and so for all practical purposes diamonds are indeed “forever.” Situations such as these emphasize the important distinction between the thermodynamic and the kinetic aspects of a process. In this particular case, diamonds are said to be thermodynamically unstable but kinetically stable under ambient conditions.

Figure 13.1.2: The conversion of carbon from the diamond allotrope to the graphite allotrope is spontaneous at ambient pressure, but its rate is immeasurably slow at low to moderate temperatures. This process is known as graphitization, and its rate can be increased to easily measurable values at temperatures in the 1000–2000 K range. 

Comparison of diamond and graphite shown in its physical form as well as its molecular arrangement respectively.

Dispersal of Matter and Energy

• As we extend our discussion of thermodynamic concepts toward the objective of predicting spontaneity, consider now an isolated system consisting of two flasks connected with a closed valve. Initially there is an ideal gas on the left and a vacuum on the right (Figure 13.1.3). When the valve is opened, the gas spontaneously expands to fill both flasks. Recalling the definition of pressure-volume work from the chapter on thermochemistry, note that no work has been done because the pressure in a vacuum is zero.
  w = −PΔV = 0 (13.1.2)
  (P = 0 in a vaccum) (13.1.3)
• Note as well that since the system is isolated, no heat has been exchanged with the surroundings (q = 0). The first law of thermodynamics confirms that there has been no change in the system’s internal energy as a result of this process.
  ΔU = q + w  (First Law of Thermodynamics)
   = 0 + 0 = 0 (13.1.4)
• The spontaneity of this process is therefore not a consequence of any change in energy that accompanies the process. Instead, the movement of the gas appears to be related to the greater, more uniform dispersal of matter that results when the gas is allowed to expand. Initially, the system was comprised of one flask containing matter and another flask containing nothing. After the spontaneous process took place, the matter was distributed both more widely (occupying twice its original volume) and more uniformly (present in equal amounts in each flask).

Figure  13.1.3: An isolated system consists of an ideal gas in one flask that is connected by a closed valve to a second flask containing a vacuum. Once the valve is opened, the gas spontaneously becomes evenly distributed between the flasks.

• When the valve is closed, all of the gas molecules accumlating only in one side of the flask. The diagram with the open valve shows gas being equally distributed among the two flasks. The dispersion of the gas is labeled as spontaneous while the reverse is labeled as non spontaneous.
• Now consider two objects at different temperatures: object X at temperature T_X and object Y at temperature T_Y, with T_X > T_Y (Figure  13.1.4). When these objects come into contact, heat spontaneously flows from the hotter object (X) to the colder one (Y). This corresponds to a loss of thermal energy by X and a gain of thermal energy by Y.
  qX < 0 and qY = −qX > 0 (13.1.5)
• From the perspective of this two-object system, there was no net gain or loss of thermal energy, rather the available thermal energy was redistributed among the two objects. This spontaneous process resulted in a more uniform dispersal of energy.

Figure  13.1.4: When two objects at different temperatures come in contact, heat spontaneously flows from the hotter to the colder object.

• Two separated blocks. One is labeled X and the other labeled Y. The diagram next to it shows the two blocks in contact with one another.
• As illustrated by the two processes described, an important factor in determining the spontaneity of a process is the extent to which it changes the dispersal or distribution of matter and/or energy. In each case, a spontaneous process took place that resulted in a more uniform distribution of matter or energy.

Solved Examples

Example 1: Describe how matter and energy are redistributed when the following spontaneous processes take place:
(a) A solid sublimes.
(b) A gas condenses.
(c) A drop of food coloring added to a glass of water forms a solution with uniform color.
Ans: 

This figure has three photos labeled, “a,” “b,” and “c.” Photo a shows a glass with dry ice in water. There is a thick vapor coming from the top of the glass. Photo b shows water forming outside of a glass containing cold beverage. Photo c shows a sealed container that holds a red liquid.

• Sublimation is the conversion of a solid (relatively high density) to a gas (much lesser density). This process yields a much greater dispersal of matter, since the molecules will occupy a much greater volume after the solid-to-gas transition. However, an input of energy from the surroundings ss required for the molecules to leave the solid phase and enter the gas phase. 
• Condensation is the conversion of a gas (relatively low density) to a liquid (much greater density). This process yields a much lesser dispersal of matter, since the molecules will occupy a much lesser volume after the gas-to-liquid transition. As the gas molecules move together to form the droplets of liquid, they form intermolecular forces and thus release energy to the surroundings.
• The process in question is dilution. The food dye molecules initially occupy a much smaller volume (the drop of dye solution) than they occupy once the process is complete (in the full glass of water). The process therefore entails a greater dispersal of matter. The process may also yield a more uniform dispersal of matter, since the initial state of the system involves two regions of different dye concentrations (high in the drop, zero in the water), and the final state of the system contains a single dye concentration throughout. This process can occur with out a change in energy because the molecules have kinetic energy relative to the temperature of the water, and so will be constantly in motion.

Example 2: Describe how matter and energy are redistributed when you empty a canister of compressed air into a room.
Ans: This process entails both a greater and more uniform dispersal of matter as the compressed air in the canister is permitted to expand into the lower-pressure air of the room. The process also requires an input of energy to disrupt the intermolecular forces between the closely-spaced gas molecules that are originally compressed into the container. If you were to touch the nozzle of the canister, you would notice that it is cold because the exiting molecules are taking energy away from their surroundings, and the canister is part of the surroundings.