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Chemistry and Thermodynamics

Lost in the forest of science.

The study of science begins for everyone as a small path in the forest of ignorance, but with effort and experience, that path becomes our personal path of knowledge and information, opening many possibilities. Albert Einstein, like everyone else, started in the woods, and he showed that getting out was worth the effort, not only for him, but for all his knowledge he did for humanity. Science is not for everyone and there are few Einsteins. Unfortunately, many get lost, confused and frustrated, giving up before they can pronounce their first “Eureka”, as a gem of knowledge falls into place. Those “Eureka” moments can excite us to keep going on our particular path.

So the first step is to be motivated and want to know more.

The next important step is to pay attention to the definitions: something that is important in any area: in sports you must know the rules to play the game: it is the same for science. Knowing the definitions clears up confusions, and applying them (solving problems) solidifies them. Eventually the scientific method and thinking become a way of life, and give insight into many situations, even outside your particular area of ​​expertise.

A structure emerges. For example, life sciences and medicine are based on biochemistry and pharmacology, which is based on organic chemistry, and organic depends on physical chemistry. Physical chemistry is based on physics, and mathematics is the logic that unites them all.

Along the way there are many sidelines, too numerous to list here: new materials, nanotechnology are two important and well-known disciplines. Even different areas overlap in multidisciplinary fields, such as physical and organic chemistry (physical-organic chemistry); organic synthesis and chemical kinetics (organocatalysis), inorganic and organic chemistry (organometallic chemistry): the list goes on.

Clearly no one can become an expert in all these areas. However, a good foundation in the basics of physical science allows one to at least be in a position to appreciate the work of others in the many areas of scientific endeavor. You could end up as a lawyer, social worker or in finance. A good background in science will help the lawyer to argue his case of, say, patent infringement; helps the social worker understand the side effects of the medications that a client could take, and allows the financier to make smart decisions to invest in a mining company or another.

On the other hand, you can become a scientist which leads to many interesting careers.

Scientists and engineers

Science can be divided into two broad categories: fundamental science (research) and the applications of these ideas (engineering: also called Research and Development (R&D)). Today there are about ten times more engineers than there are scientists. It takes more effort and more people to take the fundamental ideas developed by a few, and turn them into technologies that we use to improve our quality of life.

Think about the automobile industry. The internal combustion engine, based on the Otto cycle, was developed by a few (which proved to work), and then many engineers took the basic idea and in the last hundred years developed cars that we have today.

To be a good engineer, you must start with the basics and learn the basics before you can apply them.

The macroscopic and the microscopic

A broad division of science is into the macroscopic (samples large enough that we can measure and examine), and the microscopic (atoms, molecules and collections of these, too small to observe individually).

There are two major bases of macroscopic science: Thermodynamics (the study of heat, work and efficiency), and Classical Mechanics (Newtonian physics that describes the movement of macroscopic objects).

The microscopic is governed by quantum mechanics.

Since microscopic particles have a lot of symmetry, the field of group theory (a mathematical subject) should be mentioned. This helps to visualize molecules and reactions, and has a particular relevance in the most fundamental science, which is physics. You don’t have to be a mathematician to use group theory. Mathematics is a tool of scientists: logic guides us.

The field of Statistical Mechanics relates macroscopic objects to their microscopic particles.

The example of chemistry

Chemistry is the study of making and breaking bonds, meaning that chemicals react to form different chemicals. A chemical reaction proceeds if the conditions are right: two important conditions are energy and entropy. Both are substances and entropy is as tangible as energy. How did this come about?

Engineers started noticing things a couple of hundred years ago: like horses walking in a circle and driving machinery to drill cannons. The horses walked at a constant pace, (constant energy) but a bit dull produced a lot of heat and not much work (boring the cannon was slow), but a sharp bit produced much less heat and more boring. This is the first law of thermodynamics:

Energy (horsepower) = heat (friction) + work (cannon).

Clearly energy is not cheap (horses must be purchased, fed and cared for), because it would be better to reduce heat loss and increase the work done. That is, the efficiency of energy use has become an important consideration.

In the 19th century, thermodynamics also evolved motivated by the need to increase the efficiency of the steam engine that drove the industrial revolution. The first steam engines were about 3% efficient and so improvements were definitely needed. Adding a second cylinder, for example, improved many things, but could they do more? Could the dream of 100% efficiency come true, i.e. perpetual motion?

This led Sadi Carnot in the 1830s to define a cycle for the steam engine from which entropy was discovered, and the Second Law of Thermodynamics was formulated – perpetual motion was shown to be impossible. The Otto cycle was developed for an internal combustion engine about forty years later.

Although alchemy is an old subject, it was only after the First and Second Laws of Thermodynamics were developed that chemistry really took off. Many were involved in its development. In addition to Sadi Carnot, a few notable names are James Maxwell, Rudolf Clausius, James Joule, Willard Gibbs and Ludwig Boltzmann.

The ideas they developed apply well to chemistry. When the bonds are broken, energy must be added to the system; and when the bonds are formed, energy is released to the environment. Some chemical reactions produce more randomness (higher entropy) and sometimes more order (lower entropy) as atoms rearrange to form products. Energy (heat and work) and entropy (randomness) play an important role in the spontaneity of a chemical reaction.

Here is an example. Trinitrotoluene (TNT) can explode (a rapid chemical reaction). From the chemical formula it has three nitrogen bonds. Most chemical explosives contain nitrogen by the way. The combustion of one mole of TNT releases 3,400 kJ mol-1 of energy,

C7H5N3O6(s) + 21/4 O2(g) to 7 CO2(g) + 5/2 H2O(g) + 3/2 N2 (g) †H = -3,400 kJmol-1

Compare this, however, with the energy of burning sugar such as sucrose (a slow chemical reaction),

C12H22O11(s) + 12 O2(g) to 12 CO2(g) + 11 H2O(l) †H = -5 644 kJ mol-1

Sucrose produces much more energy per mole than TNT! So why isn’t sucrose also an explosive? Sucrose burns slowly relative to TNT, with a correspondingly slow release of carbon dioxide. TNT burns so fast that a lot of energy is released in a short time. Also, solid TNT occupies a small volume, but the final volume is equal to 11 moles of gas (about 250 liters at STP). The destruction is not caused so much by the heat released but by the rapid expansion of the gases produced. Using the First Law, the energy released by a mole, (3,400 kJ) goes into some heat, but a lot of work is done to the environment as the gas expands, and this can cause damage.

This is where entropy comes in. Notice that the right hand of the TNT combustion has only 21/4 = 5.25 moles of gas, while the RHS has 11 moles of gas. This means that there is more clutter on the RHS than the LHS. Clearly, the rapid expansion in the explosive combustion of TNT can lead to destruction (it will knock Humpty Dumpty off his wall) and cause greater disorder and therefore entropy increases. Energy and entropy are favorable for this reaction to proceed. This is not always the case, especially biological processes, where entropy, not energy, is the main driving force.

Thermodynamics tells us which chemical reactions will proceed and which will not. Chemical Kinetics tells us how fast reactions occur, and how much energy is required to start a reaction. TNT is not very sensitive to shock because it has a high activation energy. On the other hand, Nitroglycerine, (NG), another chemical explosive (with many nitrogen bonds), explodes with a small shock and cannot be transported in liquid form at room temperature. It has a low activation energy. Alfred Nobel solved the nitroglycerin problem by inventing dynamite: reducing shock sensitivity by soaking NG in sawdust, paper or some absorbent material. The patent was so successful that it left us the legacy of the Nobel Prize.

Equilibrium thermodynamics is a closed field today without fundamental new research. It is a beautiful, complete and compact theory that gives the relationship between the macroscopic quantities that we can measure: energy, heat capacity, compression factors and much more, with a wide application.

Thermodynamics is essential knowledge for all chemists. However, thermodynamics fails to explain why these relationships exist. This is given by another elegant theory called Statistical Mechanics.

Physical chemistry covers all these.

There is much more to say, but this is a summary. Actually, many say that thermodynamics is not a good name because it describes equilibrium properties, not dynamics. A better name would be thermostatic – but nobody calls it that.

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