LEWIS THEORY - CHEMISTRY TUTORIALS



In the period from 1916 to 1919, two Americans, G. N. Lewis and Irving Langmuir, and a German, Walther Kossel, advanced an important proposal about chemical bonding:

Something unique in the electron configurations of noble gas atoms accounts for their inertness, and atoms of other elements combine with one another to acquire electron configurations like those of noble gas atoms.

The theory that grew out of this model has been most closely associated with G. N. Lewis and is called the Lewis theory. Some fundamental ideas associated with Lewis s theory follow:

1. Electrons, especially those of the outermost (valence) electronic shell, play a fundamental role in chemical bonding.

2. In some cases, electrons are transferred from one atom to another. Positive and negative ions are formed and attract each other through electrostatic forces called ionic bonds.

3. In other cases, one or more pairs of electrons are shared between atoms. A bond formed by the sharing of electrons between atoms is called a covalent bond.

4. Electrons are transferred or shared in such a way that each atom acquires an especially stable electron configuration. Usually this is a noble gas configuration, one with eight outer-shell electrons, or an octet.

Lewis developed a special set of symbols for his theory. A Lewis symbol consists of a chemical symbol to represent the nucleus and core (inner-shell) electrons of an atom, together with dots placed around the symbol to represent the valence (outer-shell) electrons.

A Lewis structure is a combination of Lewis symbols that represents either the transfer or the sharing of electrons in a chemical bond.

In Lewis theory, we use square brackets to identify ions, as we did in equation (10.1). The charge on the ion is given as a superscript.

Lewis s work dealt mostly with covalent bonding, which we will emphasize throughout this chapter. However, Lewis s ideas also apply to ionic bonding, and we briefly describe this application next.

ATOMIC RADIUS - BASIC INFORMATION AND TUTORIALS



Unfortunately, atomic radius is hard to define. The probability of finding an electron decreases with increasing distance from the nucleus, but nowhere does the probability fall to zero, so there is no precise outer boundary to an atom.

We might describe an effective atomic radius as, say, the distance from the nucleus within which 95% of all the electron charge density is found, but in fact, all that we can measure is the distance between the nuclei of adjacent atoms (internuclear distance).

Even though it varies, depending on whether atoms are chemically bonded or merely in contact without forming a bond, we define atomic radius in terms of internuclear distance.

Because we are primarily interested in bonded atoms, we will emphasize an atomic radius based on the distance between the nuclei of two atoms joined by a chemical bond. The covalent radius is one-half the distance between the nuclei of two identical atoms joined by a single covalent bond.

The ionic radius is based on the distance between the nuclei of ions joined by an ionic bond. Because the ions are not identical in size, this distance must be properly apportioned between the cation and anion. One way to apportion the electron density between the ions is to define the radius of one ion and then infer the
radius of the other ion.

The convention we have chosen to use is to assign an ionic radius of 140 pm. An alternative apportioning scheme is to use as the reference ionic radius.

When using ionic radii data, one should carefully note which convention is used and not mix radii from the different conventions. Starting with a radius of 140 pm for the radius of Mg2+ can be obtained from the internuclear distance in MgO, the radius of from the internuclear distance in and the radius of from the internuclear distance in NaCl.

For metals, we define a metallic radius as one-half the distance between the nuclei of two atoms in contact in the crystalline solid metal. Similarly in a solid sample of a noble gas the distance between the centers of neighboring atoms is called the van der Waals radius.

There is much debate about the values of the atomic radii of noble gases because the experimental determination of the van der Waals radii is difficult; consequently, the atomic radii of noble gases are left out of the discussion of trends in atomic radii.

THE SCIENTIFIC METHOD USE IN CHEMISTRY BASICS


Science differs from other fields of study in the method that scientists use to acquire knowledge and the special significance of this knowledge. Scientific knowledge can be used to explain natural phenomena and, at times, to predict future events.

The ancient Greeks developed some powerful methods of acquiring knowledge, particularly in mathematics. The Greek approach was to start with certain basic assumptions, or premises. Then, by the method known as deduction, certain conclusions must logically follow.

For example, if and then Deduction alone is not enough for obtaining scientific knowledge, however. The Greek philosopher Aristotle assumed four fundamental substances: air, earth, water, and fire. All other materials, he believed, were formed by combinations of these four elements.

Chemists of several centuries ago (more commonly referred to as alchemists) tried, in vain, to apply the four-element idea to turn lead into gold. They failed for many reasons, one being that the four-element assumption is false.

The scientific method originated in the seventeenth century with such people as Galileo, Francis Bacon, Robert Boyle, and Isaac Newton. The key to the method is to make no initial assumptions, but rather to make careful observations of natural phenomena.

When enough observations have been made so that a pattern begins to emerge, a generalization or natural law can be formulated describing the phenomenon. Natural laws are concise statements, often in mathematical form, about natural phenomena.

The form of reasoning in which a general statement or natural law is inferred from a set of observations is called induction. For example, early in the sixteenth century, the Polish astronomer Nicolas Copernicus (1473 1543), through careful study of astronomical observations, concluded that Earth revolves around the sun in a circular orbit, although the general teaching of the time, not based on scientific study, was that the sun and other heavenly bodies revolved around Earth.

We can think of Copernicus s statement as a natural law. Another example of a natural law is the radioactive decay law, which dictates how long it takes for a radioactive substance to lose its radioactivity.

The success of a natural law depends on its ability to explain, or account for, observations and to predict new phenomena. Copernicus s work was a great success because he was able to predict future positions of the planets more accurately than his contemporaries.

We should not think of a natural law as an absolute truth, however. Future experiments may require us to modify the law. For example, Copernicus s ideas were refined a half-century later by Johannes Kepler, who showed that planets travel in elliptical, not circular, orbits. To verify a natural law, a scientist designs experiments that show whether the conclusions deduced from the natural law are supported by experimental results.

A hypothesis is a tentative explanation of a natural law. If a hypothesis survives testing by experiments, it is often referred to as a theory. In a broader sense, a theory is a model or way of looking at nature that can be used to explain natural laws and make further predictions about natural phenomena.

When differing or conflicting theories are proposed, the one that is most successful in its predictions is generally chosen. Also, the theory that involves the smallest number of assumptions the simplest theory is preferred. Over time, as new evidence accumulates, most scientific theories undergo modification,
and some are discarded.

The scientific method is the combination of observation, experimentation, and the formulation of laws, hypotheses, and theories. Scientists may develop a pattern of thinking about their field, known as a paradigm.

Some paradigms may be successful at first but then become less so. When that happens, a new paradigm may be needed or, as is sometimes said, a paradigm shift occurs. In a way, the method of inquiry that we call the scientific method is itself a paradigm, and some people feel that it, too, is in need of change.

In any case, merely following a set of procedures, rather like using a cookbook, will not guarantee scientific success. Another factor in scientific discovery is chance, or serendipity. Many discoveries have been made by accident.

For example, in 1839, the American inventor Charles Goodyear was searching for a treatment for natural rubber that would make it less brittle when cold and less tacky when warm. In the course of this work, he accidentally spilled a rubber sulfur mixture on a hot stove and found that the resulting product had exactly the properties he was seeking.

Other chance discoveries include X-rays, radioactivity, and penicillin. So scientists and inventors always need to be alert to unexpected observations. Perhaps no one was more aware of this than Louis Pasteur, who wrote, Chance favors the prepared mind.

FRIEDEL-CRAFTS REACTIONS BASIC INFORMATION


Several chemicals are manufactured by application of the Friedel-Crafts condensation reaction. Efficient operation of any such process depends on:

1. The preparation and handling of reactants
2. The design and construction of the apparatus
3. The control of the reaction so as to lead practically exclusively to the formation of the specific products desired
4. The storage of the catalyst (aluminum chloride)

Several of the starting reactants, such as acid anhydrides, acid chlorides, and alkyl halides, are susceptible to hydrolysis. The absorption of moisture by these chemicals results in the production of compounds that are less active, require more aluminum chloride for condensation, and generally lead to lower yields of desired product.

Furthermore, the ingress of moisture into storage containers for these active components usually results in corrosion problems.

Anhydrous aluminum chloride needs to be stored in iron drums under conditions that ensure the absence of moisture. When, however, moisture contacts the aluminum chloride, hydrogen chloride is formed, the quantity of hydrogen chloride thus formed depends on the amount of water and the degree of agitation of the halide.

If sufficient moisture is present, particularly in the free space in the container or reaction vessel or at the point of contact with the outside atmosphere, then hydrochloric acid is formed and leads to corrosion of the storage container.

In certain reactions, such as the isomerization of butane and the alkylation of isoparaffins, problems of handling hydrogen chloride and acidic sludge are encountered. The corrosive action of the aluminum chloride–hydrocarbon complex, particularly at 70 to 100oC, has long been recognized and various reactor liners have been found satisfactory.

The rate of reaction is a function of the efficiency of the contact between the reactants, i.e., stirring mechanism and mixing of the reactants. In fact, mixing efficiency has a vital influence on the yield and purity of the product. Insufficient or inefficient mixing may lead to uncondensed reactants or to excessive reaction on heated surfaces.

PLANT CAPITAL COST ESTIMATION VIA SCALING FACTOR


Given that the total capital investment (TCI) of a 50,000-ton/year polypropylene unit is $60,000,000 (in 2002 dollars), find the TCI required for a 75,000-ton/year polypropylene unit via the scaling factor method.

Calculation Procedure
1. Apply the appropriate power-function formula. In the scaling factor method, the TCI is estimated via the following formula (a power function):
TCI2 = TCI1(C2/C1)E
where TCI1 and TCI2 = total capital investment of existing and planned unit, respectively, in dollars
TCI1 = $60,000,000
C1,C2 = capacity of existing and planned unit, respectively, in tons/year
C1 = 50,000 and C2 = 75,000
E = scaling exponent = 0.70

Thus
TCI2 = 60,000(75,000/50,000)0.70 = $80,000,000 (rounded)

Related Calculations. The scaling factor method is an appropriate procedure for estimating the TCI only under the following conditions:

1. The existing and planned units are identical (or nearly so), in terms of processing steps, end products, major equipment items used, and other respects.

2. The desired estimate falls within the category of “order-of-magnitude/screening/scoping” cost estimates (i.e., those estimates with a presumed accuracy less precise than ±30%).

3. The capacity of the planned unit falls within the capacity range for which the scaling exponent is valid. Rarely is the power function relationship between TCI and capacity a smooth curve over the entire capacity range.

Typically, the scaling exponent increases in value with increasing capacity. However, as the scaling exponent approaches unity, it becomes less costly to build two units, each with half the capacity of the large plant, than to construct a single, large-capacity plant.

4. The costs of both the existing and planned units are expressed in dollars of the same period. In this example, the TCIs are in 2002 dollars. If the costs are not of the same vintage, the cost of the existing plant (which is likely older) will have to be adjusted to the same year dollars as that of the planned unit.

However, unless the cost vintages are much different (e.g., five years or more), adjustments for escalation would be “fine tuning,” compared to the relative inaccuracy of these scaling factor estimates.

DETERMINING THE LABORATORY-REACTOR SIZE NEEDED FOR SEEDING A BIOLOGICAL REACTION



SIZING OF BIO-REACTOR EXAMPLE AND TUTORIALS

Assuming a minimum 12% inoculum volume, what size of laboratory vessel would be required to initiate the seeding of a 20,000-L full-scale cell-culture bioreactor?

Calculation Procedure

1. Determine the size of reactor that would be required to seed the 20,000-L bioreactor. Since the seed volume must represent 12% of the vessel before reaction starts, the bioreactor being specified in this step would have to have a size 12% that of the 20,000-L bioreactor, or (0.12)(20,000), or 2400 L.

2. Determine the size of bioreactor needed to seed the 2400-L bioreactor of Step 1. Applying the same logic as in step 1, we see that the bioreactor being sought in this second step must be sized at 12% of 2400 L, or (0.12)(2400), or 288 L.

3. Repeat Step 2 successively until a bioreactor of reasonable laboratory volume is reached. Twelve percent of 288 L is 34.6 L; then, 12% of 34.6 is 4.15 L; and 12% of 4.15 L is 500 ml. Thus, a 4.15-L laboratory vessel can be used if available.

Otherwise, use a 500-ml vessel. The contents of the 500-ml vessel provide seeding for the 4.15-L vessel; the contents of the latter vessel then seed the 34.6-L bioreactor; the contents of this latter then seed the 288-L bioreactor; and so on.

ESTERIFICATION BASIC INFORMATION AND TUTORIALS



A variety of solvents, monomers, medicines, perfumes, and explosives are made from esters of nitric acid. Ethyl acetate, n-butyl acetate, iso-butyl acetate, glycerol trinitrate, pentaerythritol tetranitrate (PETN), glycol dinitrate, and cellulose nitrate are examples of such reactions.

Ester manufacture is a relatively simple process in which the alcohol and an acid are heated together in the presence of a sulfuric acid catalyst, and the reaction is driven to completion by removing the products as formed (usually by distillation) and employing an excess of one of the reagents. 

In the case of ethyl acetate, esterification takes place in a column that takes a ternary azeotrope. Alcohol can be added to the condensed overhead liquid to wash out the alcohol, which is then purified by distillation
and returned to the column to react.

Amyl, butyl, and iso-propyl acetates are all made from acetic acid and the appropriate alcohols. All are useful lacquer solvents and their slow rate of evaporation (compared to acetone or ethyl acetate) prevents the surface of the drying lacquer from falling below the dew point, which would cause condensation on the film and a mottled surface appearance (blushing). 

Other esters of importance are used in perfumery and in plasticizers and include methyl salicylate, methyl anthranilate, diethyl-phthalate, dibutyl-phthalate, and di-2-ethylhexyl-phthalate.

Unsaturated vinyl esters for use in polymerization reactions are made by the esterification of olefins. The most important ones are vinyl esters: vinyl acetate, vinyl chloride, acrylonitrile, and vinyl fluoride. The addition reaction may be carried out in either the liquid, vapor, or mixed phases, depending on the properties of the acid. 

Care must be taken to reduce the polymerization of the vinyl ester produced. Esters of allyl alcohol, e.g., diallyl phthalate, are used as bifunctional polymerization monomers and can be prepared by simple esterification of phthalic anhydride with allyl alcohol. 

Several acrylic esters, such as ethyl or methyl acrylates, are also widely used and can be made from acrylic acid and the appropriate alcohol. The esters are more volatile than the corresponding acids.

WHY DOES SALT WATER MAKE METAL RUST FASTER?


If you had pure iron and put it into pure water, very little would happen, since there would be no oxygen to react with the iron. And if you put the pure iron into pure dry oxygen, very little would also happen.

The outer iron atoms would rust, but then that layer of rust would stand between the iron and the remaining oxygen.

Water helps iron react with oxygen. The first step in getting oxygen to react with iron is to break up the oxygen molecule. In water, oxygen can steal some electrons from iron to make four hydroxyl ions (the OH− ions in the following reaction):

O2 + 4 e− + 2 H2O ! 4 OH−

The electrons come from the iron:
Fe ! Fe2+ + 2 e−
Diethylene glycol
O
O
O
H H

But to make rust we need another reaction with iron:
4 Fe2+ + O2 ! 4 Fe3+ + 2 O2

In the process of making rust, the ferrous (Fe2+) and ferric (Fe3+) ions also react with water to form Fe(OH)2 and Fe(OH)3 (ferrous hydroxide and ferric hydroxide) and hydrogen. These hydroxides can then lose their water to form still more iron compounds.

It is all these reactions that end up making the rust flaky, so it falls off the iron and exposes new iron that can start to rust.

All of these reactions are sped up by acids and by having more ions in the water, so it conducts electricity better, so that the iron and oxygen can exchange electrons. Adding salt to the water makes the iron corrode more quickly, but adding an acid makes it corrode even faster than that.

HIGH DENSITY POLYETHYLENE BASIC INFORMATION


Most HDPE is actually a copolymer containing up to 1% of 1-butene or less commonly 1-hexene. The comonomer is required, particularly when metal oxide catalysts are used, to avoid formation of molecular weights so high that the polymer becomes intractable. The copolymer also has improved low temperature properties.

The production of HDPE is much less energy intensive than that of LDPE. Reaction temperatures can be as low as 60°C and pressures as low as 1 bar. Nonetheless, temperatures of 130–270°C and pressures of 10–160 bar are used commercially. Conversion per pass approaches 100%.

High-density polyethylene is manufactured in solution, slurry, or fluidized-bed processes. In the slurry process, the catalyst is dispersed in a solvent such as hexane, and the ethylene is polymerized batchwise in a series of reactors.

The gas phase, fluidized-bed processes were devised first by Union Carbide and subsequently by BP and BASF. Small HDPE particles are fluidized by gaseous ethylene and comonomer (e.g., 1-butene) at 85–105°C and 20 bar.

Catalyst is continuously sprayed into the reactor. The ethylene and comonomer copolymerize around the preformed polymer particles. At the same time, the gaseous ethylene removes the heat of reaction.

The initial particles grow to an average diameter of 500 microns over a period of three to five hours, during which time only about 2–3% of the ethylene polymerizes. The unconverted reactants are recycled.

Polyethylene, once prepared, is melted, mixed with stabilizers and other additives, and extruded to form spaghetti-like rods, which are then cut into small pellets. The extrusion is an energy-intensive operation.

An objective of the fluidized bed process (Carbide’s Unipol process), not achieved initially, was to obtain the polymer as a powder with uniform-sized particles that could be used as such for molding and extrusion.

Further development has apparently made this possible, although the value of the powder is questionable, because its low-bulk density increases shipping costs. But, serendipitously, the gas-phase process has proved to be an economical way to prepare both high- and linear low-density polyethylenes. It has been licensed extensively and is the most important process in use today.

STANDARD FIRST AID TREATMENT FOR CHEMICAL EXPOSURES


Splashes on the skin 
Flood the splashed surface thoroughly with large quantities of running water for ≥10 min or until satisfied that no chemical remains in contact with the skin

Use soap to help remove splashes of solvents, solutions and chemicals known to be insoluble in water

Remove all contaminated clothing, taking care not to contaminate yourself in the process

If necessary, arrange for transport to hospital or refer for medical advice to nearest doctor

Information to accompany the casualty:
Chemical involved
Details of treatment already given
(Special procedures apply to certain chemicals, e.g. anhydrous hydrogen fluoride, aqueous hydrofluoric acid, phenol and related compounds)

Splashes in the eye 
Flood the eye thoroughly with large quantities of clean, cool water or sterile liquid from a sealed container and continue for 10–15 min

Ensure that the water bathes the eyeball by gently prising open the eyelids and keeping them apart until treatment is completed. Do not attempt to remove anything that is embedded

All eye injuries from chemicals require medical advice. Apply an eye pad and arrange transport to hospital

Information to accompany the casualty:
Chemical involved
Details of treatment already given

Inhalation of gas 
Remove the casualty from the danger area after first ensuring your own safety

Loosen clothing; administer oxygen if available
If the casualty is unconscious, place in the recovery position and watch to see if breathing stops

If breathing has stopped, apply artificial respiration by the mouth-to-mouth method; if no pulse is detectable, start cardiac compressions

If necessary, arrange transport to hospital

Information to accompany the casualty:
Gas involved
Details of treatment already given
(Special procedures apply to certain chemicals, e.g. hydrogen cyanide)

Ingestion of poisonous chemical
If the chemical has been confined to the mouth, give large quantities of water as a mouthwash; ensure that the mouthwash is not swallowed

If the chemical has been swallowed, small amounts of water may be administered, more if the chemical is corrosive; administer a specific antidote if one exists

Do not induce vomiting

Arrange transport to hospital

Information to accompany the casualty:
Chemical swallowed
Details of treatment already given
Estimate of quantity/concentration of chemical consumed