Primordial Helium and the Big Bang Theory

Where did we come from? How did the universe begin? Humans have asked these questions for as long as we have been able to think. The search for answers provides an example of the scientific method.

In the 1940s the Russian-American physicist George Gamow hypothesized that our universe burst into being billions of years ago in a gigantic explosion, or Big Bang. In its earliest moments, the universe occupied a tiny volume and was unimaginably hot. This blistering fireball of radiation mixed with microscopic particles of matter gradually cooled enough for atoms to form. Under the influence of gravity, these atoms clumped together to make billions of galaxies including our own Milky Way Galaxy.

Gamow’s idea is interesting and highly provocative. It has been tested experimentally in a number of ways. First, measurements showed that the universe is expanding; that is, galaxies are all moving away from one another at high speeds. This fact is consistent with the universe’s explosive birth. By imagining the expansion running backward, like a movie in reverse, astronomers have deduced that the universe was born about 13 billion years ago. The second observation that supports Gamow’s hypothesis is the detection of cosmic background radiation. Over billions of years, the searingly hot universe has cooled down to a mere 3 K (or 2270°C)! At this temperature, most energy is in the microwave region. Because the Big Bang would have occurred simultaneously throughout the tiny volume of the forming universe, the radiation it generated should have filled the entire universe. Thus, the radiation should be the same in any direction that we observe. Indeed, the microwave signals recorded by astronomers are independent of direction.

A color photo of some distant galaxy, including the position of a quasar.

The third piece of evidence supporting Gamow’s hypothesis is the discovery of primordial helium. Scientists believe that helium and hydrogen (the lightest elements) were the first elements formed in the early stages of cosmic evolution. (The heavier elements, like carbon, nitrogen, and oxygen, are thought to have originated later via nuclear reactions involving hydrogen and helium in the center of stars.) If so, a diffuse gas of hydrogen and helium would have spread through the early universe before many of the galaxies formed. In 1995, astronomers analyzed ultraviolet light from a distant quasar (a strong source of light and radio signals that is thought to be an exploding galaxy at the edge of the universe) and found that some of the light was absorbed by helium atoms on the way to Earth. Because this particular quasar is more than 10 billion light-years away (a light-year is the distance traveled by light in a year), the light reaching Earth reveals events that took place 10 billion years ago. Why wasn’t the more abundant hydrogen detected? A hydrogen atom has only one electron, which is stripped by the light from a quasar in a process known as ionization. Ionized hydrogen atoms cannot absorb any of the quasar’s light. A helium atom, on the other hand, has two electrons. Radiation may strip a helium atom of one electron, but not always both. Singly ionized helium atoms can still absorb light and are therefore detectable.

Proponents of Gamow’s explanation rejoiced at the detection of helium in the far reaches of the universe. In recognition of all the supporting evidence, scientists now refer to Gamow’s hypothesis as the Big Bang theory.

The Importance of Units

Artist’s conception of the Martian Climate Orbiter.

In December 1998, NASA launched the 125-million dollar Mars Climate Orbiter, intended as the red planet’s first weather satellite. After a 416-million mi journey, the spacecraft was supposed to go into Mars’ orbit on September 23, 1999. Instead, it entered Mars’ atmosphere about 100 km (62 mi) lower than planned and was destroyed by heat. The mission controllers said the loss of the spacecraft was due to the failure to convert English measurement units into metric units in the navigation software.

Engineers at Lockheed Martin Corporation who built the spacecraft specified its thrust in pounds, which is an English unit. Scientists at NASA’s Jet Propulsion Laboratory, on the other hand, had assumed that thrust data they received were expressed in metric units, as newtons. Normally, pound is the unit for mass. Expressed as a unit for force, however, 1 lb is the force due to gravitational attraction on an object of that mass. To carry out the conversion between pound and newton, we start with 1 lb = 0.4536 kg and from Newton’s second law of motion,

force    = mass ˣ acceleration

= 0.4536 kg ˣ 9.81 m/s²

= 4.45 kg m/s²

= 4.45 N

because 1 newton (N) = 1 kg m/s². Therefore, instead of converting one pound of force to 4.45 N, the scientists treated it as 1 N. The considerably smaller engine thrust expressed in newtons resulted in a lower orbit and the ultimate destruction of the spacecraft. Commenting on the failure of the Mars mission, one scientist said: “This is going to be the cautionary tale that will be embedded into introduction to the metric system in elementary school, high school, and college science courses till the end of time.”

Distribution of Elements on Earth and in Living Systems

The majority of elements are naturally occurring. How are these elements distributed on Earth, and which are essential to living systems?

Earth’s crust extends from the surface to a depth of about 40 km (about 25 mi). Because of technical difficulties, scientists have not been able to study the inner portions of Earth as easily as the crust. Nevertheless, it is believed that there is a solid core consisting mostly of iron at the center of Earth. Surrounding the core is a layer called the mantle, which consists of hot fluid containing iron, carbon, silicon, and sulfur.

Of the 83 elements that are found in nature, 12 make up 99.7 percent of Earth’s crust by mass. They are, in decreasing order of natural abundance, oxygen (O), silicon (Si), aluminum (Al), iron (Fe), calcium (Ca), magnesium (Mg), sodium (Na), potassium (K), titanium (Ti), hydrogen (H), phosphorus (P), and manganese (Mn). In discussing the natural abundance of the elements, we should keep in mind that (1) the elements are not evenly distributed throughout Earth’s crust, and (2) most elements occur in combined forms. These facts provide the basis for most methods of obtaining pure elements from their compounds, as we will see in later chapters.

The accompanying table lists the essential elements in the human body. Of special interest are the trace elements, such as iron (Fe), copper (Cu), zinc (Zn), iodine (I), and cobalt (Co), which together make up about 0.1 percent of the body’s mass. These elements are necessary for biological functions such as growth, transport of oxygen for metabolism, and defense against disease. There is a delicate balance in the amounts of these elements in our bodies. Too much or too little over an extended period of time can lead to serious illness, retardation, or even death.

Structure of Earth’s interior.

(a) Natural abundance of the elements in percent by mass. For example, oxygen’s abundance is 45.5 percent. This means that in a 100-g sample of Earth’s crust there are, on the average, 45.5 g of the element oxygen. (b) Abundance of elements in the human body in percent by mass.

The Exploding Tire

Instant flat tire repair

It was supposed to be a routine job: Fix the flat tire on Harvey Smith’s car. The owner of Tom’s Garage, Tom Lee, gave the tire to Jerry to work on, while he went outside to pump gas. A few minutes later, Tom heard a loud bang. He rushed inside to find the tire blown to pieces, a wall collapsed, equipment damaged, and Jerry lying on the floor, unconscious and bleeding. Luckily Jerry’s injury was not serious. As he lay in the hospital recovering, the mystery of the exploding tire unfolded.

The tire had gone fl at when Harvey drove over a nail. Being a cautious driver, Harvey carried a can of instant tire repair in the car, so he was able to reinflate the tire and drive safely home. The can of tire repair Harvey used contained latex (natural rubber) dissolved in a liquid propellant, which is a mixture of propane (C₃H₈) and butane (C₄H₁₀). Propane and butane are gases under atmospheric conditions but exist as liquids under compression in the can. When the valve on the top of the can is pressed, it opens, releasing the pressure inside. The mixture boils, forming a latex foam which is propelled by the gases into the tire to seal the puncture while the gas reinflates the tire.

The pressure in a flat tire is approximately one atmosphere, or roughly 15 pounds per square inch (psi). Using the aerosol tire repair, Harvey reinflated his damaged tire to a pressure of 35 psi. This is called the gauge pressure, which is the pressure of the tire above the atmospheric pressure. Thus, the total pressure in the tire was actually (15 + 35) psi, or 50 psi. One problem with using natural gases like propane and butane as propellants is that they are highly flammable. In fact, these gases can react explosively when mixed with air at a concentration of 2 percent to 9 percent by volume. Jerry was aware of the hazards of repairing Harvey’s tire and took precautions to avoid an accident. First he let out the excess gas in the tire. Next he reinflated the tire to 35 psi with air. And he repeated the procedure once. Clearly, this is a dilution process intended to gradually decrease the concentrations of propane and butane. The fact that the tire exploded means that Jerry had not diluted the gases enough. But what was the source of ignition?

When Jerry found the nail hole in the tire, he used a tire reamer, a metal file-like instrument, to clean dirt and loose rubber from the hole before applying a rubber plug and liquid sealant. The last thing Jerry remembered was pulling the reamer out of the hole. The next thing he knew he was lying in the hospital, hurting all over. To solve this mystery, make use of the following clues.


ps: Adapted with permission from “The Exploding Tire,” by Jay A. Young, CHEM MATTERS, April, 1988, p. 12. Copyright

1995 American Chemical Society.

Discovery of Helium and the Rise and Fall of Coronium

Scientists know that our sun and other stars contain certain elements. How was this information obtained?

In the early nineteenth century, the German physicist Josef Fraunhofer studied the emission spectrum of the sun and noticed certain dark lines at specific wavelengths. We interpret the appearance of these lines by supposing that originally a continuous band of color was radiated and that, as the emitted light moves outward from the sun, some of the radiation is reabsorbed at those wavelengths by the atoms in space. These dark lines are therefore absorption lines. For atoms, the emission and absorption of light occur at the same wavelengths. By matching the absorption lines in the emission spectra of a star with the emission spectra of known elements in the laboratory, scientists have been able to deduce the types of elements present in the star.

Another way to study the sun spectroscopically is during its eclipse. In 1868 the French physicist Pierre Janssen observed a bright yellow line (see Figure) in the emission spectrum of the sun’s corona during the totality of the eclipse. (The corona is the pearly white crown of light visible around the sun during a total eclipse.) This line did not match the emission lines of known elements, but did match one of the dark lines in the spectrum sketched by Fraunhofer. The name helium (from Helios, the sun god in Greek mythology) was given to the element responsible for the emission line. Twenty-seven years later, helium was discovered on Earth by the British chemist William Ramsay in a mineral of uranium. On Earth, the only source of helium is through radioactive decay processes—a particles emitted during nuclear decay are eventually converted to helium atoms.

Fraunhofer’s original drawing, in 1814, showing the dark absorption lines in the sun’s emission spectrum. The top of the diagram shows the overall brightness of the sun at different colors.

The search for new elements from the sun did not end with helium. Around the time of Janssen’s work, scientists also detected a bright green line in the spectrum from the corona. They did not know the identity of the element giving rise to the line, so they called it coronium because it was only found in the corona. Over the following years, additional mystery coronal emission lines were found. The coronium problem proved much harder to solve than the helium case because no matchings were found with the emission lines of known elements. It was not until the late 1930s that the Swedish physicist Bengt Edlén identified these lines as coming from partially ionized atoms of iron, calcium, and nickel. At very high temperatures (over a million degrees Celsius), many atoms become ionized by losing one or more electrons. Therefore, the mystery emission lines come from the resulting ions of the metals and not from a new element. So, after some 70 years the coronium problem was finally solved. There is no such element as coronium after all!

During the total eclipse of the sun, which lasts for only a few minutes, the corona becomes visible.

Out of Oxygen

In September 1991 four men and four women entered the world’s largest glass bubble, known as Biosphere II, to test the idea that humans could design and build a totally self-contained ecosystem, a model for some future colony on another planet. Biosphere II (Earth is considered Biosphere I) was a 3-acre mini-world, complete with a tropical rain forest, savanna, marsh, desert, and working farm that was intended to be fully self-sufficient. This unique experiment was to continue for 2 to 3 years, but almost immediately there were signs that the project could be in jeopardy.

Soon after the bubble had been sealed, sensors inside the facility showed that the concentration of oxygen in Biosphere II’s atmosphere had fallen from its initial level of 21 percent (by volume), while the amount of carbon dioxide had risen from a level of 0.035 percent (by volume), or 350 ppm (parts per million). Alarmingly, the oxygen level continued to fall at a rate of about 0.5 percent a month and the level of carbon dioxide kept rising, forcing the crew to turn on electrically powered chemical scrubbers, similar to those on submarines, to remove some of the excess CO₂. Gradually the CO₂ level stabilized around 4000 ppm, which is high but not dangerous. The loss of oxygen did not stop, though. By January 1993—16 months into the experiment—the oxygen concentration had dropped to 14 percent, which is equivalent to the O₂ concentration in air at an elevation of 4360 m (14,300 ft). The crew began having trouble performing normal tasks. For their safety it was necessary to pump pure oxygen into Biosphere II.

With all the plants present in Biosphere II, the production of oxygen should have been greater as a consequence of photosynthesis. Why had the oxygen concentration declined to such a low level? A small part of the loss was blamed on unusually cloudy weather, which had slowed down plant growth. The possibility that iron in the soil was reacting with oxygen to form iron(III) oxide or rust was ruled out along with several other explanations for lack of evidence. The most plausible hypothesis was that microbes (microorganisms) were using oxygen to metabolize the excess organic matter that had been added to the soils to promote plant growth. This turned out to be the case.

Identifying the cause of oxygen depletion raised another question. Metabolism produces carbon dioxide. Based on the amount of oxygen consumed by the microbes, the CO₂ level should have been at 40,000 ppm, 10 times what was measured. What happened to the excess gas? After ruling out leakage to the outside world and reactions between CO₂ with compounds in the soils and in water, scientists found that the concrete inside Biosphere II was consuming large amounts of CO₂ !

Concrete is a mixture of sand and gravel held together by a binding agent that is a mixture of calcium silicate hydrates and calcium hydroxide. The calcium hydroxide is the key ingredient in the CO₂ mystery. Carbon dioxide diffuses into the porous structure of concrete, then reacts with calcium hydroxide to form calcium carbonate and water:

Ca(OH)₂(s) + CO₂(g) → CaCO₃(s) + H₂O(l)

Vegetations in Biosphere II

Under normal conditions, this reaction goes on slowly. But CO₂ concentrations in Biosphere II were much higher than normal, so the reaction proceeded much faster. In fact, in just over 2 years, CaCO₃ had accumulated to a depth of more than 2 cm in Biosphere II’s concrete. Some 10,000 m² of exposed concrete was hiding 500,000 to 1,500,000 moles of CO₂.

The water produced in the reaction between Ca(OH)₂ and CO₂ created another problem:

CO₂ also reacts with water to form carbonic acid (H₂CO₃), and hydrogen ions produced by the acid promote the corrosion of the reinforcing iron bars in the concrete, thereby weakening its structure. This situation was dealt with effectively by painting all concrete surfaces with an impermeable coating.

In the meantime, the decline in oxygen (and hence also the rise in carbon dioxide) slowed, perhaps because there was now less organic matter in the soils and also because new lights in the agricultural areas may have boosted photosynthesis. The project was terminated prematurely and in 1996, the facility was transformed into a science education and research center. As of 2007, the Biosphere is under the management of the University of Arizona.

The Biosphere II experiment is an interesting project from which we can learn a lot about Earth and its inhabitants. If nothing else, it has shown us how complex Earth’s ecosystems are and how difficult it is to mimic nature, even on a small scale.

ps: Adapted with permission from “Biosphere II: Out of Oxygen,” by Joe Alper, CHEM MATTERS, February, 1995, p. 8.

Copyright 1995 American Chemical Society.

Who Killed Napoleon?

A lock of Napoleon’s hair.

After his defeat at Waterloo in 1815, Napoleon was exiled to St. Helena, a small island in the Atlantic Ocean, where he spent the last six years of his life. In the 1960s, samples of his hair were analyzed and found to contain a high level of arsenic, suggesting that he might have been poisoned. The prime suspects are the governor of St. Helena, with whom Napoleon did not get along, and the French royal family, who wanted to prevent his return to France.

Elemental arsenic is not that harmful. The commonly used poison is actually arsenic(III) oxide, As₂O₃, a white compound that dissolves in water, is tasteless, and if administered over a period of time, is hard to detect. It was once known as the “inheritance powder” because it could be added to grandfather’s wine to hasten his demise so that his grandson could inherit the estate!

In 1832 the English chemist James Marsh devised a procedure for detecting arsenic. This test, which now bears Marsh’s name, combines hydrogen formed by the reaction between zinc and sulfuric acid with a sample of the suspected poison. If As₂O₃ is present, it reacts with hydrogen to form a toxic gas, arsine (AsH₃). When arsine gas is heated, it decomposes to form arsenic, which is recognized by its metallic luster. The Marsh test is an effective deterrent to murder by As₂O₃, but it was invented too late to do Napoleon any good, if, in fact, he was a victim of deliberate arsenic poisoning.

Doubts about the conspiracy theory of Napoleon’s death developed in the early 1990s, when a sample of the wallpaper from his drawing room was found to contain copper arsenate (CuHAsO₄), a green pigment that was commonly used at the time Napoleon lived. It has been suggested that the damp climate on St. Helena promoted the growth of molds on the wallpaper. To rid themselves of arsenic, the molds could have converted it to trimethyl arsine [(CH₃)₃As], which is a volatile and highly poisonous compound. Prolonged exposure to these vapors would have ruined Napoleon’s health and would also account for the presence of arsenic in his body, though it may not have been the primary cause of his death. This provocative theory is supported by the fact that Napoleon’s regular guests suffered from gastrointestinal disturbances and other symptoms of arsenic poisoning and that their health all seemed to improve whenever they spent hours working outdoors in the garden, their main hobby on the island.

We will probably never know whether Napoleon died from arsenic poisoning, intentional or accidental, but this exercise in historical sleuthing provides a fascinating example of the use of chemical analysis. Not only is chemical analysis used in forensic science, but it also plays an essential part in endeavors ranging from pure research to practical applications, such as quality control of commercial products and medical diagnosis.

The Disappearance of The Dinosaurs

Dinosaurs dominated life on Earth for millions of years and then disappeared very suddenly. To solve the mystery, paleontologists studied fossils and skeletons found in rocks in various layers of Earth’s crust. Their findings enabled them to map out which species existed on Earth during specific geologic periods. They also revealed no dinosaur skeletons in rocks formed immediately after the Cretaceous period, which dates back some 65 million years. It is therefore assumed that the dinosaurs became extinct about 65 million years ago.

Among the many hypotheses put forward to account for their disappearance were disruptions of the food chain and a dramatic change in climate caused by violent volcanic eruptions. However, there was no convincing evidence for any one hypothesis until 1977. It was then that a group of paleontologists working in Italy obtained some very puzzling data at a site near Gubbio. The chemical analysis of a layer of clay deposited above sediments formed during the Cretaceous period (and therefore a layer that records events occurring after the Cretaceous period) showed a surprisingly high content of the element iridium (Ir). Iridium is very rare in Earth’s crust but is comparatively abundant in asteroids.

This investigation led to the hypothesis that the extinction of dinosaurs occurred as follows. To account for the quantity of iridium found, scientists suggested that a large asteroid several miles in diameter hit Earth about the time the dinosaurs disappeared. The impact of the asteroid on Earth’s surface must have been so tremendous that it literally vaporized a large quantity of surrounding rocks, soils, and other objects. The resulting dust and debris floated through the air and blocked the sunlight for months or perhaps years. Without ample sunlight most plants could not grow, and the fossil record confirms that many types of plants did indeed die out at this time. Consequently, of course, many plant-eating animals perished, and then, in turn, meat-eating animals began to starve. Dwindling food sources would obviously affect large animals needing great amounts of food more quickly and more severely than small animals. Therefore, the huge dinosaurs, the largest of which might have weighed as much as 30 tons, vanished due to lack of food.