ISBN-10:
0470171723
ISBN-13:
9780470171721
Pub. Date:
11/03/2008
Publisher:
Wiley
Handbook of Environmental Data on Organic Chemicals, 4 Volume Set / Edition 5

Handbook of Environmental Data on Organic Chemicals, 4 Volume Set / Edition 5

by Karel VerschuerenKarel Verschueren
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Overview

This book contains all the information needed to use potentially dangerous chemicals prudently. Arranged in alphabetical order by chemical name, this reference provides: synonyms, CAS numbers, and molecular and structural formulas. It covers natural and man-made sources of a substance, as well as its uses and various formulations. Each substance is categorized by physical and chemical properties, air pollution factors, water and soil pollution factors, and biological effects. Pesticides, detergents, phtalates, polynuclear aromatics, and polychlorinated biphenyls are all investigated in detail. The book also features information on aquatic toxicity and biological effects, odor thresholds, sampling and analysis data, and structural formulas of over 3,000 chemicals. Tables have been refined to focus on environmentally related materials.

Product Details

ISBN-13: 9780470171721
Publisher: Wiley
Publication date: 11/03/2008
Edition description: 5th Revised ed.
Pages: 4486
Product dimensions: 8.60(w) x 11.00(h) x 1.80(d)

About the Author

Karel Verschueren, internationally known expert on air and water pollution control is President, Verschueren Environmental Consultancy.

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Note: The Figures and/or Tables mentioned in this chapter do not appear on the web.


INTRODUCTION


Since the publication of the first edition of this handbook in 1977, much more information has become available about the presence and fate of new and existing organic chemicals in the environment. These data, when given a wide distribution, will no doubt reduce the misuse of dangerous chemicals and hence their impact on the environment. The Handbook of Environmental Data on Organic Chemicals has now been updated for the third time and covers individual substances as well as mixtures and preparations.

I. ARRANGEMENT OF CATEGORIES

The information in the categories listed below is given for each product in the sequence indicated; where entries are incomplete, it may be assumed that no reliable data were provided by the references utilized.

  • Name: the commonly accepted name is the key entry.
  • Synonym: alternative names, as well as trivial names and identifiers, are indicated. Obsolete and slang names have been eliminated as far as possible.
  • Formula: the molecular and structural formulas are given.
  • CAS: the Chemical Abstracts Service number
  • Manufacturing source
  • Use, users, and formulations
  • Natural sources and occurrence
  • Man-caused sources

A. PROPERTIES The chemical and physical properties typically given are physical appearance; molecular weight (mw); melting point (mp); boiling point (bp) at 760 mm Hg unless otherwise stated; vapor pressure (vp) at different temperatures; relative vapor density (vd), the relative vapor density of air = 1; saturation concentration in air at different temperatures (sat. conc.); the maximum solubility in water at various temperatures (solub.); the liquid or solid density at room temperature; the logarithm of the octanol/ water partition coefficient (log Poct ); the logarithm of the dimensionless constant of Henry (log H).

B. AIR POLLUTION FACTORS The following data are given: conversion factors (between volume and mass units of concentration); odor threshold values and characteristics; atmospheric reactions; natural sources (and background concentrations); man-made sources (and ground level concentra-tions caused by such sources); emission control methods (and results); methods of sampling and analysis.

C. WATER AND SOIL POLLUTION FACTORS Analogous to the previous category, the following data are listed: biodegradation rate and mechanisms; oxidation parameters, such as BOD, COD, and ThOD; impact on treatment processes and on the BOD test; reduction of amenities through taste, odor, and color of the water or aquatic organisms; the quality of surface water and underground water and sediment; natural sources; man-made sources; waste water treatment methods and results; methods of sampling and analysis.

D. BIOLOGICAL EFFECTS Residual concentrations, bioaccumulation values, and toxicological effects of exposing the products to ecosystems, bacteria, plants, algae, protozoans, worms, molluscs, insects, crustaceans, fishes, amphibians and birds. The "explanatory notes" give a more detailed description of the compiled data, explain the definitions and abbreviations used throughout the book, and indicate how the data can be used to prevent or reduce environmental pollution.

II. ARRANGEMENT OF CHEMICALS

The chemicals are listed in strict alphabetical order; those that comprise two or more words are alphabetized as though they were a single word. The many prefixes used in organic chemistry are disregarded in alphabetizing because they are not considered an integral part of the name; these include ortho-, meta-, para-, alpha-, beta-, gamma-, sec, tert, sym-, as-, uns-, cis-, trans-, d-, l-, dl-, n, and N-, as well as all numerals denoting structure. However, there are certain prefixes that are an integral part of the names (iso-, di-, tri-, tetra-, cyclo-, bio-, neo-, pseudo-), and in these cases, the name is placed in its normal alphabetical position. For example, dimethylamine appears under D and isobutane under I.

III. ORDER OF ELEMENTS

Readers who are not acquainted with the definitions and abbreviations used throughout the book should consult the appropriate sections of this chapter. The data are given in the following sequence (each item will be discussed in detail).

A. PROPERTIES

    1. 1. formula
    2. 2. physical appearance
    3. 3. molecular weight (mw)
    4. 4. melting point (mp)
    5. 5. boiling point (bp)
    6. 6. vapor pressure (vp)
    7. 7. vapor density (vd)
    8. 8. saturation concentration (sat. conc.)
    9. 9. solubility (solub.)
    10. 10. density (d)
    11. 11. logarithm of the octanol/water distribution coefficient (log Poct)
    12. 12. logarithm of the dimensionless Henry's constant (log H)

B. AIR POLLUTION FACTORS

    1. 13. conversion factors
    2. 14. odor
    3. 15. atmospheric reactions
    4. 16. natural sources
    5. 17. man-made sources
    6. 18. control methods
    7. 19. air quality

C. WATER AND SOIL POLLUTION FACTORS

    1. 20. biodegradation
    2. 21. oxidation parameters
    3. 22. impact on biodegradation processes
    4. 23. odor and taste thresholds
    5. 24. water, soil, and sediment quality
    6. 25. natural sources
    7. 26. man-made sources
    8. 27. waste water treatment
    9. 28. degradation in soil
    10. 29. soil sorption

D. BIOLOGICAL EFFECTS

  • residual concentrations
  • bioaccumulation values
  • toxicological effects
      30. ecosystems
    1. 31. bacteria
    2. 32. algae
    3. 33. plants
    4. 34. worms
    5. 35. molluscs
    6. 36. insects
    7. 37. crustaceans
    8. 38. fishes
    9. 39. amphibians
    10. 40. birds

IV. EXPLANATORY ELEMENTS

A. PROPERTIES

Only the most relevant chemical and physical properties are given. Flash points, flammability limits, autoignition temperature, and the like have been omitted because they are not of direct concern to the environmentalist. These and other dangerous properties of chemicals can be found in Dangerous Properties of Industrial Materials by I. Sax. Chemicals are never 100% pure, but the nature and quantity of the impurities can have a significant impact on most environmental qualities. The following parameters are very sensitive to the presence of impurities: water solubility, odor characteristic and threshold values, BOD, and toxicity.

1. Boiling Points

The boiling points of the members of a given homologous series increase with increasing molecular weight. The boiling points rise in a uniform manner as shown in Figure 1.
If a hydrogen atom of one of the paraffin hydrocarbons is replaced by another atom or a group, an elevation of the boiling point results. Thus alkyl halides, alcohols, aldehydes, ketones, acids, etc. boil at higher temperatures than the hydrocarbons with the same carbon skeleton.
If the group introduced is of such a nature that it promotes association, a very marked rise in boiling point occurs. This effect is especially pronounced in the alcohols and acids, because hydrogen bonding can occur.

2. Vapor Pressure

The vapor pressure of a liquid or solid is the pressure of the gas in equilibrium with the liquid or solid at a given temperature. Volatilization, the evaporative loss of a chemical, depends on the vapor pressure of the chemical and on environmental conditions that influence diffusion from the evaporative surface. Volatilization is an important source of material for airborne transport and may lead to the distribution of a chemical over wide areas and into bodies of water (e. g., in rainfall) far from the site of release. Vapor pressure values give indications of the tendency of pure substances to vaporize in an unperturbed situation and thus provide a method for ranking the relative volatilities of chemicals. Vapor pressure data combined with solubility data permit calculations of rates of evaporation of dissolved organics from water using Henry's Law constants, as discussed by MacKay and Leinonen (1943) and Dilling (1944).

Chemicals with relatively low vapor pressures, high adsorptivity onto solids, or high solubility in water are less likely to vaporize and become airborne than chemicals with high vapor pressures or less affinity for solution in water or adsorption to solids and sediments. In addition, chemicals that are likely to be gases at ambient temperatures and that have low water solubility and low adsorptive tendencies are less likely to transport and persist in soils and water. Such chemicals are less likely to biodegrade or hydrolyze but are prime candidates for photolysis and for involvement in adverse atmospheric effects (such as smog formation and stratospheric alterations). On the other hand, nonvolatile chemicals are less frequently involved in significant atmospheric transport, so concerns regarding them should focus on soils and water.

Vapor pressures are expressed in mm Hg (abbreviated mm), in atmospheres (atm), in mbars, or in hectoPascals (hPa).

If vapor pressure data for certain compounds are not available, they can be derived graphically from the compounds' boiling points and the boiling point/ vapor pressure relationship for homologous series. An example is shown in Figure 2.

3. Vapor Density

The density of a gas indicates whether it will be transported along the ground, possibly subjecting surrounding populations to high exposure, or will disperse rapidly.

The concentration term vapor density is often used in discussion of vapor phase systems. Vapor density is related to equilibrium vapor pressure through the equation of state for a gas:

PV = nRT

When the mass of the substance and the gram molecular weight are substituted for the number of moles n, the following equation is obtained:

vapor density (vd) = PM/RT

    1. where
    2. P = equilibrium vapor pressure in atmospheres
    3. R = 0.082 liter atmospheres/ mol/ K
    4. M = gram molecular weight
    5. T = absolute temperature in kelvins (K)

In this book the relative vapor density (air = 1) is given because it indicates how the gas will behave upon release.

4. Water Solubility

4.1. Objectives. The water solubility of a chemical is an important characteristic for establishing that chemical's potential environmental movement and distribution. In general, highly soluble chemicals are more likely than poorly soluble chemicals to be distributed by the hydrological cycle.

Water solubility can also affect adsorption and desorption on soils and volatility from aquatic systems. Substances that are more soluble are more likely to desorb from soils and less likely to volatilize from water. Water solubility can also affect possible transformation by hydrolysis, photolysis, oxidation, reduction, and biodegradation in water. Finally, the design of most chemical tests and of many ecological and health tests requires precise knowledge of the water solubility of chemicals. Water solubility is an important parameter for assessment of all solid and liquid chemicals. Water solubility is generally not useful for gases, because their solubility in water is measured when the gas above the water is at a partial pressure of one atmosphere. Thus the solubility of gases does not usually apply to environmental assessment, because the actual partial pressure of a gas in the environment is extremely low.

4.2. Interpretation of Data. It is not unusual to find in the literature a wide range of solubilities for the same product. The oldest literature generally yields the highest solubility values. The reasons are twofold: First, in the years before and immediately after World War II, products were not as pure as they are today. Second, recent determinations are based on specific methods of analysis, such as gas chromatography. Nonspecific determinations do not distinguish between the dissolved product and the dissolved impurities; the latter, when they are much more soluble than the original product, move to the aqueous phase and are recorded as dissolved product. Nonspecific methods include turbidity measurement and TOD (Total Oxygen Demand).

The measurement of aqueous solubility does not usually impose excessive demands on chemical techniques, but measuring the solubility of very sparingly soluble compounds requires specialized procedures. This problem is well illustrated by the variability in the values quoted in the literature for products such as DDT and PCBs. This situation happens to be of some consequence; many of the compounds that are known to be significant environmental contaminants, such as DDT and PCBs, are those that have very low water solubilities.

4.3. Influence of the Composition of Natural Waters. The composition of natural waters can vary greatly. Environmental variables such as pH, water hardness, cations, anions, naturally occurring organic substances (e. g., humic and fulvic acids and hemicelluloses), and organic pollutants all affect the solubility of chemicals in water. Some bodies of water contain enough organic and inorganic impurities to significantly alter the solubility of poorly soluble chemicals.

The solubility of lower n -paraffins in salt water compared with fresh, distilled water is higher by about one order of magnitude, this difference decreasing with an increase in the molecular weight of the hydrocarbon. The increased solubility in seawater is due to simultaneous physical and chemical factors. The solubility of several higher n -paraffins (C 10 and higher) has been determined in both distilled water and seawater. In all cases, the paraffins were less soluble in seawater than in distilled water. The magnitude of the salting out effect increases with increasing molar volume of the paraffins, in accordance with the McDevit-Long Theory. This theory of salt effects attributes salting in or salting out to the effect of electrolytes on the structure of water. Because the data in the literature indicate that the lower paraffins (below C 10 ) are more soluble, and the higher n -paraffins (C 10 and higher) less soluble, in seawater than in distilled water, it is possible to speculate upon the geochemical fate of dissolved normal paraffins entering the ocean from rivers. If fresh water is saturated or near saturated with respect to normal paraffins (e. g., because of pollution), salting out of the higher paraffins will occur in the estuary. The salted out molecules may either adsorb on suspended minerals and on particulate organic matter or rise to the surface as slicks. In either case, they will follow a different biochemical pathway than if they had been dissolved. The salting out of dissolved organic molecules in estuaries applies not to n -paraffins alone, but to all natural or pollutant organic molecules whose solubilities are decreased by addition of electrolytes. Thus it is possible that regardless of the levels of dissolved organic pollutants in river water, only given amounts will enter the ocean in dissolved form because of salting out effects of estuaries. Estuaries may act to limit the amount of dissolved organic carbon entering the ocean, but they may increase the amount of particulate organic carbon entering the marine environment.

4.4. Molecular Structure-Solubility Relationship. Because water is a polar compound, it is a poor solvent for hydrocarbons. Olefinic and acetylenic linkages and benzenoid structures do not greatly affect the polarity. Hence, unsaturated or aromatic hydrocarbons are not very different from paraffins in their water solubility. The introduction of halogen atoms does not alter the polarity appreciably. It does increase the molecular weight, and for this reason the water solubility always falls off. On the other hand, salts are extremely polar. Other compounds lie between these two extremes. Here are found the alcohols, esters, ethers, acids, amines, nitriles, amides, ketones, and aldehydes-to mention a few of the classes that occur frequently.

As might be expected, acids and amines generally are more soluble than neutral compounds. The amines probably owe their abnormally high solubility to their tendency to form hydrogen-bonded complexes with water molecules. This theory is in harmony with the fact that the solubility of amines diminishes as the basicity decreases. It also explains the observation that many tertiary amines are more soluble in cold than in hot water. Apparently, at lower temperatures the solubility of the hydrate is involved, whereas at higher temperatures the hydrate is unstable and the solubility measured is that of the free amine.

Monofunctional ethers, esters, ketones, aldehydes, alcohols, nitriles, amides, acids, and amines may be considered together with respect to water solubility. As a homologous series is ascended, the hydrocarbon (nonpolar) part of the molecule continually increases while the polar function remains essentially unchanged. There follows, then, a trend toward a decrease in the solubility in polar solvents such as water.

In general, an increase in molecular weight leads to an increase in intermolecular forces in a solid. Polymers and other compounds of high molecular weight generally exhibit low solubilities in water and ether. Thus formaldehyde is readily soluble in water, whereas paraformaldehyde is insoluble:

Glucose is soluble in water, but its polymers-starch, glycogen, and cellulose-are insoluble. Many amino acids are soluble in water, but their condensation polymers, the proteins, are insoluble.

Lindenberg (1803) proposed a relationship between the logarithm of the solubility of a hydrocarbon in water and the molar volume of the hydrocarbon. If the logarithm of the solubilities of the hydrocarbons in water is plotted against the molar volumes of the hydrocarbons, a straight line is obtained. This relationship has been worked out further by C. McAuliffe, and solubilities as a function of molar volumes for a number of homologous series of hydrocarbons have been presented graphically.

From the given correlation between molecular structure and solubility, the following conclusions may be drawn:

    Branching increases water solubility for paraffin, olefin, and acetylene hydrocarbons, but not for cycloparaffins, cyclo-olefins, and aromatic hydrocarbons.
    For a given carbon number, ring formation increases water solubility.
    Addition of a double bond to the molecule, ring, or chain increases water solubility. The addition of a second and third double bond to a hydrocarbon of given carbon number proportionately increases water solubility (Table 1).
    A triple bond in a chain molecule increases water solubility to a greater extent than two double bonds.

Table 1. Influence of Double Bonds on Aqueous Solubility of Cyclic Hydrocarbons (at room temperature) (242).

Cary T. Chiou et al. (382) found a good correlation between solubilities of organic compounds and their octanol/ water partition coefficients. Furthermore, functional groups such as chlorine atoms, methyl groups, hydroxyl groups, and benzene rings showed additive effects on the logarithm of the octanol/water partition coefficient (log P oct) of the parent molecule. This allowed the calculation of log P oct values for many organic compounds based on the log P oct value for the parent compound and the additive effects of the functional groups. Because of the correlation between solubilities of organic compounds and log P oct, it is not surprising to find the same additive effects of functional groups on their water solubility. Table 2 shows this influence of functional groups on the solubility of benzene derivatives. Solubilities of homologous series of organic compounds are plotted in Figures 3, 4, and 5.

Effects that cannot be accounted for by this additive-constitutive character of the solubility are

  • steric effects that cause shielding of an active function
  • intra-and intermolecular hydrogen bonding (e. g., trihydroxyphenols)
  • branching
  • inductive effects of one substituent on another
  • conformational effects, such as "balling up" of an aliphatic chain

4.5. Solubility of Mixtures. Mixtures of compounds, whether they are natural such as oil or formulations such as many pesticides, behave differently from the single compounds when brought into contact with water. Indeed, each component of the mixture will partition between the aqueous phase and the mixture.

Components with a high aqueous solubility tend to move toward the aqueous phase while the "unsoluble" components remain in the other phase. From this, it follows that the fractional composition of the water soluble fraction (WSF) will differ from the original composition of the mixture and that concentrations of the components of the WSF are generally lower than the maximum solubilities for the individual components. Examples are shown in Tables 3 and 4.

5. Octanol/ Water Partition Coefficient

The ability of some chemicals to move through the food chain, resulting in higher and higher concentrations at each trophic level, has been termed biomagnification or bioconcentration. The widespread distributions of DDT and the polychlorinated biphenyls (PCBs) have become classic examples of such movement.

From an environmental point of view, this phenomenon becomes important when the acute toxicity of the agent is low and the physiological effects go unnoticed until the chronic effects become evident. For this reason, prior knowledge of the bioconcentration potential of new or existing chemicals is desired. However, determining the bioconcentration factor of a chemical on a number of animals or in a food chain is expensive and time-consuming. If a simple relationship could be established between physico-chemical properties of a chemical and its ability to bioconcentrate, it would be of great benefit in planning the future direction of any development work on a new chemical and in directing research efforts to determine the distribution and ultimate fate of a limited number of selected chemicals.

Table of Contents

Introduction.

I. Arrangement of Categories.

A. .Properties.

B. Air Pollution Factors.

C. Water and Soil Pollution Factors.

D. Biological Effects.

II. Arrangement of Chemicals.

III. Order of Elements.

A. Properties.

B. Air Pollution Factors.

C. Water and Soil Pollution Factors.

D. Biological Effects.

IV. Explanatory Elements.

A. Properties.

1. Boiling Points.

2. Vapor Pressure.

3. Vapor Density.

4. Water Solubility.

5. Octanol/Water Partition Coefficient.

6. Henry's Constant (H).

B. Air Pollution Factors.

1. Conversion between Volume and Mass Units of Concentration.

2. Odor.

3. Hazard Potentials of Atmospheric Pollutants.

4. Natural Sources.

5. Manmade Sources.

6. Control Methods.

C. Water Pollution Factors.

1. Biodegradation.

2. Oxidation Parameters.

3. Impact on Biodegradation Process.

4. Waste Water Treatment.

5. Alteration and Degradation Processes.

D. Biological Effects.

1. Arrangement of Data.

2. Classification List.

3. Organisms Used in Experimental Work with Polluting Substances or in Environmental.

Surveys.

4. Discussion of Biological Effects Tests.

Glossary.

Abbreviations.

Environmental Data.

Bibliography.

Molecular Index.

Cas Cross-Index.

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