Fluorescent tubes operate at very low pressure; roughly 1/1000th of an atmosphere. They do not explode when broken; they implode. The atmospheric pressure surrounding the tube crushes it as soon as it begins to crack. The tube shape of a typical fluorescent tube is chosen because it can withstand the enormous compressive forces of the atmosphere better than most other shapes.
For an atom to determine that it cannot make a particular transition (that its electron cannot move from one particular orbital to another), it must first “test the water”. The atom effectively tries to make particular transition but finds that this transition is not possible. However, if the atom experiences a collision during the test period, the atom may “accidentally” undergo the forbidden transition. It is as though the atom was prevented from canceling the experiment.
The lamp first heats the filaments in its electrodes red hot so that they begin to emit electrons and then tries to start a discharge across the lamp. If there are not enough electrons leaving the electrodes to sustain a steady discharge, the lamp will blink briefly but will not stay on. The lamp will try again; first heating its filaments and then trying to start the discharge. The lamp may blink several times before the discharge becomes strong enough to keep the electrodes hot and sustain the discharge.
They absorb the light and light energy by transferring electrons from low energy valence levels to high-energy conduction levels. These electrons wander about inside the phosphors briefly, losing energy as heat, and then fall back down to empty valence levels. Since they have lost some of their energy to heat, the light that they emit has less energy than the light they absorbed. Incoming ultraviolet light is converted to outgoing visible light.
At low pressure, a mercury lamp emits mostly 254-nanometer ultraviolet light. That light is created when an electron in the mercury atom goes from its lowest excited orbital to its ground (normal) orbital. The other wavelengths of light emitted by the low-pressure lamp are weak and widely spaced in wavelength. An electron must sent into a very highly excited orbital in order to emit one of these other wavelengths. But at high pressure, mercury atoms have trouble sending their favorite 254 nanometer light out of the lamp. Whenever one of the atoms emits a particle of 254-nanometer light (moving its electron from the first excited orbital to the ground orbital), another nearby atom absorbs that particle of light (moving its electron from the ground orbital to the first excited orbital). As a result the 254-nanometer light cannot escape from the lamp; it becomes trapped in the mercury gas! Instead, the atoms begin to send their energy out of the lamp by concentrating on radiative transitions between highly excited orbitals and that lowest excited orbital. These wavelengths become more common in the light emission from the lamp as its pressure rises. But some radiative transitions that are forbidden at low pressure (that cannot occur because an electron is not able to move from one particular excited orbital to another particular excited orbital) become allowed at high pressure. Collisions break many of the rules that govern atomic behavior, allowing otherwise forbidden events to occur. In the case of the mercury lamp, collisions at high pressure permit the mercury atoms to emit wavelengths of light that they cannot emit a low pressure when collisions are rare.
A fluorescent lamp consists of a gas-filled glass tube with an electrode at each end. This lamp emits light when a current of electrons passes through it from one electrode to the other and excites mercury atoms in the tube’s vapor. The electrons are able to leave the electrodes because those electrodes are heated to high temperatures and an electric field, powered by the electric company, propels them through the tube. However, the light that the mercury atoms emit is actually in the ultraviolet, where it can’t be seen. To convert this ultraviolet light to visible light, the inside surface of the glass tube is coated with a fluorescent powder. When this fluorescent powder is exposed to ultraviolet light, it absorbs the light energy and reemits some of it as visible light, a process called “fluorescence.” The missing light energy is converted to thermal energy, making the tube slightly hot. By carefully selecting the fluorescent powders (called “phosphors”), the manufacturer of the light can tailor the light’s coloration. The most common phosphor mixtures these days are warm white, cool white, deluxe warm white, and deluxe cool white.
The only other significant component of the fluorescent lamp is its ballast. This device is needed to control the current flow through the tube. Gas discharges such as the one that occurs inside the lamp are notoriously unstable—they’re hard to start and, once they do start, tend to become too intense. To regulate the discharge, the ballast controls the amount of current flowing through the tube. In most older lamps, this control is done by an electromagnetic device called an inductor. An inductor opposes current changes and keeps a relatively constant current flowing through the tube (although that current does stop and reverse directions each time the power line current reverses directions — 120 times a second or 60 full cycles, over and back, in the United States). Some modern fluorescent lamps use electronic ballasts—sophisticated electronic controls that regulate current with the help of transistor-like components.
I’m not aware of any tendency to change colors as it begins to burn out, but many fluorescent bulbs are relatively blue in color. The phosphor coatings used to convert the mercury vapor’s ultraviolet emission into visible light don’t create pure white. Instead, they create a mixture of different colors that is a close approximation to white light. There are a number of different phosphor mixtures, each with its own characteristic spectrum of light: cool white, deluxe cool white, warm white, deluxe warm white, and others. The cool white bulbs are most energy efficient but emit relatively bluish light. This light gives the bulbs a cold, medicinal look. The warm white bulbs are less energy efficient, but more pleasant to the eye.
Some ultraviolet fluorescent tubes are simply the mercury discharge tubes (as in a normal fluorescent tube) but without any phosphor coating on the inside of the tube and with a quartz glass tube that transmits 254 nanometer light. In such a bulb, the 254-nanometer light emitted by mercury vapor in a discharge is emitted directly from the tube without being converted into visible light. A filter somewhere in the system absorbs the small amount of visible light emitted by a low-pressure mercury discharge. For the longer wavelength black light used in most applications, other gases that emit lots of 300-400 nanometer light are used. Again, these tubes have no phosphor coatings to convert the ultraviolet light into visible light. One other way to make longer wavelength black light is to use a mercury discharge but to coat the inside of the tube with a phosphor that fluoresces ultraviolet light between 300 and 400 nanometer.
Each atom has certain wavelengths of light that it is particularly capable of absorbing and emitting. For mercury, that special wavelength is about 254 nanometer (ultraviolet). For sodium, it is about 590 nanometer (orange-yellow). If you send a photon of the right 590 nanometer light at a sodium atom, there is a good chance that that atom will absorb it, hold it for a few billionths of a second, and then reemit it. The newly reemitted light will probably not be traveling in the same direction as before. Now if you have a dense gas of sodium vapor and send in your special photon of light, that photon will find itself bouncing from one sodium atom to another, like the metal ball in a huge pinball game. The photon will eventually emerge from the gas, but not before it has traveled a very long distance and spent a long time in the gas. It was “trapped” in the sodium vapor. This radiation trapping makes it hard for high-pressure gas discharges to emit their special wavelengths because those wavelengths of light become trapped in the gas.
Most “neon” lamps are mercury lamps with a colored phosphor coating on the inside. However the true neon lamp (that special red glow) is really neon gas glowing directly. Take a close look at an advertising lamp that contains a variety of colors. The mercury/phosphor ones will seem to emit light from their frosted glass walls. You are seeing the phosphors glowing. But the real neon lamp will emit light from its inside. The glass will be clear and you will see the glow originate in the gas itself.