Systems, States and Processes | Chemistry Optional Notes for UPSC PDF Download

Forms of Energy

• The forms of energy include thermal energy, radiant energy, electrical energy, nuclear energy, and chemical energy (Figure  12.1.1). Thermal energy results from atomic and molecular motion; the faster the motion, the greater the thermal energy. The temperature of an object is a measure of its thermal energy content. Radiant energy is the energy carried by light, microwaves, and radio waves. Objects left in bright sunshine or exposed to microwaves become warm because much of the radiant energy they absorb is converted to thermal energy.
• Electrical energy results from the flow of electrically charged particles. When the ground and a cloud develop a separation of charge, for example, the resulting flow of electrons from one to the other produces lightning, a natural form of electrical energy. Nuclear energy is stored in the nucleus of an atom, and chemical energy is stored within a chemical compound because of a particular arrangement of atoms.

Figure 12.1.1: Forms of Energy. (a) Thermal energy results from atomic and molecular motion; molten steel at 2,000°C has high thermal energy. (b) Radiant energy (e.g., from the sun) is the energy in light, microwaves, and radio waves. (c) Lightning is an example of electrical energy, which is due to the flow of electrically charged particles. (d) Nuclear energy is released when particles in the nucleus of the atom are rearranged. (e) Chemical energy results from the particular arrangement of atoms in a chemical compound; the heat and light produced in this reaction are due to energy released during the breaking and reforming of chemical bonds. 

• Electrical energy, nuclear energy, and chemical energy are different forms of potential energy (PE), which is energy stored in an object because of the relative positions or orientations of its components. A brick lying on the windowsill of a 10th-floor office has a great deal of potential energy, but until its position changes by falling, the energy is contained. In contrast, kinetic energy (KE) is energy due to the motion of an object. 
• When the brick falls, its potential energy is transformed to kinetic energy, which is then transferred to the object on the ground that it strikes. The electrostatic attraction between oppositely charged particles is a form of potential energy, which is converted to kinetic energy when the charged particles move toward each other.
• Energy can be converted from one form to another (Figure  12.1.2) or, as we saw with the brick, transferred from one object to another. For example, when you climb a ladder to a high diving board, your body uses chemical energy produced by the combustion of organic molecules. As you climb, the chemical energy is converted to mechanical work to overcome the force of gravity. When you stand on the end of the diving board, your potential energy is greater than it was before you climbed the ladder: the greater the distance from the water, the greater the potential energy.
• When you then dive into the water, your potential energy is converted to kinetic energy as you fall, and when you hit the surface, some of that energy is transferred to the water, causing it to splash into the air. Chemical energy can also be converted to radiant energy; one common example is the light emitted by fireflies, which is produced from a chemical reaction.

Figure 12.1.2: Interconversion of Forms of Energy. When a swimmer steps off the platform to dive into the water, potential energy is converted to kinetic energy. As the swimmer climbs back up to the top of the diving platform, chemical energy is converted to mechanical work.

• Although energy can be converted from one form to another, the total amount of energy in the universe remains constant. This is known as the law of conservation of energy: Energy cannot be created or destroyed.

Kinetic and Potential Energy

The kinetic energy of an object is related to its mass  m and velocity  v:
KE = 1/2 mv² (12.1.1)

For example, the kinetic energy of a 1360 kg (approximately 3000 lb) automobile traveling at a velocity of 26.8 m/s (approximately 60 mi/h) is
 (12.1.2)

Because all forms of energy can be interconverted, energy in any form can be expressed using the same units as kinetic energy. The SI unit of energy, the joule (J), is named after the British physicist James Joule (1818–1889), an early worker in the field of energy, is defined as 1 kilogram·meter²/second² (kg·m²/s²). Because a joule is such a small quantity of energy, chemists usually express energy in kilojoules (1 kJ = 10³ J). For example, the kinetic energy of the 1360 kg car traveling at 26.8 m/s is 4.88 × 10⁵ J or 4.88 × 10² kJ. It is important to remember that the units of energy are the same regardless of the form of energy, whether thermal, radiant, chemical, or any other form. Because heat and work result in changes in energy, their units must also be the same.

To demonstrate, let’s calculate the potential energy of the same 1360 kg automobile if it were parked on the top level of a parking garage 36.6 m (120 ft) high. Its potential energy is equivalent to the amount of work required to raise the vehicle from street level to the top level of the parking garage, which is
w = Fd. (12.1.3)
The force (F) exerted by gravity on any object is equal to its mass (m, in this case, 1360 kg) times the acceleration (a) due to gravity (g, 9.81 m/s² at Earth’s surface). The distance (d) is the height (h) above street level (in this case, 36.6 m). Thus the potential energy of the car is as follows:
 (12.1.4)
The units of potential energy are the same as the units of kinetic energy. Notice that in this case the potential energy of the stationary automobile at the top of a 36.6 m high parking garage is the same as its kinetic energy at 60 mi/h.

If the vehicle fell from the roof of the parking garage, its potential energy would be converted to kinetic energy, and it is reasonable to infer that the vehicle would be traveling at 60 mi/h just before it hit the ground, neglecting air resistance. After the car hit the ground, its potential and kinetic energy would both be zero.

Potential energy is usually defined relative to an arbitrary standard position (in this case, the street was assigned an elevation of zero). As a result, we usually calculate only differences in potential energy: in this case, the difference between the potential energy of the car on the top level of the parking garage and the potential energy of the same car on the street at the base of the garage.

Units of Energy

• The units of energy are the same for all forms of energy. Energy can also be expressed in the non-SI units of calories (cal), where 1 cal was originally defined as the amount of energy needed to raise the temperature of exactly 1 g of water from 14.5 °C to 15.5 °C.We specify the exact temperatures because the amount of energy needed to raise the temperature of 1 g of water 1 °C varies slightly with elevation. 
• To three significant figures, however, this amount is 1.00 cal over the temperature range 0 °C–100 °C. The name is derived from the Latin calor, meaning “heat.” Although energy may be expressed as either calories or joules, calories were defined in terms of heat, whereas joules were defined in terms of motion. Because calories and joules are both units of energy, however, the calorie is now defined in terms of the joule:
  1cal ≡ 4.184J (exactly) (12.1.5)
  1 J = 0.2390 cal (12.1.6)
• In this text, we will use the SI units—joules (J) and kilojoules (kJ)—exclusively, except when we deal with nutritional information.

Solved Example

Example: (a) If the mass of a baseball is 149 g, what is the kinetic energy of a fastball clocked at 100 mi/h?
(b) A batter hits a pop fly, and the baseball (with a mass of 149 g) reaches an altitude of 250 ft. If we assume that the ball was 3 ft above home plate when hit by the batter, what is the increase in its potential energy?
Given: mass and velocity or height
Asked for: kinetic and potential energy
Strategy: Use Equation 12.1.1 to calculate the kinetic energy and Equation 12.1.4 to calculate the potential energy, as appropriate.
Ans: (a) The kinetic energy of an object is given by 1/2mv² In this case, we know both the mass and the velocity, but we must convert the velocity to SI units:

The kinetic energy of the baseball is therefore (via Equation  12.1.1)

(b) 

Systems and Surroundings

• To study the flow of energy during a chemical reaction, we need to distinguish between a system, the small, well-defined part of the universe in which we are interested (such as a chemical reaction), and its surroundings, the rest of the universe, including the container in which the reaction is carried out (Figure 12.1.3). In the discussion that follows, the mixture of chemical substances that undergoes a reaction is always the system, and the flow of heat can be from the system to the surroundings or vice versa.

Figure 12.1.3: A System and Its Surroundings. The system is that part of the universe we are interested in studying, such as a chemical reaction inside a flask. The surroundings are the rest of the universe, including the container in which the reaction is carried out.

• Three kinds of systems are important in chemistry. An open system can exchange both matter and energy with its surroundings. A pot of boiling water is an open system because a burner supplies energy in the form of heat, and matter in the form of water vapor is lost as the water boils. A closed system can exchange energy but not matter with its surroundings. The sealed pouch of a ready-made dinner that is dropped into a pot of boiling water is a closed system because thermal energy is transferred to the system from the boiling water but no matter is exchanged (unless the pouch leaks, in which case it is no longer a closed system). An isolated system exchanges neither energy nor matter with the surroundings.
• Energy is always exchanged between a system and its surroundings, although this process may take place very slowly. A truly isolated system does not actually exist. An insulated thermos containing hot coffee approximates an isolated system, but eventually the coffee cools as heat is transferred to the surroundings. In all cases, the amount of heat lost by a system is equal to the amount of heat gained by its surroundings and vice versa. That is, the total energy of a system plus its surroundings is constant, which must be true if energy is conserved.
• The state of a system is a complete description of a system at a given time, including its temperature and pressure, the amount of matter it contains, its chemical composition, and the physical state of the matter. A state function is a property of a system whose magnitude depends on only the present state of the system, not its previous history. Temperature, pressure, volume, and potential energy are all state functions. The temperature of an oven, for example, is independent of however many steps it may have taken for it to reach that temperature.
• Similarly, the pressure in a tire is independent of how often air is pumped into the tire for it to reach that pressure, as is the final volume of air in the tire. Heat and work, on the other hand, are not state functions because they are path dependent. For example, a car sitting on the top level of a parking garage has the same potential energy whether it was lifted by a crane, set there by a helicopter, driven up, or pushed up by a group of students (Figure  12.1.4).
• The amount of work expended to get it there, however, can differ greatly depending on the path chosen. If the students decided to carry the car to the top of the ramp, they would perform a great deal more work than if they simply pushed the car up the ramp (unless, of course, they neglected to release the parking brake, in which case the work expended would increase substantially!). The potential energy of the car is the same, however, no matter which path they choose.

Figure  12.1.4: Elevation as an Example of a State Function. The change in elevation between state 1 (at the bottom of the parking garage) and state 2 (at the top level of the parking garage) is the same for both paths A and B; it does not depend on which path is taken from the bottom to the top. In contrast, the distance traveled and the work needed to reach the top do depend on which path is taken. Elevation is a state function, but distance and work are not state functions. 

Summary

• Thermochemistry is a branch of chemistry that qualitatively and quantitatively describes the energy changes that occur during chemical reactions. Energy is the capacity to do work. Mechanical work is the amount of energy required to move an object a given distance when opposed by a force. Thermal energy is due to the random motions of atoms, molecules, or ions in a substance. The temperature of an object is a measure of the amount of thermal energy it contains. Heat (q) is the transfer of thermal energy from a hotter object to a cooler one.
• Energy can take many forms; most are different varieties of potential energy (PE), energy caused by the relative position or orientation of an object. Kinetic energy (KE) is the energy an object possesses due to its motion. Energy can be converted from one form to another, but the law of conservation of energy states that energy can be neither created nor destroyed. The most common units of energy are the joule (J), defined as 1 (kg·m²)/s², and the calorie, defined as the amount of energy needed to raise the temperature of 1 g of water by 1°C (1 cal = 4.184 J).