You are on page 1of 118

CHE 103 Chemistry

B. SC AIRCRAFT MAINTENANCE ENGINEERING INDEX

MODULE MODULE 1 MODULE 2 MODULE 3 MODULE 4 MODULE 5 MODULE 6 MODULE 7

TOPIC ATOMIC STRUCTURE ACIDS AND BASES: FUNDAMENTALS CHEMICAL KINETICS FUNDAMENTALS OF ORGANIC CHEMISTRY ELECTROCHEMISTRY GASEOUS STATE ENVIRONMENTAL CHEMISTRY

PAGE NOS. 4 - 26 27 - 37 38 - 59 60 - 72 73 - 82 83 - 91 92 - 118

CONTENTS
MODULE 1 ATOMIC STRUCTURE
Module 1A Module 1B Module 1C Module 1D Module 1E Module 1F Module 1G Module 1H Atomic Structure Introduction Sub-Atomic Particles Discovery of Electron Discovery of Protons and Neutrons Atomic Models Wave Nature of Electromagnetic Radiation Electronic Energy Levels: Atomic Spectra Chemical Bonding

MODULE 2 ACIDS AND BASES: FUNDAMENTALS


Module 2A Module 2B Module 2C Module 2D Module 2E Module 2F Module 2G Module 2H Arrhenius Theory Bronstedt-Lowry Theory Lewis Acids and Bases Reactions of Acids and Bases with Water Equilibrium Equations Strengths of Acids and Bases (The pH and pOH Scales) pH Concept Weak acids and Weak Bases

MODULE 3 CHEMICAL KINETICS


Module 3A Module 3B Module 3C Module 3D Module 3E Module 3F Module 3G Module 3H Module 3I Module 3J Laws of Thermodynamics Rates of Reaction and the Rate Law for a Reaction Different Ways of Expressing the Rate of Reaction Order of Molecularity Reaction Rates Rate Laws Integrated forms of Rate Laws Simple Second Order Rate Equations Reaction Mechanisms Chain Reactions

MODULE 4 Module 4A Module 4B Module 4C Module 4D Module 4E MODULE 5 Module 5A Module 5B Module 5C Module 5D

FUNDAMENTALS OF ORGANIC CHEMISTRY Introduction Empirical and Molecular Formulas Structural Isomerism Naming of Alkanes The Importance of Functional Groups ELECTROCHEMISTRY Faradays Laws Redox Reactions Electrochemical Cells Industrial Electrochemistry:

MODULE 6

GASEOUS STATE

Module 6A Boyles Law Module 6B Charles Law Module 6C Grahams Law of Gaseous Diffusion MODULE7 Module 7A Module 7B Module 7C Module 7D Module 7E Module 7F Module 7G Module 7H Module 7I Module 7J ENVIRONMENTAL CHEMISTRY The Atmosphere The Hydrosphere The Geosphere The Biosphere The Flora and Fauna Natural Resources Consumption Atmospheric Chemistry Air Pollution Aquatic Chemistry and Water pollution Soil Chemistry

MODULE 1 ATOMIC STRUCTURE _____________________________________________


Module 1A - ATOMIC STRUCTURE -INTRODUCTION The existence of atoms has been proposed since the time of early Indian and Greek philosophers (400 B.C.) who were of the view that atoms are the fundamental building blocks of matter. According to them, the continued subdivisions of matter would ultimately yield atoms which would not be further divisible. The word atom has been derived from the Greek word a-tomio which means uncutable or non-divisible. These earlier ideas were mere speculations and there was no way to test them experimentally. These ideas remained dormant for a very long time and were revived again by scientists in the nineteenth century. An atom is composed of three different types of particles; protons, neutrons, and electrons. Because atoms are neutrally charged, an atom will always have the same number of protons and electrons. This idea that atoms are neutral is by definition. Atoms always have the same number of negative and positive charges. By the way, atoms become ions when they become charged. This change can occur when an atom has either lost or gained some electrons. So ions do not have the same number of protons and electrons.

Figure 1

The example atom to the left or above, represents Helium which is usually a gas. Helium has 2 protons, 2 neutrons, and 2 electrons. The protons and neutrons form the nucleus and the electrons (see Figure 1). Now what is it about this atom that makes it a Helium atom? It is the number of protons that determines what kind of element the atom will be. A Helium atom will always have 2 protons. If it is a non-charged atom, it will also have 2 electrons. There are; However, several varieties of Helium and they differ in the number of neutrons. Scientists call these varieties isotopes. Most of the Helium that we breath in our air is Helium 4 which has 2 neutrons. There are also a small number of Helium 3 atoms in our air as well. Both of these varieties of Helium are stable. They do not break down. So they are not radioactive. The atomic theory of matter was first proposed on a firm scientific basis by John Dalton, a British school teacher in 1808. His theory, called Daltons atomic theory, regarded the atom as the ultimate particle of matter. form a cloud that surrounds the nucleus

Module 1B

Sub-Atomic Particles

Daltons atomic theory was able to explain the law of conservation of mass, law of constant composition and law of multiple proportion very successfully. However, it failed to explain the results of many experiments, for example, it was known that substances like glass or ebonite when rubbed with silk or fur generate electricity. Many different kinds of sub-atomic particles were discovered in the twentieth century. However, in this section we will talk about only two particles, namely electron and proton. Parts of the Atom Electronsvery small subatomic particles with negative charge, move through this volume of space outside the nucleus. This volume of space is organized into shells, subshells, and orbitals. That involves quantum mechanics, which we will postpone as long as possible. The nucleusthe central portion of the atom containing most of the mass but least of its volume. 5

It is composed of Protonspositively charged subatomic particles. Each element has a unique number of protons. Neutronsneutral subatomic particles are called nuetrons. The atoms of an element may have different numbers of neutrons. If so, they are said to be isotopes of one another. For example, carbon has three different naturally occurring isotopes. All of the isotopes of carbon have six protons in their nuclei. One of the isotopes has six neutrons, one has seven, and one has eight. Properties of Fundamental Particles Absolute Charge / C -1.6022 X 10-19 +1.6022 X 10-19 0 Relative Charge -1 +1 0

Name Electron Proton Neutron

Symbol e p n

Mass / kg 9.10939 X 10-31 1.67262 X 10-27 1.67493 X 10-27

Atomic numberthe number of proton in an atom of an element. For example, all of the atoms of the element iron have 26 protons, so the mass number of iron is 26. The atomic number is unique for each element. During nuclear reactions, an element may change into another. For clarity and as an aid to balancing nuclear reaction equations, the atomic number may be written as part of the atomic symbol. If so, it appears at the bottom left, as 26Fe. Mass numberthe number of protons and neutrons in an atom of a specific isotope of an element. For example, oxygen has an atomic number of eight. The isotope of oxygen having ten neutrons has a mass number of 18. The atomic symbol may include the mass number, if it is relevant. The mass number is written at the top left, as 18O. Atomic weightthe average mass of the atoms of an element taking into account the masses of the various isotopes and their relative abundance. For example, oxygen has an atomic weight of 15.9994. This means that the average of the atoms masses is 15.9994 atomic mass units (amu). A proton has a mass of slightly more than one amu as does a neutron. An electrons mass is so small that it would close to two thousand electrons to be as massive as a proton. Most of the naturally occurring atoms of oxygen have eight protons, eight neutrons,

and eight electrons giving a mass of close to 16 amu. Many students assume that the mass number (always an integer) is a rounded form of the atomic weight (never an integer). NOPE. The atomic weight is an average while the mass number is a particle count. The atomic weight can be found on the periodic table. It is never written as part of an atomic symbol. Law of conservation of matter (or mass): During any ordinary chemical reaction, mass is neither lost nor gained. This was known in Daltons time. It is explained by the idea that atoms are finite and indestructible, so a sample of matter cant lose or gain mass because it doesnt lose or gain atoms. Law of constant composition: A compound always contains the same types of elements in the same relative proportions by mass. For example, water is always formed from hydrogen and oxygen and no other elements, and, water has 8 grams of oxygen for every gram of hydrogen. This law was known in Daltons day. It is explained by the idea that chemical reactions are groupings of atoms. Law of multiple proportions: If two or more elements can combine to form two or more compounds, for a fixed amount of one of the elements, the other(s) will be present in the compounds in small whole number ratios. For example, carbon reacts with oxygen to form two compounds, carbon monoxide and carbon dioxide. So, what is the difference between the law of constant composition and the law of multiple proportions? The law of constant composition compares the amounts of two elements in one compound while the law of multiple proportions compares the amounts of two elements in two compounds. Actually, by reducing one of the elements to unity, the law of multiple proportions finds a whole number ratio of the other one element in two compounds (and, therefore, is much more complicated). Atomic Number and Mass Number: The presence of positive charge on the nucleus is due to the protons in the nucleus. As established earlier, the charge on the proton is equal but opposite to that of electron. The number of protons present in the nucleus is equal to atomic number (Z ). For example, the number of protons in the hydrogen nucleus is 1, in sodium atom it is 11, therefore their atomic numbers are 1 and 11 respectively. In order to keep the electrical neutrality, the number of electrons in an atom is equal to the number of protons (atomic number, Z ). For example, number of electrons in hydrogen atom and sodium atom 7

are 1 and 11 respectively. Atomic number (Z) = number of protons in the nucleus of an atom = number of electrons in a nuetral atom. While the positive charge of the nucleus is due to protons, the mass of the nucleus, due to protons and neutrons. It is known that protons and neutrons present in the nucleus are collectively known as nucleons. The total number of nucleons is termed as mass number (A) of the atom. mass number (A) = number of protons (Z) + number of neutrons (n). Isobars and Isotopes: The composition of any atom can be represented by using the normal element symbol (X) with super-script on the left hand side as the atomic mass number (A) and subscript (Z) on the left hand side as the atomic number (i.e., AZX). Isobars are the atoms with same mass number but different atomic number for example, 6C and 7N. On the other hand, atoms with identical atomic number but different atomic mass number are known as Isotopes. In other words (according to equation 2.4), it is evident that difference between the isotopes is due to the presence of different number of neutrons present in the nucleus. For example, considering of hydrogen atom again, 99.985% of hydrogen atoms contain only one proton. This isotope is called protium (11H). Rest of the percentage of hydrogen atom contains two other isotopes, the one containing 1 proton and 1 neutron is called deuterium (12D, 0.015%) and the other one possessing 1 proton and 2 neutrons is called tritium (13T). The latter isotope is found in trace amounts on the earth. Other examples of commonly occuring isotopes are: carbon atoms containing 6, 7 and 8 neutrons besides 6 protons (12C, 13C, 14C); chlorine atoms containing 18 and 20 neutrons besides 17 protons ( 35Cl, 37Cl ). Lastly an important point to mention regarding isotopes is that chemical properties of atoms are controlled by the number of electrons, which are determined by the number of protons in the nucleus. Number of neutrons present in the nucleus have very little effect on the chemical properties of an element. Therefore, all the isotopes of a given element show same chemical behaviour. Module 1C Discovery of Electron

In 1830, Michael Faraday showed that if electricity is passed through a solution of an electrolyte, chemical reactions occurred at the electrodes, which resulted in the liberation and deposition of matter at the electrodes. He formulated certain laws which you will study in class XII. These results suggested the particulate nature of electricity. An insight into the

structure of atom was obtained from the experiments on electrical discharge through gases. Before we discuss these results we need to keep in mind a basic rule regarding the behaviour of charged particles : Like charges repel each other and unlike charges attract each other.

Figure 2 Cathode ray tube In mid 1850s many scientists mainly Faraday began to study electrical discharge in partially evacuated tubes, known as cathode ray discharge tubes. It is depicted in Figure 2. A cathode ray tube is made of glass containing two thin pieces of metal, called electrodes, sealed in it. The electrical discharge through the gases could be observed only at very low pressures and at very high voltages. The pressure of different gases could be adjusted by evacuation. When sufficiently high voltage is applied across the electrodes, current starts flowing through a stream of particles moving in the tube from the negative electrode (cathode) to the positive electrode (anode). These were called cathode rays or cathode ray particles. The flow of current from cathode to anode was further checked by making a hole in the anode and coating the tube behind anode with phosphorescent material zinc sulphide. When these rays, after passing through anode, strike the zinc sulphide coating, a bright spot on the coating is developed(same thing happens in a television set) The results of these experiments are summarised below; (i) The cathode rays start from cathode and move towards the anode. (ii) These rays

themselves are not visible but their behaviour can be observed with the help of certain kind of materials (fluorescent or phosphorescent) which glow when hit by them. Television picture 9

tubes are cathode ray tubes and television pictures result due to fluorescence on the television screen coated with certain fluorescent or phosphorescent materials. (iii) In the absence of electrical or magnetic field, these rays travel in straight lines. (iv) In the presence of electrical or magnetic field, the behaviour of cathode rays are similar to that expected from negatively charged particles, suggesting that the cathode rays consist of negatively charged particles, called electrons. (v) The characteristics of cathode rays (electrons) do not depend upon the material of electrodes and the nature of the gas present in the cathode ray tube. Thus, we can conclude that electrons are basic constituent of all the atoms. Charge to Mass Ratio of Electron: In 1897, British physicist J.J. Thomson measured the ratio of electrical charge (e) to the mass of electron (m e ) by using cathode ray tube and applying electrical and magnetic field perpendicular to each other as well as to the path of electrons. Thomson argued that the amount of deviation of the particles from their path in the presence of electrical or magnetic field depends upon: (i) the magnitude of the negative charge on the particle, greater the magnitude of the charge on the particle, greater is the interaction with the electric or magnetic field and thus greater is the deflection. (ii) the mass of the particle lighter the particle, greater the deflection. (iii) the strength of the electrical or magnetic field the deflection of electrons from its original path increases with the increase in the voltage across the electrodes, or the strength of the magnetic field. Module 1D Discovery of Protons and Neutrons

Electrical discharge carried out in the modified cathode ray tube led to the discovery of particles carrying positive charge, also known as canal rays. The characteristics of these positively charged particles are listed below. (i) unlike cathode rays, the positively charged particles depend upon the nature of gas present in the cathode ray tube. These are simply the positively charged gaseous ions. (ii) The charge to mass ratio of the particles is found to depend on the gas from which these originate. (iii) Some of the positively charged particles carry a multiple of the fundamental unit of electrical charge. (iv) The behaviour of these particles in the magnetic or electrical field is opposite to that observed for electron or cathode rays. The smallest and lightest positive ion was obtained from hydrogen and was called proton. This positively charged particle was characterised in 1919. Later, a need was

10

felt for the presence of electrically neutral particle as one of the constituent of atom. These particles were discovered by Chadwick (1932) by bombarding a thin sheet of beryllium by particles. When electrically neutral particles having a mass slightly greater than that of the protons was emitted. He named these particles as neutrons. Module 1E Atomic Models

Daltons Atomic Theory There were a few important theories that tried to explain what was happening on a fundamental level during chemical changes. Some chemistry professors will want their students to know which ancient Greek first postulated the existence of the atom, for example. Although everybody agrees, in principle, that a foundation in the history of chemistry is nice, the guys who actually expect you to know this stuff coming in to General Chemistry are in the minority. However, everyone will expect you to know Dalton and his theory. That is because half of the first semester lab experiments are based on Daltons model of the atom. Postulates of Daltons theory: a) Matter is made up of tiny, indivisible particles called atoms, b) The atoms of any given element are identical to one another and different from the atoms of any other element, c) Atoms are neither created nor destroyed during ordinary chemical reactions, nor are they converted to another type of atom, d) During chemical changes atoms are regrouped to form chemical compounds which always contain the same type and relative proportion of atoms. Thomson Model of Atom J. J. Thomson, in 1898, proposed that an atom possesses a spherical shape (radius approximately 1010 m) in which the positive charge is uniformly distributed. The electrons are embedded into it in such a manner as to give the most stable electrostatic arrangement (Fig. 2.4). Many different names are given to this model, for example, plum pudding, raisin pudding or watermelon. This model can be visualised as a pudding or watermelon of positive charge with plums or seeds (electrons) embedded into it. An important feature of this model is that the mass of the atom is assumed to be uniformly distributed over the atom. Although this model was able to explain the overall neutrality of the atom, but was not consistent with the 11

results of later experiments. Thomson was awarded Nobel Prize for physics in 1906, for his theoretical and experimental investigations on the conduction of electricity by gases. Henri Becqueral (1852-1908) observed that there are certain elements which emit radiation on their own and named this phenomenon as radioactivity and the elements known as radioactive elements. This field was developed by Marie Curie, Piere Curie, Rutherford and Fredrick Soddy. It was observed that three kinds of rays i.e., , - and -rays are emitted. Rutherford found that -rays consists of high energy particles carrying two units of positive charge and four unit of atomic mass. He concluded that - particles are helium nuclei as when - particles combined with two electrons yielded helium gas. -rays are negatively charged particles similar to electrons. The -rays are high energy radiations like X-rays, are neutral in nature and do not consist of particles. As regards penetrating power, -particles are the least, followed by -rays (100 times that of particles) and -rays (1000 times of that -particles). Rutherfords Nuclear Model of Atom Rutherford and his students (Hans Geiger and Ernest Marsden) bombarded very thin gold foil with particles. Rutherfords famous particle scattering experiment is given below:

A stream of high energy particles from a radioactive source was directed at a thin foil (thickness 100 nm) of gold metal. The thin gold foil had a circular fluorescent zinc sulphide screen around it. Whenever particles struck the screen, a tiny flash of light was produced at that point. The results of scattering experiment were quite unexpected. According to Thomson model of atom, the mass of each gold atom in the foil should have been spread evenly over the 12

entire atom, and particles had enough energy to pass directly through such a uniform distribution of mass. It was expected that the particles would slow down and change directions only by a small angles as they passed through the foil. It was observed that : i) most of the particles passed through the gold foil un-deflected. ii) a small fraction of the particles was deflected by small angles. iii) a very few particles (1 in 20,000) bounced back, that is, were deflected by nearly 180. On the basis of the observations, Rutherford drew the following conclusions regarding the structure of atom : a) A few positively charged particles were deflected. The deflection must be due to enormous repulsive force showing that the positive charge of the atom is not spread throughout the atom as Thomson had presumed. The positive charge has to be concentrated in a very small volume that repelled and deflected the positively charged particles, b) Calculations by Rutherford showed that the volume occupied by the nucleus is negligibly small as compared to the total volume of the atom. The radius of the atom is about 1010 m, while that of nucleus is 1015 m. One can appreciate this difference in size by realising that if a cricket ball represents a nucleus, then the radius of atom would be about 5 km. On the basis of above observations and conclusions, Rutherford proposed the nuclear model of atom (after the discovery of protons). According to this model : a) The positive charge and most of the mass of the atom was densely concentrated in extremely small region. This very small portion of the atom was called nucleus by Rutherford; b) The nucleus is surrounded by electrons that move around the nucleus with a very high speed in circular paths called orbits. Thus, Rutherfords model of atom resembles the solar system in which the nucleus plays the role of sun and the electrons that of revolving planets; c) Electrons and the nucleus are held together by electrostatic forces of attraction. BOHRS Atomic Model Neils Bohr (1913) was the first to explain quantitatively the general features of hydrogen atom structure and its spectrum. Though the theory is not the modern quantum mechanics, it can still be used to rationalize many points in the atomic structure an d spectra. Bohrs model for hydrogen atom is based on the following postulates ai) The electron in the hydrogen atom can move around the nucleus in a circular path of fixed radius and energy. These paths are called orbits, stationary states or allowed energy states. These orbits are arranged concentrically around the nucleus, b) The energy of an electron in the orbit does not change 13

with time. However, the electron will move from a lower stationary state to a higher stationary state when required amount of energy is absorbed by the electron or energy is emitted when electron moves from higher stationary state to lower stationary state. The energy change does not take place in a continuous manner. Thus an electron can move only in those orbits for which its angular momentum is integral multiple of h/2 that is why only certain fixed orbits are allowed. The details regarding the derivation of energies of the stationary states used by Bohr, are quite complicated and will be discussed in higher classes. However, according to Bohrs theory for hydrogen atom: a) The stationary states for electron are numbered n = 1,2,3.......... These integral numbers (Section 2.6.2) are known as Principal quantum numbers. b) The radii of the stationary states are expressed as : r n = n2 a0 (2.12) where a0 = 52,9 pm. Thus the radius of the first stationary state, called the Bohr radius, is 52.9 pm. Normally the electron in the hydrogen atom is found in this orbit (that is n=1). As n increases the value of r will increase. In other words the electron will be present away from the nucleus. c) The most important property associated with the electron, is the energy of its stationary state. It is given by the expression. Quantum Mechanical Model of the Atom: Classical mechanics, based on Newtons laws of motion, successfully describes the motion of all macroscopic objects such as a falling stone, orbiting planets etc., which have essentially a particle-like behaviour as shown in the previous section. However it fails when applied to microscopic objects like electrons, atoms, molecules etc. This is mainly because of the fact that classical mechanics ignores the concept of dual behaviour of matter especially for subatomic particles and the uncertainty principle. The branch of science that takes into account this dual behaviour of matter is called quantum mechanics. Quantum mechanics is a theoretical science that deals with the study of the motions of the microscopic objects that have both observable wave like and particle like properties. It specifies the laws of motion that these objects obey. When quantum mechanics is applied to macroscopic objects (for which wave like properties are insignificant) the results are the same as those from the classical mechanics.

14

Quantum mechanics was developed independently in 1926 by Werner Heisenberg and Erwin Schrdinger. Here, however, we shall be discussing the quantum mechanics which is based on the ideas of wave motion. The fundamental equation of quantum mechanics was developed by Schrdinger and it won him the Nobel Prize in Physics in 1933. This equation which incorporates wave-particle duality of matter as proposed by de Broglie is quite complex and knowledge of higher mathematics is needed to solve it. You will learn its solutions for different systems in higher classes. For a system (such as an atom or a molecule whose energy does not change with time) the Schrdinger equation is written as H = E where H is a mathematical operator called Hamiltonian. Schrdinger gave a recipe of constructing this operator from the expression for the total energy of the system. The total energy of the system takes into account the kinetic energies of all the sub-atomic particles (electrons, nuclei), attractive potential between the electrons and nuclei and repulsive potential among the electrons and nuclei individually. Solution of this equation gives E and . Module 1F Wave Nature of Electromagnetic Radiation

James Maxwell (1870) was the first to give a comprehensive explanation about the interaction between the charged bodies and the behaviour of electrical and magnetic fields on macroscopic level. He suggested that when electrically charged particle moves under accelaration, alternating electrical and magnetic fields are produced and transmitted. These fields are transmitted in the forms of waves called electromagnetic wavesor electromagnetic radiation.

Figure 3 Electromagnetic Spectrum 15

Light is the form of radiation known from early days and speculation about its nature dates back to remote ancient times. In earlier days (Newton) light was supposed to be made of particles (corpuscules). It was only in the 19th century when wave nature of light was established. Maxwell was again the first to reveal that light waves are associated with oscillating electric and magnetic character. Although electromagnetic wave motion is complex in nature, we will consider here only a few simple properties. (i) The oscillating electric and magnetic fields produced by oscillating charged particles are perpendicular to each other and both are perpendicular to the direction of propagation of the wave. Simplified picture of electromagnetic wave. (ii) Unlike sound waves or water waves, electromagnetic waves do not require medium and can move in vacuum. It is now well established that there are many types of electromagnetic radiations, which differ from one another in wavelength (or frequency). These constitute what is called electromagnetic spectrum (Figure 3). Different regions of the spectrum are identified by different names. Some examples are: radio frequency region around 106 Hz, used for broadcasting; microwave region around 1010 Hz used for radar; infrared region around 1013 Hz used for heating; ultraviolet region around 1016Hz a component of suns radiation. The small portion around 1015 Hz, is what is ordinarily called visible light. It is only this part which our eyes can see (or detect). Special instruments are required to detect non-visible radiation. Different kinds of units are used to represent electromagnetic radiation. These radiations are characterised by the properties, namely, frequency ( ) and wavelength (). The SI unit for frequency ( ) is hertz (Hz, s1), after Heinrich Hertz. It is defined as the number of waves that pass a given point in one second. Wavelength should have the units of length and as you know that the SI units of length is meter (m). Since electromagnetic radiation consists of different kinds of waves of much smaller wavelengths, smaller units are used. Figure 3 shows various types of electro-magnetic radiations which differ from one another in wavelengths and frequencies. In vacuum all types of electromagnetic radiations, regardless of wavelength, travel at the same speed, i.e., 3.0 108 m s1 (2.997925 108 m s1, to be precise). This is called speed of light and is given the symbol c. The frequency ( ), wavelength () and velocity of light (c) are related by the equation. c = . The other commonly used quantity specially in spectroscopy, is the wave number ( ). It is defined as the number of wavelengths per unit length. Its units are reciprocal of wavelength unit, i.e., m1. However commonly used unit is cm1 (not SI unit). The

16

proportionality constant, h is known as Plancks constant and has the value 6.62610 34 J s. With this theory, Planck was able to explain the distribution of intensity in the radiation from black body as a function of frequency or wavelength at different temperatures. Albert Einstein, a German born American physicist, is regarded by many as one of the two great physicists the world has known (the other is Isaac Newton). His three research papers (on special relativity, Brownian motion and the photoelectric effect), fetched him the Nobel Prize in Physics in 1921 for his explanation of the photoelectric effect. Einstein (1905) was able to explain the photoelectric effect using Plancks quantum theory of electromagnetic radiation as a starting point. Shining a beam of light on to a metal surface can, therefore, be viewed as shooting a beam of particles, the photons. When a photon of sufficient energy strikes an electron in the atom of the metal, it transfers its energy instantaneously to the electron during the collision and the electron is ejected without any time lag or delay. Greater the energy possessed by the photon, greater will be transfer of energy to the electron and greater the kinetic energy of the ejected electron. In other words, kinetic energy of the ejected electron is proportional to the frequency of the electromagnetic radiation. Since the striking photon has energy equal to h and the minimum energy required to eject the electron is h0 (also called work function, W0; then the difference in energy (h h0 ) is transferred as the kinetic energy of the photoelectron. Following the conservation of energy principle, the kinetic energy of the ejected electron is given by the equation h= h0 + 1/2mv2 where m is the mass of the electron (e) and v is the velocity associated with the ejected electron. Lastly, a more intense beam of light consists of larger number of photons, consequently the number of electrons ejected is also larger as compared to that in an experiment in which a beam of weaker intensity of light is employed. Module 1G Electronic Energy Levels: Atomic Spectra

The speed of light depends upon the nature of the medium through which it passes. As a result, the beam of light is deviated or refracted from its original path as it passes from one medium to another. It is observed that when a ray of white light is passed through a prism, the 17

wave with shorter wavelength bends more than the one with a longer wavelength. Since ordinary white light consists of waves with all the wavelengths in the visible range, a ray of white light is spread out into a series of coloured bands called spectrum. The light of red colour which has longest wavelength is deviated the least while the violet light, which has shortest wavelength is deviated the most. The spectrum of white light, that we can see, ranges from violet at 7.50 1014 Hz to red at 41014 Hz. Such a spectrum is called continuous spectrum. Continuous because violet merges into blue, blue into green and so on. A similar spectrum is produced when a rainbow forms in the sky. Remember that visible light is just a small portion of the electromagnetic radiation (Fig.2.7). When electromagnetic radiation interacts with matter, atoms and molecules may absorb energy and reach to a higher energy state. With higher energy, these are in an unstable state. For returning to their normal (more stable, lower energy states) energy state, the atoms and molecules emit radiations in various regions of the electromagnetic spectrum. Emission and Absorption Spectra: The spectrum of radiation emitted by a substance that has absorbed energy is called an emission spectrum. Atoms, molecules or ions that have absorbed radiation are said to be excited. To produce an emission spectrum, energy is supplied to a sample by heating it or irradiating it and the wavelength (or frequency) of the radiation emitted, as the sample gives up the absorbed energy, is recorded. An absorption spectrum is like the photographic negative of an emission spectrum. A continuum of radiation is passed through a sample which absorbs radiation of certain wavelengths. The missing wavelength which corresponds to the radiation absorbed by the matter, leave dark spaces in the bright continuous spectrum. The study of emission or absorption spectra is referred to as spectroscopy. The spectrum of the visible light, as discussed above, was continuous as all wavelengths (red to violet) of the visible light are represented in the spectra. The emission spectra of atoms in the gas phase, on the other hand, do not show a continuous spread of wavelength from red to violet, rather they emit light only at specific wavelengths with dark spaces between them. Such spectra are called line spectra or atomic spectra because the emitted radiation is identified by the appearance of bright lines in the spectra. Line emission spectra are of great interest in the study of electronic structure. Each element has a unique line emission spectrum. The 18

characteristic lines in atomic spectra can be used in chemical analysis to identify unknown atoms in the same way as finger prints are used to identify people. The exact matching of lines of the emission spectrum of the atoms of a known element with the lines from an unknown sample quickly establishes the identity of the latter, German chemist, Robert Bunsen (18111899) was one of the first investigators to use line spectra to identify elements. Elements like rubidium (Rb), caesium (Cs) thallium (Tl), indium (In), gallium (Ga) and scandium (Sc) were discovered when their minerals were analysed by spectroscopic methods. The element helium (He) was discovered in the sun by spectroscopic method. Schrdinger Equation: When Schrdinger equation is solved for hydrogen atom, the solution gives the possible energy levels the electron can occupy and the corresponding wave function(s) () of the electron associated with each energy level. These quantized energy states and corresponding wave functions which are characterized by a set of three quantum numbers (principal quantum number n, azimuthal quantum number l and magnetic quantum number ml ) arise as a natural consequence in the solution of the Schrdinger equation. When an electron is in any energy state, the wave function corresponding to that energy state contains all information about the electron. The wave function is a mathematical function whose value depends upon the coordinates of the electron in the atom and does not carry any physical meaning. Such wave functions of hydrogen or hydrogen like species with one electron are called atomic orbitals. Such wave functions pertaining to one-electron species are called one-electron systems. The probability of finding an electron at a point within an atom is proportional to the ||2 at that point. The quantum mechanical results of the hydrogen atom successfully predict all aspects of the hydrogen atom spectrum including some phenomena that could not be explained by the Bohr model. In view of the shortcoming of the Bohrs model, attempts were made to develop a more suitable and general model for atoms. Two important developments which contributed significantly in the formulation of such a model were : Dual behaviour of matter and Heisenberg uncertainty principle. Dual Behaviour of Matter: The French physicist, de Broglie in 1924 proposed that matter, like radiation, should also exhibit dual behaviour i.e., both particle and wavelike properties. This means that just as the photon has momentum as well as wavelength, electrons should

19

also have momentum as well as wavelength, de Broglie, from this analogy, gave the following relation between wavelength () and momentum (p) of a material particle. E = hf and = h/p (de Broglie relations)

Heisenbergs Uncertainty Principle: Werner Heisenberg a German physicist in 1927, stated uncertainty principle which is the consequence of dual behaviour of matter and radiation. It states that it is impossible to determine simultaneously, the exact position and exact momentum (or velocity) of an electron. The uncertainty principle can be best understood with the help of an example. Suppose you are asked to measure the thickness of a sheet of paper with an unmarked meter stick. Obviously, the results obtained would be extremely inaccurate and meaningless, In order to obtain any accuracy, you should use an instrument graduated in units smaller than the thickness of a sheet of the paper. Analogously, in order to determine the position of an electron, we must use a meter stick calibrated in units of smaller than the dimensions of electron (keep in mind that an electron is considered as a point charge and is therefore, dimensionless). To observe an electron, we can illuminate it with light or electromagnetic radiation. The light used must have a wavelength smaller than the dimensions of an electron. The high momentum photons would change the energy of electrons by collisions. In this process we, no doubt, would be able to calculate the position of the electron, but we would know very little about the velocity of the electron after the collision. One of the important implications of the Heisenberg Uncertainty Principle is that it rules out existence of definite paths or trajectories of electrons and other similar particles. The trajectory of an object is determined by its location and velocity at various moments. If we know where a body is at a particular instant and if we also know its velocity and the forces acting on it at that instant, we can tell where the body would be sometime later. We, therefore, conclude that the position of an object and its velocity fix its trajectory. Since for a sub-atomic object such as an electron, it is not possible simultaneously to determine the position and velocity at any given instant to an arbitrary degree of precision, it is not possible to talk of the trajectory of an electron.

20

Pauli Exclusion Principle: The number of electrons to be filled in various orbitals is restricted by the exclusion principle, given by the Austrian scientist Wolfgang Pauli (1926). According to this principle : No two electrons in an atom can have the same set of four quantum numbers. Pauli exclusion principle can also be stated as : Only two electrons may exist in the same orbital and these electrons must have opposite spin. This means that the two electrons can have the same value of three quantum numbers n, l and ml, but must have the opposite spin quantum number. The restriction imposed by Paulis exclusion principle on the number of electrons in an orbital helps in calculating the capacity of electrons to be present in any subshell. For example, subshell 1s comprises of one orbital and thus the maximum number of electrons present in 1s subshell can be two, in p and dsubshells, the maximum number of electrons can be 6 and 10 and so on. This can be summed up as : the maximum number of electrons in the shell with principal quantum number n is equal to 2n2. Hunds Rule of Maximum Multiplicity: This rule deals with the filling of electrons into the orbitals belonging to the same subshell (that is, orbitals of equal energy, called degenerate orbitals). It states : pairing of electrons in the orbitals belonging to the same subshell (p, d or f) does not take place until each orbital belonging to that subshell has got one electron each i.e., it is singly occupied. Since there are three p, five d and seven f orbitals, therefore, the pairing of electrons will start in the p, d and f orbitals with the entry of 4th, 6th and 8th electron, respectively. It has been observed that half filled and fully filled degenerate set of orbitals acquire extra stability due to their symmetry The electronic configuration of the elements sodium (Na, 1s22s22p63s1) to argon (Ar,1s22s22p63s23p6), follow exactly the same pattern as the elements from lithium to neon with the difference that the 3s and 3porbitals are getting filled now. This process can be simplified if we represent the total number of electrons in the first two shells by the name of element neon (Ne). The electronic configuration of the elements from sodium to argon can be written as (Na, [Ne]3s1) to (Ar, [Ne] 3s23p6). The electrons in the completely filled shells are known as core electrons and the electrons that are added to the electronic shell with the highest principal quantum number are called valence electrons. For example, the electrons in Ne are the core electrons and the electrons from Na to Ar are the valence electrons. In

21

potassium (K) and calcium (Ca), the 4sorbital, being lower in energy than the 3d orbitals, is occupied by one and two electrons respectively. A new pattern is followed beginning with scandium (Sc). The 3d orbital, being lower in energy than the 4p orbital, is filled first. Consequently, in the next ten elements, scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) and zinc (Zn), the five 3d orbitals are progressively occupied. We may be puzzled by the fact that chromium and copper have five and ten electrons in 3d orbitals rather than four and nine as their position would have indicated with two-electrons in the 4s orbital. The reason is that fully filled orbitals and half-filled orbitals have extra stability (that is, lower energy). Thus p3, p6, d5, d10,f 7, f14 etc. configurations, which are either half-filled or fully filled, are more stable. Chromium and copper therefore adopt the d5 and d10 configuration. Electronic Configuration: To indicate the electronic configuration of the atom, that is to say, where the electrons reside, we use the following notation.

Given a periodic table, all we need to know to write the electronic configuration for a given atom is the atomic number Z, which tells us the number of electrons in the neutral atom. We start by writing the first potential energy level (n=1), then the possible types of orbitals in this level (s, p, etc.), and then the number of electrons occupying that orbital, which is always either 1or 2. It will always be 2 unless Z is an odd number and were down to the last electron in the valence shell. The filling of electrons into the orbitals of different atoms takes place according to the aufbau principle which is based on the Paulis exclusion principle, the Hunds rule of maximum multiplicity and the relative energies of the orbitals.

22

Aufbau Principle: The word aufbau in German means building up. The building up of orbitals means the filling up of orbitals with electrons. The principle states : In the ground state of the atoms, the orbitals are filled in order of their increasing energies. In other words, electrons first occupy the lowest energy orbital available to them and enter into higher energy orbitals only after the lower energy orbitals are filled. The order in which the energies of the orbitals increase and hence the order in which the orbitals are filled is as follows : 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 4f, 5d, 6p, 7s... The order may be remembered by using the method given in Fig. 2.17. Starting from the top, the direction of the arrows gives the order of filling of orbitals, that is starting from right top to bottom left as shown in Figure 5. Orbitals and Quantum Numbers : A large number of orbitals are possible in an atom. Qualitatively these orbitals can be distinguished by their size, shape and orientation. An orbital of smaller size means there is more chance of finding the electron near the nucleus. Similarly shape and orientation mean that there is more probability of finding the electron along certain directions than along others. Atomic orbitals are precisely distinguished by what are known as quantum numbers. Each orbital is designated by three quantum numbers labelled as n, l and ml. The principal quantum number determines the size and to large extent the energy of the orbital. For hydrogen atom and hydrogen like species (He+, Li2+, .... etc.) energy and size of the orbital depends only on n. The principal quantum number also identifies the shell. With the increase in the value of n, the number of allowed orbital increases and are given by n2 All the orbitals of a given value of n constitute a single shell of atom and are represented by the following n = 1 2 3 4 and Shell = K L M N The quantum numbers are parameters that describe the distribution of electrons in the atom,. They are: letters:

23

1.

Principal quantum number (n) - Represents the main energy level, or shell, occupied by an electron. It is always a positive integer, that is n = 1, 2, 3 ...

2.

Secondary quantum number (l ) - Represents the energy sublevel, or type of orbital, occupied by the electron. The value of l depends on the value of n such that l = 0, 1, ... n-1. This number is sometimes also called azimuthal, or subsidiary.

3.

Magnetic

quantum number (ml) - Represents the number of possible

orientations in 3-D space for each type of orbital. Since the type of orbital is determined by l, the value of ml ranges between -l and +l such that ml = -l, ...0, ...+l. 4. Spin quantum number (mS) - Represents the two possible orientations that an electron can have in the presence of a magnetic field, or in relation to another electron occupying the same orbital. Only two electrons can occupy the same orbital, and they must have opposite spins. When this happens, the electrons are said to be paired. The allowed values for the spin quantum number ms are +1/2 and -1/2. Size of an orbital increases with increase of principal quantum number n. In other words the electron will be located away from the nucleus. Since energy is required in shifting away the negatively charged electron from the positively charged nucleus, the energy of the orbital will increase with increase of n. Azimuthal quantum number: l is also known as orbital angular momentum or subsidiary quantum number. It defines the three dimensional shape of the orbital. For a given value of n, l can have n values ranging from 0 to n 1, that is, for a given value of n, the possible value of l are : l = 0, 1, 2, .......... (n 1). Electron spin s : The three quantum numbers labelling an atomic orbital can be used equally well to define its energy, shape and orientation. But all these quantum numbers are not enough to explain the line spectra observed in the case of multi-electron atoms, that is, some 24

of the lines actually occur in doublets (two lines closely spaced), triplets (three lines, closely spaced) etc. This suggests the presence of a few more energy levels than predicted by the three quantum numbers. Orbit, orbital and its importance: Orbit and orbital are not synonymous. An orbit, as proposed by Bohr, is a circular path around the nucleus in which an electron moves. A precise description of this path of the electron is impossible according to Heisenberg uncertainty principle. Bohr orbits, therefore, have no real meaning and their existence can never be demonstrated experimentally. An atomic orbital, on the other hand, is a quantum mechanical concept and refers to the one electron wave function in an atom. It is characterized by three quantum numbers (n, l and ml) and its value depends upon the coordinates of the electron. has, by itself, no physical meaning. It is the square of the wave function i.e., ||2 which has a physical meaning. ||2 at any point in an atom gives the value of probability density at that point. Probability density (||2) is the probability per unit volume and the product of ||2 and a small volume (called a volume element) yields the probability of finding the electron in that volume (the reason for specifying a small volume element is that ||2 varies from one region to another in space but its value can be assumed to be constant within a small volume element). The total probability of finding the electron in a given volume can then be calculated by the sum of all the products of ||2 and the corresponding volume elements. It is thus possible to get the probable distribution of an electron in an orbital. An electron spins around its own axis, much in a similar way as earth spins around its own axis while revolving around the sun. In other words, an electron has, besides charge and mass, intrinsic spin angular quantum number. Spin angular momentum of the electron a vector quantity, can have two orientations relative to the chosen axis. These two orientations are distinguished by the spin quantum numbers m which can take the values of + or . These are called the two spin states of the electron and are normally represented by two arrows, (spin up) and (spin down). Two electrons that have different m s values (one + and the other ) are said to have opposite spins. An orbital cannot hold more than two electrons and these two electrons should have opposite spins.

25

Figure 5 Module 1H Chemical Bonding

All chemistry except for nuclear reactions involves electron transfers from one atom to another. More specifically, this electron trade takes place at the valence shells of the atoms. In general chemistry, we learn about two major types of chemical bonds, namely ionic and covalent. Ionic bonding is more likely to take place between elements of highly different electro-negativities, especially between metals and nonmetals. We can use Lewis formulas to indicate the manner of the electron transfer in a highly simplified fashion. The dots around the atomic symbol represent the electrons in the valence shell of each element. In the classic example of the reaction between sodium and chlorine, the only electron in the valence shell of sodium is completely transferred to the valence shell of chlorine. Sodium then forms a positive ion and chlorine a negative ion. The electrostatic attraction between oppositely charged ions forms the basis of the ionic bond and is the force that keeps the atoms together. Covalent bonding is more likely to take place between elements of similar electro-negativities, especially between nonmetals. In the reaction between two hydrogen atoms, for instance, the electron transfer is never complete. Instead, the two atoms share the electrons, which in this case spend equal amounts of time around both nuclei. There is no formation of full positive or negative charges and therefore there is no electrostatic attraction. The force that keeps the atoms together is the fulfillment of the octet rule

*************************************************************************** 26

ACIDS AND BASES: FUNDAMENTALS


Module 2A - Arrhenius Theory
a) b) Acids contain H+ and bases contain OH-

MODULE 2

_________________________________________________

Neutralization reaction occurs hydrogen ions and hydroxide ions react to form water.

Arrhenius defined bases as substances that dissolve in water to release hydroxide ions (OH-) into solution. For example, a typical base according to the Arrhenius definition is sodium hydroxide (NaOH): NaOH + H2O - Na+(aq) + OH- (aq) The Arrhenius definition of acids and bases explains a number of things. Arrhenius's theory explains why all acids have similar properties to each other (and, conversely, why all bases are similar): because all acids release H+ into solution (and all bases release OH-). The Arrhenius definition also explains Boyle's observation that acids and bases counteract each other. This idea, that a base can make an acid weaker, and vice versa, is called neutralization Svante Arrhenius first defined acids to be proton (H+) donors and bases to be hydroxide ion (OH-) donors in aqueous solution. The Arrhenius model of acids and bases is summarized by the following two reactions: Arrhenius acids HA (aqueous) Arrhenius bases BOH (aqueous) H+ (aqueous) + OH- (aqueous) H+ (aqueous) + A- (aqueous)

The Arrhenius model of acids and bases, where A = acid and B = base 27

At the time that Arrhenius proposed these definitions, water was virtually the only solvent used in chemistry, and nearly all known acids and bases contained protons (H+) and hydroxyl groups (OH), respectively. His definition was sufficient for the chemistry that was understood then. But progress in chemistry necessitated new definitions: it was discovered that ammonia behaves like a base, and HCl donates protons in non-aqueous solvents. The Bronsted-Lowry model of acids and bases serves that need by describing acids as proton donors and bases as proton acceptors. These definitions remove the role of solvent and allow bases like ammonia and fluoride ion to be classified as bases, so long as they bond to protons. The BronstedLowry model implies that there is a relationship between acids and bases (acids transfer protons to bases) and allows us to define conjugate acids and conjugate bases

Module 2B
a) b)

Bronstedt-Lowry Theory

Acids are proton donors and bases are proton acceptors. Conjugate acid base pairs are the two chemicals (one on each side) that differ only by a hydrogen ion (sometimes just called a proton).

Despite the usefulness of the Bronsted-Lowry definition, there is an even more general definition of acids and bases provided by G. N. Lewis. The Lewis model of acids and bases proposes that an acid is an electron pair acceptor while a base is an electron pair donor. This model of acidity and basicity broadens the characterization of acid-base reactions to include reactions like the following which do not involve any hydrogen transfers. The nitrogen atom in ammonia donates an electron pair to complete the valence octet of boron.

Module 2C

Lewis Acids and Bases

The final and most general definition of acids and bases is the Lewis definition: acids are electron pair acceptors and bases are electron pair donors. Acids are recognizable because they have vacant orbitals that can accommodate electron pairs. Bases have lone pairs of 28

electrons available for sharing. A significant aspect of this definition is that it helps clarify the acidity of most transition metal ion solutions. These highly charged ions draw water

molecules to their centers. As the electron rich oxygen end of water has its charge density slide towards the transition metal d orbital vacancies, the poor hydrogens become vulnerable to the surroundings they are more apt to be lost thus the complex ion behaves as an acid.

Because we are more interested now in describing terms and processes that involve proton transfers (pH, titration), we will focus on the Bronsted-Lowry definitions of acids and bases. We will leave consideration of the Lewis model of acids and bases for studying reactions in organic chemistry. Module 2D Reactions of Acids and Bases with Water

As you may have noted already in the acid-base reactions above, we use arrows in both reaction directions to indicate that these are equilibrium processes. Proportions of reagents and products at equilibrium can be described by an equilibrium constant. The equilibrium constant given in is for the reaction of an acid, HA, with water as shown. HA (aq) + H2O (l) A- (aq) + H3O+ (aq)

Although water is a reactant in the above reaction and belongs in the equilibrium constant, its value of 55.6 M in aqueous solution is so large in comparison with the change in water concentration at equilibrium that we will assume that the value of [H 2O] is constant. Using that assumption, we will define the acid dissociation constant, K a, in to be the following: HA (aq) + H2O (l) K(aq) H2O = Ka = [A-] [H3O+] / [HA] 29 A- (aq) + H3O+ (aq)

Definition of the acid dissociation constant: From the form of the above equation we can see that stronger acids, those that dissociate to a greater extent, will have larger values of K a whereas weaker acids will have smaller values of K a. A practical range for K a values runs from 10-12 for very weak acids to 1013 for the strongest acids. Knowing this practical range of acidity constants will aid in judging how reasonable your answers are when you calculate values for K a in problems. In an analogous way, we define K b, the base constant in to be the following: HB (aq) + H2O (l) K(aq) H2O = Kb = [BH+] [OH-] / [B] Definition of the base dissociation constant: Stronger bases have larger values of K b while weaker bases have smaller values of K b. K b's of typical bases in inorganic chemistry tend to have a range of values between 10-11 and 103. Water can act as both an acid and as a base. For this reason water is said to be amphiprotic. Water is often incorrectly termed amphoteric. An amphiprotic species like water can either donate or accept a proton. Amphoteric species can both donate and accept hydroxide ions, as water cannot. The following reaction in , called the autoionization of water, has the equilibrium constant K w defined in the manner of K a and K b. The dissociation constant K w for water is 1 x 10-14 at room temperature (298 K), and tends to rise with higher temperatures. B- (aq) + OH- (aq)

H2O + H2O

H3O+ + OH-

K(aq) [H2O]2 = Kw = [H3O+] [OH-] = 1.0 X 10-14 The autoionization of water Knowing that K w = 1 x 10-14 is useful because the relationship between K aand K b for a conjugate acid-base pair is K a * K b = K w. Therefore, you can calculate the K a of the conjugate acid of a base when given its K b.

30

Module 2E

Equilibrium Equations

Water is by far the major constituent and thus it is essentially pure; it's not included in the equilibrium expression. These expressions are only written for weak bases and acids not strong, since K would be very large. For ammonia in water: NH3(aq) + H2O(l) <-> NH4+(aq) + OH-(aq) Kb = [NH4+][OH-] [NH3] To model conjugate acid base pairs, follow the H+ ion reading the forward and reverse reactions. In the reaction above, the ammonia is the base and the ammonium ion is its conjugate acid. Water is acting as the acid and the hydroxide ion is its conjugate base. Conjugate pairs ONLY differ by an H+ ion move the H and move the + charge.) See top of page 673 for additional examples. For a weak acid, the Ka expression includes the hydronium ion, H3O+. This recognizes the role of water as a base. By accepting a proton, the water becomes H3O+. Species like H2O that can act as an acid or a base are said to be amphiprotic. For sulfurous acid in water: H2SO3 (aq) + H2O(l) <-> HSO3-(aq) + H3O+(aq); Ka = [HSO3-][H3O+] [H2SO3] Module 2F Strengths of Acids and Bases (The pH and pOH Scales) Due to the large range of proton concentration values ([H+]) in aqueous solution (typically from 10-15 to 10 M), a logarithmic scale of acidity makes the most sense to put the values into manageable numbers. The pH scale of acidity defines pH as the negative common logarithm of the concentration of H+: pH = - log [H+].

31

Before proceeding with our discussion on pH, let's review some properties of Logarithms (affectionately called "logs"). A common logarithm is a function that computes what exponent would be on 10 to obtain the input number. For example, the logarithm of 100 (written "log 100") is 2 because 102 = 100. Likewise, log 1,000,000 = 6. To add logs, multiply their arguments: log 100 + log 1000 = log

(100 x 1000) = log (100,000) = 5. To subtract logs, divide their arguments: log 100 - log 1000 = log (100/1000) = log (0.1) = - 1. Given those simple rules, you can now manipulate logs well enough to do any problem involving logs in acid-base chemistry. The pH scale in water is centered around 7, which is called neutral pH. This value is not randomly selected, but rather it comes from the fact that the [H+] in pure water is 10-7 (recall that K w = 10-14). An acidic solution has a pH value less than 7 because [H+] is greater than that of pure water. A basic solution has a pH greater than 7 because there is a lower [H+] than that of pure water (and consequently a larger [OH-]). Chemists use a pOH scale analogous to the pH acidity scale to gage hydroxide ion concentrations of aqueous solutions. pOH is defined as the negative common logarithm of the concentration of OH-: pOH = - log [OH- ]. In the pOH scale, 7 is neutral, less than 7 is basic, and greater than 7 is acidic. A useful relationship (which you should be able to derive using the definition of K w) is that pH + pOH = 14. This formula will allow you to readily convert between values of pH and pOH. A comparison of the pH and pOH scales is provided. Note that because K w is constant, the product of [H+] and [OH-] is always equal to 10-14. The prefix "p" in front of a symbol means "take the negative log". We have defined pH and pOH as values to describe the acidic or basic strength of solutions. Now we can talk about pK a(- log K a) and pK b (- log K b) as measures of acidity and basicity, respectively, for standard acids and bases. An acid with a pK a less than zero is called a strong acid because it almost completely dissociates in water, giving an aqueous solution a relatively low pH. Acids with pK a's greater than zero are called weak acids because they only partially dissociate in water, to make solutions with larger pH's than those strong acids produce at the same concentration. Similarly, bases with pK b's less than zero are strong bases and bases with pK b's greater than zero are called weak bases.

32

Factors Affecting Acidity: Now that we have the tools to be able to describe the acidity and basicity of compounds with known pK a's, let's analyze trends in acidity and basicity to reach an intuitive understanding of those trends. First, let's consider the acidity of the halogen acids-HF, HCl, HBr, and HI-- collectively abbreviated HX as shown in , where X represents the halogen. From the data in the figure below, you can see that the major factor affecting the acidity of halogen acids is the strength of the H-X bond. Intuitively, a larger electronegativity difference should lead to a stronger acid due to the polarization of electrons away from hydrogen. However, the trend in bond strength is enough to overrule that competing trend in electronegativity. The smaller the halogen, the closer in size it is to the proton and the greater the orbital overlap; so HF is most the strongly bonded and weakly acidic of the halogen acids. Generalizing that result, we can say that when the an H-A bond is strong, the acid is weak. Experimental confirmation of this postulate comes from the oxyacid series of compounds. An oxyacid is a molecule of the form AOn(OH)m, where A is a non-metal. Pauling and Ricci derived the following approximate equation for oxyacid acidity from experimental observations: pK a = 8 - 9f + 4n The variable f is the formal charge on A when all oxygens are singly bound to A. The variable n represents the number of O atoms bound to A that are not bound to an H. A general trend, summarized in the Pauling-Ricci rule above, is that the more electron withdrawing (more electropositive) the non- metal center, the stronger the acid due to a weakening of the O-H bond. In summary, we note the following trend regarding acidity: hydrogens are more weakly bound to more electronegative groups, and this produces stronger acids. By using the relationship K w = K a * K b, you should be able to figure out that we need only to discuss the acidity of compounds to describe basicity. From the above discussion, we can deduce that bases with weaker conjugate acids are more basic than those with stronger conjugate acids. Therefore, bases that form stronger bonds to H will have larger K b's and are stronger bases.

33

Module 2G

pH Concept

Under the Brnsted-Lowry definition, both acids and bases are related to the concentration of hydrogen ions present. Acids increase the concentration of hydrogen ions, while bases decrease the concentration of hydrogen ions (by accepting them). The acidity or basicity of something, therefore, can be measured by its hydrogen ion concentration. For example, a solution with [H+] = 1 x 10-7 moles/liter has a pH equal to 7 (a simpler way to think about pH is that it equals the exponent on the H+concentration, ignoring the minus sign). The pH scale ranges from 0 to 14. Substances with a pH between 0 and less than 7 are acids (pH and [H+] are inversely related - lower pH means higher [H+]). Substances with a pH greater than 7 and up to 14 are bases (higher pH means lower [H+]). Right in the middle, at pH = 7, are neutral substances. The relationship between [H+] and pH is shown in the table below [H+] 1 X 100 1 x 10-1 1 x 10-2 Acids 1 x 10-3 1 x 10-4 1 x 10-5 1 x 10-6 Neutral 1 x 10-7 1 x 10-8 1 x 10-9 1 x 10-10 Bases 1 x 10-11 1 x 10-12 1 x 10-13 1 x 10-14 pH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Examples HCl Stomach acid Lemon juice Vinegar Soda Rainwater Milk Pure water Egg whites Baking soda Tums antacid Ammonia Mineral lime - Ca(OH)2 Drano NaOH

The self-ionization of water is described below: H2O(l) + H2O(l) <-> OH- (aq) + H3O+(aq) 34

The equilibrium equation for the above reaction is as follows. Kw = [H3O+] [OH-] = 1.0 x10-14 The significance of this relationship is that it applies to ALL aqueous solutions. Kw is an important value to remember. It is the ion product of water. The following related equations are very useful and for practical purposes should be memorized. pH = -log[H3O+] [H3O+] [OH-] = 1.0 x10-14 10-pH = [H3O+] pOH = -log[OH-] pH + pOH = 14 10-pOH = [OH-]

& & &

Module 2H

Weak acids and Weak Bases

The key to recognizing weak acids and bases lies in memorizing the strong acids and bases. If you know these, all other examples must be weak. Just because a molecule contains H does not make it an acid. The H must be ionizable like those that are bound to many polyatomic ions, some monatomic ions, and carboxylic acids. See below for examples: nitrous acid hydrofluoric acid ethanoic acid (acetic acid) HNO2 HF CH3COOH (HC2H3O2)

Note that ethanoic acid is commonly written as the formula in parenthesis but the formula preceding it actually conveys the bonding pattern specific to carboxylic acids, namely a carbon both double bonded to one oxygen and single bonded to another which in turn is bonded to the hydrogen. Weak bases are less familiar. Ammonia is often used in problems because it is a weak base and many are familiar with it. If you examine Table 16.4 on page 694, youll notice that several of the weak bases listed contain N and many have one H of th e ammonia molecule substituted with an organic fragment. Nitrogen shows its tendency to form a coordinate covalent bond with an H+ it's acting as a base.

35

Besides calculating the pH of weak acid/base systems, sometimes one is asked to calculate the percent ionization. For some, it gives a more tangible feel for how weak the acid is. The formula is as follows: percent ionization = molarity of H+ from HA x 100% Initial molarity of HA Understand that the percent ionization of a weak acid or base increases as the solution becomes more dilute.

Polyprotic Acids: Polyprotic acids may appear to present a more challenging situation but in reality the qualitative understanding of K values allows problems like these to be quite straightforward. I will do a problem on the board to highlight the key ideas. As a bonus, it will clearly set us on the way to understand the acid base character of ions. Ions as Acids and Bases: An important qualitative idea is that if an acid is weak its conjugate base must also be weak. For another

example, if you have a strong acid, by definition its conjugate base must be ridiculously weak (irrelevant).
The quantitative idea is derived from the definition of the equilibrium expression and is as follows: Ka x Kb = Kw The product of the ionization constants of an acid and its conjugate base (or vice versa) equals the ion product of water.

36

If one dissolves salts in water, frequently the pH shifts because most commons salts contain one or two ions that are conjugates of either weak acids or bases. The useful summary statement is this: Oxyacids: Strength of acid increases with the number of oxygens attached to central atom. The strongly electronegative O withdraws electrons towards it and weakens the remaining OH bond.

37

MODULE 3 CHEMICAL KINETICS _________________________________________________


Module 3A Laws of Thermodynamics Chemical reactions proceed if the products of the reaction have lower free energies than do the reactants The first law of thermodynamics the total energy of a system is constant. U = Q + w Enthalpy, H, is a function that describes energy changes at constant pressure. Hp = cp(T)p For a biological system it defines the internal energy of a system HEAT H = (+) positive heat is absorbed = ENDOTHERMIC REACTION H = (-) negative heat is evolved (given out) = EXOTHERMIC REACTION The general Reaction Profile

``

38

The second law of thermodynamics Spontaneous processes are those which increase the entropy of the universe (i.e.system + surroundings). Entropy is equal to a measurement of the randomness of a system.

The Gibbs free energy Both enthalpy and entropy changes are important in determining whether a reaction will occur or not. A relationship between these two factors can be expressed by a new thermodynamic term known as Gibbs Free Energy (named after the American physicist J.W. Gibbs [18391903]). Gibbs Free Energy Equation G = H - TS Where; G = Gibbs Free Energy, in kJ; H = enthalpy change; T = temperature, in Kelvin; S = entropy change (in kJ K-1) Free energy change is the net driving force of a chemical reaction

whether the reaction will be spontaneous or not can be assessed from the below points; i) If G < 0 (exergonic, signify work-producing) the forward reaction is

spontaneous. (ii) If G > 0 (endergonic, signifying work-consuming) the reverse reaction is spontaneous. (iii) If G0 = 0 the reaction is at equilibrium. For example: G for the following reaction at 25C. Will the reaction occur (be spontaneous)? How do you know? NH3(g) + HCl(g) NH 4Cl(s) Also given for this reaction: H = -176.0 kJ; JK-1 39 S = -284.8

Solution We will calculate G using the formula G = H - TS but first we need to convert units for S and temperature to Kelvin: S = -284.8 JK-1 = -0.2848 kJK-1 K = 273 + C = 273 + 25 = 298 K Now we can solve the equation: G = -176.0 - (298)(-0.2848) G = -176.0 - (-84.9) = -91.1 kJ, Since G < 0 the reaction will be spontaneous. Module 3B Rates of Reaction and the Rate Law for a Reaction

The term rate is often used to describe the change in a quantity that occurs per unit of time. The rate of inflation, for example, is the change in the average cost of a collection of standard items per year. The rate at which an object travels through space is the distance traveled per unit of time, such as miles per hour or kilometers per second. In chemical kinetics, the distance traveled is the change in the concentration of one of the components of the reaction. The rate of a reaction is therefore the change in the concentration of one of the reactants - (X)- that occurs during a given period of time - t. Rate of Reaction = X / t The rate of the reaction between phenolphthalein and the OH- ion isn't constant; it changes with time. Like most reactions, the rate of this reaction gradually decreases as the reactants are consumed. This means that the rate of reaction changes while it is being measured. To minimize the error this introduces into our measurements, it seems advisable to measure the rate of reaction over periods of time that are short compared with the time it takes for the reaction to occur. We might try, for example, to measure the infinitesimally small change in

40

concentration

d(X)

that occurs over an infinitesimally short period of time

dt. The

ratio of these quantities is known as the instantaneous rate of reaction. Rate = d(X) / dT The instantaneous rate of reaction at any moment in time can be calculated from a graph of the concentration of the reactant (or product) versus time. The graph below shows how the rate of reaction for the decomposition of phenolphthalein can be calculated from a graph of concentration versus time. The rate of reaction at any moment in time is equal to the slope of a tangent drawn to this curve at that moment.

The instantaneous rate of reaction can be measured at any time between the moment at which the reactants are mixed and the reaction reaches equilibrium. Extrapolating these data back to the instant at which the reagents are mixed gives the initial instantaneous rate of reaction. Module 3C Different Ways of Expressing the Rate of Reaction

There is usually more than one way to measure the rate of a reaction. We can study the decomposition of hydrogen iodide, for example, by measuring the rate at which either H 2 or I2 is formed in the following reaction or the rate at which HI is consumed. 2 HI(g) H2(g) + I2(g)

41

Experimentally we find that the rate at which I2 is formed is proportional to the square of the HI concentration at any moment in time.

What would happen if we studied the rate at which H2 is formed? The balanced equation suggests that H2 and I2 must be formed at exactly the same rate.

What would happen, however, if we studied the rate at which HI is consumed in this reaction? Because HI is consumed, the change in its concentration must be a negative number. By convention, the rate of a reaction is always reported as a positive number. We therefore have to change the sign before reporting the rate of reaction for a reactant that is consumed in the reaction.

The negative sign does two things. Mathematically, it converts a negative change in the concentration of HI into a positive rate. Physically, it reminds us that the concentration of the reactant decreases with time. What is the relationship between the rate of reaction obtained by monitoring the formation of H2 or I2 and the rate obtained by watching HI disappear? The stoichiometry of the reaction says that two HI molecules are consumed for every molecule of H2 or I2 produced. This means that the rate of decomposition of HI is twice as fast as the rate at which H2 and I2 are formed. We can translate this relationship into a mathematical equation as follows.

42

As a result, the rate constant obtained from studying the rate at which H 2 and I2 are formed in this reaction (k) is not the same as the rate constant obtained by monitoring the rate at which HI is consumed (k') The Rate Law Versus the Stoichiometry of a Reaction In the 1930s, Sir Christopher Ingold and coworkers at the University of London studied the kinetics of substitution reactions such as the following. CH3Br(aq) + OH-(aq) CH3OH(aq) + Br-(aq)

They found that the rate of this reaction is proportional to the concentrations of both reactants. Rate = k(CH3Br)(OH-) When they ran a similar reaction on a slightly different starting material, they got similar products. (CH3)3CBr(aq) + OH-(aq) (CH3)3COH(aq) + Br-(aq)

But now the rate of reaction was proportional to the concentration of only one of the reactants. Rate = k((CH3)3CBr) These results illustrate an important point: The rate law for a reaction cannot be predicted from the stoichiometry of the reaction; it must be determined experimentally. Sometimes, the rate law is consistent with what we expect from the stoichiometry of the reaction. 2 HI(g) H2(g) + I2(g) Rate = k(HI)2 4 NO2(g) + O2(g) Rate = k(N2O5)

Often, however, it is not. 2 N2O5(g)

43

Module 3D

Order of Molecularity

Some reactions occur in a single step. The reaction in which a chlorine atom is transferred from ClNO2 to NO to form NO2 and ClNO is a good example of a one-step reaction. ClNO2(g) + NO(g) NO2(g) + ClNO(g)

Other reactions occur by a series of individual steps. N2O5, for example, decomposes to NO2 and O2 by a three-step mechanism. Step 1 Step 2 Step 3 : : : N2O5 NO2 + NO3 NO2 + NO + O2 2 NO2

NO2 + NO3 NO + NO3

The steps in a reaction are classified in terms of molecularity, which describes the number of molecules consumed. When asingle molecule is consumed, the step is called unimolecular. When two molecules are consumed, it is bimolecular. Reactions can also be classified in terms of their order. The decomposition of N2O5 is a firstorder reaction because the rate of reaction depends on the concentration of N2O5 raised to the first power. Rate = k(N2O5) The decomposition of HI is a second-order reaction because the rate of reaction depends on the concentration of HI raised to the second power. Rate = k(HI)2 When the rate of a reaction depends on more than one reagent, we classify the reaction in terms of the order of each reagent. The difference between the molecularity and the order of a reaction is important. The molecularity of a reaction, or a step within a reaction, describes what happens on the molecular level. The order of a reaction describes what happens on the macroscopic scale. We 44

determine the order of a reaction by watching the products of a reaction appear or the reactants disappear. The molecularity of the reaction is something we deduce to explain these experimental results. Module 3E Reaction Rates

Chemical kinetics is the branch of chemistry which addresses the question: "how fast do reactions go?" Chemistry can be thought of, at the simplest level, as the science that concerns itself with making new substances from other substances. Or, one could say, chemistry is taking molecules apart and putting the atoms and fragments back together to form new molecules. (OK, so once in a while one uses atoms or gets atoms, but that doesn't change the argument.) All of this is to say that chemical reactions are the core of chemistry. If Chemistry is making new substances out of old substances (i.e., chemical reactions), then there are two basic questions that must be answered: 1. 2. Does the reaction want to go? This is the subject of chemical thermodynamics. If the reaction wants to go, how fast will it go? This is the subject of chemical kinetics. Here are some examples. Consider the reaction, 2 H2(g) + O2(g) 2 H2O(l). We can calculate rGo for this reaction from tables of free energies of formation (actually this one is just twice the free energy of formation of liquid water). We find that rGo for this reaction is very large and negative, which means that the reaction wants to go very strongly. A more scientific way to say this would be to say that the equilibrium constant for this reaction is very large. However, we can mix hydrogen gas and oxygen gas together in a bulb or other container, even in their correct stoichiometric proportions, and they will stay there for centuries, perhaps even forever, without reacting. (If we drop in a catalyst - say a tiny piece of platinum - or introduce a spark, or even illuminate the mixture with sufficiently high frequency uv light, or compress and heat the mixture, the mixture will explode.) The problem is not that the 45

reactants do not want to form the products, they do, but they cannot find a "pathway" to get from reactants to products. Another example: consider the reaction, C(diamond) C(graphite). If you calculate rGo for this reaction from data in the tables of thermodynamic properties you will find once again that it is negative (not very large, but still negative). This result tells us that diamonds are thermodynamically unstable. Yet diamonds are highly regarded as gem stones ("diamonds are forever") and are considered by some financial advisors as a good longterm investment hedge against inflation. On the other hand, if you were to vaporize a diamond in a furnace, under an inert atmosphere, and then condense the vapor, the carbon would come back as graphite and not as diamond. How can all these things be? The answer is that thermodynamics is not the whole story in chemistry. Not only do we have to know whether a reaction is thermodynamically favored, we also have to know whether the reaction can or will proceed at a finite rate. The study of the rate of reactions is called chemical kinetics. Consider the reaction, 2 NO(g) + O2(g) 2 NO2(g). We can specify the rate of this reaction by telling the rate of change of the partial pressures of one the gases. However, it is convenient to convert these pressures into concentrations, so we will write our rates and rate equations in terms of concentrations, where square brackets, [ ], mean concentration in mol/L. We might try to write the rate variously as,

or as 46

but these are not the same because each molecule of O2 gives two molecules of NO2. To arrive at an unambiguous definition of reaction rate we define the "reaction velocity," v, as

This is unambiguous. The negative sign tells us that that species is being consumed and the fractions take care of the stoichiometry. Any one of the three derivatives can be used to define the rate of the reaction. For a general reaction, aA + bB cC + dD, the reaction velocity can be written in a number of different but equivalent ways,

As in our previous example, the negative signs account for material that is being consumed in the reaction and the positive signs account for material that is being formed in the reaction. The stoichiometry is preserved by dividing the rate of change of concentration of each substance by its stoichiometric coefficient. Module 3F Rate Laws

A rate law is an equation that tells us how fast the reaction proceeds and how the reaction rate depends on the concentrations of the chemical species involved. A rate law is an equation of the form,

Equation 4 is gives us a first order differential equation in t because the reaction velocity is related to a time-derivative of one of the concentrations

(as in Equation 3). 47

The rate law may contain substances which are not in the balanced reaction and may not contain some things that are in the balanced equation (even on the reactant side). Usually rate laws take the form,

where x, y, z, are small whole numbers or simple fractions and k is called the "rate constant." The sum of x + y + z + . . . is called the "order" of the reaction.

Common types of rate laws: 1. First Order Reactions In a first order reaction the rate is proportional to the concentration of one of the reactants. That is, v = rate = k[B], where B is a reactant. If we have a reaction which is known to be first order in B, such as B + other reactants products, we would write the rate law as,

The

constant, k,

in

this

rate

equation

is

the

first

order

rate

constant.

2. Second Order Reactions In a second order reaction the rate is proportional to concentration squared. For example, possible second order rate laws might be written as

48

Rate = k[B]2 or as Rate = k[A][B]. That is, the rate might be proportional to the square of the concentration of one of the reactants, or it might be proportional to the product of two different concentrations. 3.Third Order Reactions There are several different ways to write a rate law for a third order reaction. One might have cases where Rate = k[A]3, or Rate = k[A]2[B], or Rate = k[A][B][C], and so on.

We will see later that there are other, more "interesting" rate laws in nature, but a large fraction of rate laws will fit in one of the above categories.

Module 3G

Integrated forms of rate laws

In order to understand how the concentrations of the species in a chemical reaction change with time it is necessary to integrate the rate law (which is given as the time-derivative of one of the concentrations) to find out how the concentrations change over time. 1. First Order Reactions Suppose we have a first order reaction of the form, B + . . . . products.

49

Then we can write the rate law and integrate it as follows (recall that the derivative is negative because the concentration of the reactant, B, is decreasing):

The first order rate law is a very important rate law, radioactive decay and many chemical reactions follow this rate law and some of the language of kinetics comes from this law. The form of Equation 14d is called an "exponential decay." This form appears in many places in nature. One of its consequences is that it gives rise to a concept called "half-life." Half-life The half-life, usually symbolized by t1/2, is the time required for [B] to drop from its initial value [B]o to [B]o/2. Using the integrated form of the first order rate law we find that

Taking the logarithm of both sides gives,

or

50

which may actually give a little more insight into what is meant by half-life. This equation demonstrates clearly that the concentration drops by a factor of two for every t1/2 increment in time.) For first order processes it is common to define a "relaxation time." , by

so that one can write the integrated form of the rate law as

is the time required for [B] to drop from [B]o to [B]o/e. Sometimes is called the "one over e" time. Although the half-life is almost always used to describe the decay rate of radioactive elements, it is common for chemists to talk about the rate of first order processes in chemistry in terms of the relaxation time

. Module 3H Simple Second Order Rate Equations

A typical simple second order reaction, where B is one of the reactants, would look like,

which can be rearranged for integration as,

51

This equation can be integrated to give,

Or

We can make a quick check to see if this result fits what we know about the system. At t = 0 we get [B] = [B]o which is correct and at t = infinity we find that [B] = 0 which is also what we would expect. Half-life We can define the half-life of a second order reaction in the same way as in first order reactions. That is, the half-life, t1/2, is the time required for [B] to fall from [B]o to [B]o/2. Thus we use Equation 3 to give

or

and, finally,

Note that the half-life for a simple second order reactions depends on the initial concentration and that it is proportional to 1/[B]o. Contrast this to what we know about first order reactions where the half-life is independent of the initial concentration. This fact may come in useful later when we try to find experimental methods for determining rate laws. 52

Mixed Second Order Rate Equations A mixed second order rate law equation, where both components A and B are reactants, would look like,

Equation 7 has two variables in it (besides time). In order to integrate this equation we need to know on [B]. We will use the following stoichiometry as an example, 2A + B P + etc (P = product). the stoichiometry so that we can tell how [A] depends

We have a choice as to which component concentration to use for our variable, we can use [A], [B], or [P]. Let's try [P] as our variable. (The form of the answer will depend on the choice of variable. A different choice of variable will give an answer that looks different even though it is algebraically equivalent, see below.) Let's assume that there is no product present at the beginning of the experiment, that is, [P]o = 0. We now need to express [A] and [B] in terms of [P]. We can see that, [A] = [A]o 2 [P]. (We obtain Equation 10 from the stoichiometry, which says that every time we make one mole of P we use up two moles of A. That is, each P formed takes away two A's.) Also, [B] = [B]o [P], because each P formed takes away only one B.

53

So our rate equation in terms of the single variable, [P] becomes,

and then

In order to make this equation easier to integrate we rearrange it as follows,

or

The left-hand side can be integrated by partial fractions, or you can look it up in a book of integral tables. Module 3I Reaction Mechanisms

Elementary Reaction Steps - Molecularity We have made a big deal out of the fact that you cannot predict the rate law for a chemical reaction from the balanced equation for that reaction. We now introduce a new class of simple reactions, called elementary reaction steps, for which the rate law IS determined by the balanced reaction equation. We also introduce a new term, molecularity, which tells us the number of molecules involved in an elementary reaction step. We emphasize that the reaction velocity for each elementary reaction step IS determined by the reaction step and, later on, we will string a sequence of elementary reaction steps together to form what is called a mechanism. A reaction mechanism is a detailed (theoretical) description of how we think the chemical reaction proceeds. That is, it describes our thought

54

about which molecule collides with which other molecule to form an intermediate product, which my go on to react with some other species, and so on, to produce the overall reaction. The elementary reaction steps must be balanced (as do all chemical reactions). We can usually tell the difference between an elementary reaction step and a balanced reaction by the fact that the elementary reaction step will have one or more rate constants associated with it, as we will see below. It is probably easiest to describe the elementary reaction steps and their associated rate laws by just telling you what they are. As we proceed you will become aware of the fact that the rate law is completely determined by the elementary reaction step you write down. (The converse is not true. We will see in the examples below that several different elementary steps may give rise to the same rate law.) Uni-molecular Reaction Steps The elementary reaction step,

, is unimolecular because there is only one molecule reacting, that is, molecule "A" is reacting. This unimolecular reaction step implies the rate law,

, or, equivalently,

. In words, these elementary reaction steps say that the molecule, A, spontaneously transforms into B at some rate k1. The algebraic sign in front of k1 tells whether you are gaining product or losing reactant depending on whether the concentration in the derivative is increasing or decreasing. For example, in Equation 2, [B] is increasing, and in Equation 3, [A] is 55

decreasing. (All of the usual rules of stoichiometry still hold in elementary reaction steps. If you use up some reactant you must gain an equivalent amount of product.) An elementary reaction step may be reversible or irreversible. Equation 1 is an irreversible unimolecular step. Equation 4 below is a reversible unimolecular step: . This reversible unimolecular step implies the following rate laws,

and/or . (Either one of these may be used, depending on whether we are trying to account for the disappearance of reactant, A, or the appearance of product, B, in our mechanism for a particular reaction.) A unimolecular reaction step can have more than one product, for example,

. The unmimolecular process given by Equation 7 implies the same rate law as the reaction in Equation 1, namely, either Equation 2 or Equation 3.

Bi-molecular Reaction Steps There are several varieties of bimolecular steps. For example,

implies the rate law,

56

, or , and so on. In above equations only one product is given, "C." We would get the same rate laws if there had been two or more products, for example as in,

. Reversible Bimolecular Steps The bimolecular reaction

implies the rate law

, or it could be written as a rate of loss of A or B as we have seen above. The reversible bimolecular reaction,

implies , and its variants.

57

Ter-molecular Reaction Steps Termolecular reaction steps require three molecules coming together at the same time. They are rare because three-body collisions in the gas phase are rare, but there are cases of termolecular reactions in the literature. There are many varieties of termolecular reactions and they may be reversible. A typical termolecular process might be,

, with its implied rate law

. A reaction mechanism is a combination of one or more elementary reaction steps which start with the appropriate reactants and end with the appropriate product(s). Further examples of the determination of rate laws from proposed mechanisms for chemical reactions we will consider two examples of a class of reactions called "chain reactions." Module 3J Chain Reactions Chain reactions usually involve free radicals. We will show how to deal with chain reactions by working out several examples. Our first example is the gas phase reaction of hydrogen with bromine to give HBr. (The temperature must be high enough that bromine is a gas and not a liquid.) H2 + Br2 2 HBr The experimental rate law is

58

Our task is to show that the postulated mechanism will give this rate law. (We will not try to invent mechanisms for particular reactions in this course.) The postulated mechanism has five elementary reaction steps:

Our goal is to find the rate law implied by this mechanism and see how it compares to the experimental rate law, Equation 2. Our first task will be to define the reaction rate. We will define the reaction rate as rate of production of the product, HBr.

Looking at the mechanism and using only the steps which yield or consume HBr we find that

We see that the rate contains two transient species, Br and H , so we set up the equations which show the rate of change of the concentrations of these two species and apply the steady state approximation. The two equations are,

and

********************************************************************

59

MODULE 4 FUNDAMENTALS OF ORGANIC CHEMISTRY


Module 4A Introduction

Organic molecules contain carbon atoms. The carbon atoms are covalently bonded to other atoms, and various chains of carbon atoms can be found in most every molecule you will deal with in this chapter. As you might recall from your introductory class, carbon has four valence electrons, and therefore will make four bonds in accordance with the octet rule. All noncarbon-to-carbon bonds will be assumed to be carbon-hydrogen bonds, as hydrogen atoms are the most commonly found attached atom. Hydrogen has one valence electron, and will make one covalent bond. Use these facts to draw the structures of the following molecules in the space provided. The carbon atom is capable of making single, double, and triple bonds, as well as bonding with oxygen, nitrogen, chlorine, or bromine. Oxygen has six valence electrons, and will make two covalent bonds. A single bond and a double bond are both possible for oxygen atoms. Nitrogen has five valence electrons, and will make three covalent bonds. Single, double, and triple bonds are all possibilities for nitrogen atoms. Chlorine and bromine each have seven valence electrons, and will make one covalent bond. The presence of carbon-carbon double or triple bonds, as well as the presence of oxygen, nitrogen, chlorine, or bromine, is very significant and worth noting, as it will be extremely important throughout your study of organic chemistry. Be sure to look for patterns in the bonding when you encounter these situations. Use your best judgment to draw the following molecules in the spaces provided. Module 4B Empirical and Molecular Formulas In the study of general chemistry, the empirical formula of a chemical compound is the simplest whole-number ratio of elements in a compound. An empirical formula makes no reference to the shape, structure, or absolute number of atoms in a compound. Empirical formulas are the standard for most ionic compounds, such as calcium chloride, CaCl2, and for macromolecules like silica, SiO2. The term empirical formula refers to the process of

60

elemental analysis, a technique of analytical chemistry used to determine the relative percent composition of a pure chemical substance by element. Much like an empirical formula, a molecular formula contains a whole-number ratio of the elements in a compound. In contrast, the molecular formula does identify the absolute number of atoms in a compound. However, no shape or structure determination can be made based on a molecular formula. Consider the empirical formula CH. From what you already know, there must be one hydrogen atom for every carbon atom. However, all three of the following molecules satisfy that requirement, and there is no discernable pattern in structure that can be discerned from the empirical formula.

Consider the molecular formula C7H16. From what you know of covalent bonding, carbon atoms make four bonds, while hydrogen atoms make only one. There are many different ways to assemble carbons and hydrogens into C7H16, with many possible structures resulting. (Two such structures for C7H16 are found on the following page. As with empirical formulas, no determination of structure can be made from a molecular formula.

61

Module 4B

Structural Formulas

Organic compounds tend to be built according to a general scheme as follows: The carbon atoms form a skeleton that runs through the middle of the molecule. Hydrogen atoms and any other are attached to the carbon skeleton. One method of drawing organic molecules involves representing every single atom, with the bonds between them drawn as lines. This is typically referred to as a structural formula. The structural formula for 1-hexanol, or C6H13OH, looks like this:

Organic molecules can also be represented in a more compact form, known as abbreviated structural formulas, also known as condensed structural formulas. This is done by omitting the bonds between atoms. The same compound, 1-hexanol, could therefore be represented as:

The skeletal formula, or carbon framework, or line-segment formula of an organic compound is a shorthand representation of its molecular structure. Skeletal formulas are ubiquitous in organic chemistry because they show complicated structures clearly and they are quick and simple to draw. In a skeletal formula, none of the bonds connecting hydrogen to the carbon skeleton are shown. Every other bond is drawn as a line segment, and a carbon atom is located at the end of each line segment. If something other than carbon is attached to the skeleton, it is specified in the drawing. In the image below, the skeletal formula of 1-hexanol is shown:

62

The simplest hydrocarbon is methane, containing only one carbon atom. Since each carbon atom can form four bonds, the formula of methane must be CH4. The bonding can be described as using sp3 hybrid orbitals on carbon, giving the molecule a tetrahedral shape.

This three-dimensional shape is not easy to show in two dimensions on a sheet of paper. One common representation is shown below as structure I. More often structure II is used because it is easier to draw, especially for more complex molecules. You should recall how to construct a Lewis dot structure from your study of inorganic chemistry. If a Lewis dot structure is required, it usually is drawn as in structure III.

It is also possible to have a double or triple bond between the carbon atoms, giving an unsaturated compound.

Module 4C Structural Isomerism For a three carbon compound, we could write the following skeletons (for simplicity, the bonds to the hydrogen atoms are shown, but not the hydrogen atoms themselves): Since the arrangement of bonds about each carbon atom is tetrahedral, rather than planar, the two structures are identical. At this point it would be very helpful for you to make a model of the 63

three-carbon compound (molecular formula C3H8). Notice that the three carbons are attached to each other in a line, with no branching of the chain. The drawings above simply show the same carbon skeleton from different viewpoints. One structure could be converted to another simply by rotating one part of the molecule about a carbon-carbon bond, relative to the rest of the molecule. You can see this best by using a model.

For the four-carbon molecule, we can simplify the representation of the carbon skeleton even further by showing only the carbon atoms and the bonds between them. In looking at this representation you must remember that each carbon will have other bonds in addition to those shown. All the other bonds are to hydrogen atoms, and each carbon has a total of four bonds.

The two skeletal structures immediately above are different. If you use models, you can see that it is not possible to change one to the other simply by rotating one part of the molecule relative to the other. The only way to convert one to the other is by breaking a carbon-carbon bond. Notice also that the first structure has four carbons in a single chain. In the second structure, the longest continuous chain is three carbons, with the fourth carbon attached to the middle of the chain. We refer to the first structure as a straight chain, and the second as a branched chain. Since the structures are different, but the molecular formulas identical (C4H10), this is an example of isomerism. This type of isomerism is known as structural isomerism. As the number of carbon atoms increases, the number of possible isomers increases rapidly. For molecules containing only single bonds, the maximum number of isomers for different numbers of carbon atoms range from 2 75 for C4 to C10 atoms.

64

Homologous Series The straight-chain alkanes (compounds containing all single carbon-carbon bonds) all could be written with the following general condensed structural formula: CH3(CH2)nCH3, where n = any number, including 0. A series of compounds showing this relationship, namely that members of the series differ only in the number of CH2 groups, is called a homologous series.

Solubilities and densities Other important physical properties of the alkanes are their low solubilities in water and their densities. The alkanes have such low solubility in water that we consider them insoluble. This is because dissolving would require that strong intermolecular forces between water molecules (due to hydrogen bonding) be broken and replaced by the much weaker van der Waals forces (London forces) between water molecules and non-polar alkane molecules. The net result of this process is energetically highly unfavorable, so it does not occur to any significant extent. All alkanes, regardless of whether they are gas, liquid, or solid, are less dense than water. Most liquid hydrocarbons have a density of about 0.7 g cm-3. Practical consequences of this property include the fact that hydrocarbons such as oil float on water. Oil fires cannot be put out with water, because the burning oil floats on top of water and may be spread more widely. Names of straight-chain alkanes The following table gives the molecular formula and the condensed structural formula of each of the first eight straight-chain alkanes, as well as its name according to the IUPAC system.

65

Module 4D

Naming of Alkanes

In the table on the previous page, we saw the names of the first eight straight-chain alkanes. We also have seen that alkanes containing more than three carbons can have branched chains. In fact, the number of branched-chain alkanes is much greater than the number of straightchain compounds. We will now see how to name these branched-chain alkanes.

The procedure is simple and logical and based on the name (already known) for the longest continuous chain in the compound. Find the points where the chain branches. The branches, or substituents, are called alkyl groups. (from alkane + yl). (a) The names of the substituents are derived from the alkane with the same number of carbons. Thus CH3 - = methyl, CH3CH2- = ethyl, and so on in the same way that the general name, alkyl group, was derived from alkane. (b) The substituent name is placed before the name of the longest chain, without a space between the two parts of the name. To indicate the position of the substituent, where there is more than one possibility, the carbons in the longest continuous chain are numbered. The numbering can be started from either end of the chain. The direction of numbering should be chosen so that when the two possible directions are compared, the number should be the lowest at the first point where the numbers differ. The numbers are separated from the rest of the name by hyphens.

66

Names of straight-chain alkenes The presence of double bonds is indicated by changing the ending -ane for an alkane to -ene for alkenes. CH3CH=CH2 propene If the multiple bond can be in more than one position in the molecule, number the position of the first carbon in the multiple bond, starting from the end of the chain which gives the lowest number. CH3CH2CH2CH=CH2 pent-1-ene (or 1-pentene)

Module 4E

The Importance of Functional Groups

All of our discussion so far has been concerned with hydrocarbons, compounds containing only carbon and hydrogen. Many organic compounds contain other elements, especially oxygen, nitrogen and occasionally, halogen. The presence of these other atoms changes both the chemical and physical properties of the compound relative to the hydrocarbon with the same carbon skeleton. These atoms, or groups of atoms, that determine the characteristic chemical and physical properties of a type of organic compound are called functional groups. The carbon-carbon double bond, even though it contains only carbon atoms and perhaps hydrogen atoms, is also considered a functional group because alkenes undergo many reactions that are not possible for alkanes. As an example of how a functional group can affect properties, let us compare some properties of ethane (CH3CH3) and ethanol (CH3CH2OH).

67

The two compounds are closely related structurally; ethanol is like ethane except for the replacement of an H by an OH. Except for combustion, a characteristic of almost all organic compounds, the physical and chemical properties of the two compounds are very different. Another example of a compound in which a functional group makes a difference is cholesterol, a compound much in the news. Cholesterol is needed by the body, but too much cholesterol is thought to be one of the factors contributing to the risk of heart disease. The structure of cholesterol looks very complex, because it has four rings attached to each other, but you can probably see that it contains two familiar functional groups: a carbon-carbon double bond and an OH group. Chemists have found that the chemistry of cholesterol is very similar to that of other compounds containing OH or C=C. Since functional groups behave similarly, whether in simple or complex molecules, our further study of the physical and

chemical properties of organic compounds will be organized according to the type of functional group present. Before dealing with the properties of functional groups, however, we need to become familiar with the structures, names and ways of representing some of the most common functional groups.

68

Structures and names of functional groups In Table 1, the names of the main functional groups are given in the first column. The common name of the type of compound in which each occurs appears in column 2. Systematic names sometimes used within the IUPAC system are given in parentheses below the common name. The structural formulas in column 3 introduce a new symbol which simplifies the writing of organic structures. R stands for any alkane in which a hydrogen has been replaced by another atom or group of atoms. Recall from Chapter 2 that such a group is called an alkyl group. The simplest possible group is that derived from methane. The alkyl group is thus CH3-, or methyl. Thus ROH can represent any alkane in which a hydrogen atom has been replaced by an OH group. Notice that the structure of cholesterol above contains two methyl groups and a C8H17 group. This also is an alkyl group, in this case the octyl group. Representing compounds in this way is consistent with the observation that the properties of the compound depend much more on the nature of the functional group than on the hydrocarbon portion of the molecule. Column 3 of the table is especially important. You should be able to recognize and write functional groups in both full and condensed forms. Ethyl ethanoate, for example, could be written in any of the following forms:

Table 1 Functional Groups 69

In the fourth column are given systematic names and formulas of specific compounds, as well as common names in parentheses. R represents an alkyl group; R', if appearing in the same structure as R, represents a second alkyl group. It may be the same or different from the first. Notice that for amines, two different structures have been written. These differ in the number of carbon-containing groups attached to the nitrogen. The number of groups can be 1, 2, or 3, and they can be any combination of alkyl or aryl (aromatic) groups. Naming compounds containing functional groups To name simple compounds with a single functional group, only a slight extension of the rules for naming hydrocarbons is needed. Rule 1: For a compound with a straight chain of carbons, name it as for an alkane, but replace the final e with an ending to indicate the functional group.

70

For aldehydes, carboxylic acids and amides, the functional groups can only occur at the ends of carbon chains, so they do not need numbers to indicate their positions. For alcohols and ketones, the groups may occur at different places in the chain, so numbers may be necessary to distinguish different isomers. For alcohols, this would apply to all compounds except methanol and ethanol. The number usually is placed immediately before the suffix indicating the functional group. Numbering starts from the end which gives the lowest number for the functional group. Examples: CH3CH2CHOHCH3 = butan-2-ol CH3CH2CH2COCH2CH3 = hexan-3-one (not hexan-4-one) In many textbooks in the U.S., these compounds would be named 2-butanol and 3-hexanone, respectively.

(a)

Esters are structurally related to carboxylic acids, with an alkyl group replacing the acidic hydrogen. They are named by placing the alkyl group first, then naming the acidic portion by replacing the e of the alkane with the same number of carbon atoms by oate.

(b)

amines are named as substituted amines, regardless of the number of alkyl groups attached to nitrogen. CH3CH2NH2 = ethylamine CH3CH2NHCH3 = ethylmethylamine (alphabetic order of alkyl

groups) (c) halogenoalkanes are named as substituted alkanes CH3CHBrCH3 = 2-bromopropane Rule 2: Branching in the main carbon chain is indicated by numbering the position of the alkyl substituent(s). Numbering starts from the carbon of a functional group if it is at the end of a chain. If the functional group is not at the end of the main chain, number from the end that will give the functional group the lowest possible number.

71

(CH3)2CHCH2COOH = 3-methylbutanoic acid CH3CHOHCH(CH3)2 = 3-methylbutan-2-ol Isomerism due to functional groups We know that isomers refer to compounds with the same molecular formula, but different structures. We have encountered these already in hydrocarbons, with different arrangements of the carbon atoms, and in compounds containing functional groups, when a substituent such as a halogen atom or hydroxyl group can be attached to different positions in the chain. In some cases, we have compounds with different functional groups but the same formula. For example, the following two compounds, an acid and an ester, are isomers, both with the molecular formula

Two other functional group isomers are propanal and propanone.

72

MODULE 5 ELECTROCHEMISTRY _____________________________________________


Electrochemistry is a sub-field within analytical chemistry focused on making electrical measurements of analytics. Module 5A Faradays Laws

The quantitative laws of electrolysis that were discovered by M. Faraday in 183334. Faradays laws express the relationship between the quantity of electricity passed through an electrolyte and the mass and chemical nature, in terms of chemical equivalents, of substances deposited or dissolved at the electrodes. Electrolysis is the separating of a compound into its constituent elements by passing an electrical current through it when in a molten or aqueous state. The word electrolysis means the process of breaking molecules to smaller parts by using an electric current. Positive and negative poles of an electric source, such as a battery, can absorb opposite ions of an electrolyte, causing separation of ions and creation of a new substance. Electricity dissociates water into the diatomic molecules of hydrogen (H2) and (O2). H2O H2 + 1/2 O2 Faradays first law of electrolysis states that the masses m of deposited or dissolved substances are proportional to the quantity of electricity q passed through the electrolyte. The second law states that the masses of different substances deposited or dissolved as a result of the passage of the same quantity of electricity through the electrolyte are proportional to the chemical equivalents A of the substances. It follows from the second law that the same quantity of electricity, called the Faraday constant F, is required for the deposition of the same gram-equivalent weight of different substances. Mathematically, Faradays laws may be written as one equation m = (A/F)q = kq, where the coefficient k = A/F is called the electrochemical equivalent.

73

Both of Faradays laws are exact if the ions of the electrolyte carry all the electricity passed through the electrolyte. Deviations from the laws are observed in certain cases; such

deviations may be associated with electrochemical side reactions that are not taken into accountfor example, the liberation of gaseous hydrogen during the electro-deposition of some metalsor with partial electron conductionfor example, during the electrolysis of certain alloys. First Law: The quantity of a substance produced by electrolysis is proportional to the quantity of electricty used. Second Law: For a given quantity of electricity the quantity of substance produced is proportional to its weight The quantity of electricity or charge contained in a current running for a specified time can be calculated: Q Q I t = Ixt = quantity of electricity or charge in coulombs (C) = current in amps (A) = time (seconds)

The Faraday constant, F, is the quantity of electricity carried by one mole of electrons. F F F = Avogadro's Number x charge on electron in coulombs = 6.022 x 1023 mol-1 x 1.602192 x 10-19 C = 96,484 C mol-1

This is usually rounded off to 96,500 C mol-1 for calculations in chemistry. The quantity of electricity required to deposit an amount of metal can be calculated: Q Q = n(e) x F = quantity of electricity in coulombs (C)

n(e) = moles of electrons 74

= Faraday constant = 96, 500 C mol-1

Electrical Energy, E, can be calculated: E = QxV E = electrical energy in joules (J) Q = quantity of electricity in coulombs (C) V = voltage (or EMF) in volts (V) 1kilowatt-hour, kWH, is a unit of electrical energy: 1 kWH = 3.6 x 106 J Module 5B Redox Reactions

A redox reaction is a reaction which involves a change in oxidation state of one or more elements. When a substance loses its electron, its oxidation state increases, thus it is oxidized. When a substance gains an electron, its oxidation state decreases, thus it is reduced. Zn(s) is being oxidized into Zn2+, and Cu2+ is being reduced into Cu(s). Zn(s) is known as a reducing agent and Cu2+ is known as an oxidizing agent. In a redox reaction, oxidation-reduction must occur simultaneously. This means that when one substance is being oxidized, the other substance must be reduced. A redox reaction is a reaction which involves a change in oxidation state of one or more elements. When a substance loses its electron, its oxidation state increases, thus it is oxidized. When a substance gains an electron, its oxidation state decreases, thus it is reduced. : Redox reactions involve transfer of electrons from one species to another: Oxidized species = loses electrons Reduced species = gains electrons Oxidizing agent (oxidant) takes electrons Reducing agent gives up electrons

75

Redox reactions, or oxidation-reduction reactions, have a number of similarities to acid-base reactions. Fundamentally, redox reactions are a family of reactions that are concerned with the transfer of electrons between species. Like acid-base reactions, redox reactions are a matched set -- you don't have an oxidation reaction without a reduction reaction happening at the same

time. Oxidation refers to the loss of electrons, while reduction refers to the gain of electrons. Each reaction by itself is called a "half-reaction", simply because we need two (2) halfreactions to form a whole reaction. In notating redox reactions, chemists typically write out the electrons explicitly: Cu (s) ----> Cu2+ + 2 eThis half-reaction says that we have solid copper (with no charge) being oxidized (losing electrons) to form a copper ion with a plus 2 charge. Notice that, like the stoichiometry notation, we have a "balance" between both sides of the reaction. We have one (1) copper atom on both sides, and the charges balance as well. The symbol "e -" represents a free electron with a negative charge that can now go out and reduce some other species, such as in the half-reaction: 2 Ag+ (aq) + 2 e- ------> 2 Ag (s) Here, two silver ions (silver with a positive charge) are being reduced through the addition of two (2) electrons to form solid silver. The abbreviations "aq" and "s" mean aqueous and solid, respectively. We can now combine the two (2) half-reactions to form a redox equation: Module 5C Galvanic Cell Galvanic cells have a spontaneous chemical reaction that generates electricity. One solution must be oxidized while the other is reduced. The net reaction is composed of 2 halfreactions, an oxidation reaction and a reduction reaction. Free energy change for the reaction is -150 kJ per mol Cd Electrochemical Cells

76

Generally oxidation-reduction or redox reactions take place in electrochemical cells. There are two types of electrochemical cells. Spontaneous reactions occur in galvanic (voltaic) cells; nonspontaneous reactions occur in electrolytic cells. Both types of cells contain electrodes where the oxidation and reduction reactions occur. Oxidation occurs at the electrode termed the anode and reduction occurs at the electrode called the cathode.

Electrodes & Charge The anode of an electrolytic cell is positive (cathode is negative), since the anode attracts anions from the solution. However, the anode of a galvanic cell is negatively charged, since the spontaneous oxidation at the anode is the source of the cell's electrons or negative charge. The cathode of a galvanic cell is its positive terminal. In both galvanic and electrolytic cells, oxidation takes place at the anode and electrons flow from the anode to the cathode. Galvanic or Voltaic Cells. The redox reaction in a galvanic cell is a spontaneous reaction. For this reason, galvanic cells are commonly used as batteries. Galvanic cell reactions supply energy which is used to perform work. The energy is harnessed by situating the oxidation and reduction reactions in separate containers, joined by an apparatus that allows electrons to flow. A common galvanic cell is the Daniell cell, shown below.

77

Electrolytic Cells The redox reaction in an electrolytic cell is non-spontaneous. Electrical energy is required to induce the electrolysis reaction. An example of an electrolytic cell is shown below, in which molten NaCl is electrolyzed to form liquid sodium and chlorine gas. The sodium ions migrate toward the cathode, where they are reduced to sodium metal. Similarly, chloride ions migrate to the anode and are oxided to form chlorine gas. This type of cell is used to produce sodium and chlorine. The chlorine gas can be collected surrounding the cell. The sodium metal is less dense than the molten salt and is removed as it floats to the top of the reaction container.

78

Many oxidation-reduction reactions occur spontaneously, giving off energy. An example involves the spontaneous reaction that occurs when zinc metal is placed in a solution of copper ions as described by the net ionic equation shown below. Cu+2 (aq) + Zn (s) -------> Cu(s) + Zn+2 (aq) The zinc metal slowly "dissolves" as its oxidation produces zinc ions which enter into solution. At the same time, the copper ions gain electrons and are converted into copper atoms which coats the zinc metal or sediments to the bottom of the container. The energy produced in this reaction is quickly dissipated as heat, but it can be made to do useful work by a device called, an electrochemical cell. This is done in the following way. An electrochemical cell is composed to two compartments or half-cells, each composed of an electrode dipped in a solution of electrolyte. These half-cells are designed to contain the oxidation half-reaction and reduction half-reaction separately as shown below (Figure 1). The half-cell, called the anode, is the site at which the oxidation of zinc occurs as shown below. Zn (s) ------ Zn+2 (aq) + 2e-

79

During the oxidation of zinc, the zinc electrode will slowly dissolve to produce zinc ions (Zn+2), which enter into the solution containing Zn+2 (aq) and SO4-2 (aq) ions. The half-cell, called the cathode, is the site at which reduction of copper occurs as shown below. Cu+2 (aq) + 2e- ------- Cu (s) When the reduction of copper ions (Cu+2) occurs, copper atoms accumulate on the surface of the solid copper electrode.The reaction in each half-cell does not occur unless the two half cells are connected to each other.

Figure 1 Basic electrochemical cell Recall that in order for oxidation to occur, there must be a corresponding reduction reaction that is linked or "coupled" with it. Moreover, in an isolated oxidation or reduction half-cell, an imbalance of electrical charge would occur, the anode would become more positive as zinc cations are produced, and the cathode would become more negative as copper cations are removed from solution. This problem can be solved by using a "salt bridge" connecting the two cells as shown in the diagram below. A "salt bridge" is a porous barrier which prevents the spontaneous mixing of the aqueous solutions in each compartment, but allows the migration of ions in both directions to maintain electrical neutrality. As the oxidationreduction reaction occurs, cations ( Zn+2) from the anode migrate via the salt bridge to the cathode, while the anion, (SO4)-2, migrates in the opposite direction to maintain electrical neutrality.

80

The two half-cells are also connected externally. In this arrangement, electrons provided by the oxidation reaction are forced to travel via an external circuit to the site of the reduction reaction. The fact that the reaction occurs spontaneously once these half cells are connected indicates that there is a difference in potential energy. This difference in potential energy is called an electomotive force (emf) and is measured in terms of volts. The zinc/copper cell has an emf of about 1.1 volts under standard conditions. Module 5D Industrial Electrochemistry: Electrochemical reactors are called electrolysis cells. The cells consist of a container, the cell body; two electrodes, the anode and cathode, where the electrochemical reactions occur;

and an electrolyte. Some cells have a diaphragm or membrane between the anode and cathode compartments to separate the anodic and cathodic products. While general purpose electrolysis cells are available, cells are usually custom designed for a particular process. The electrolysis cells used to produce the various chemicals and metals cited above differ significantly from one another. It is the responsibility of the electrochemical engineer in

industry to simultaneously manage electrical consumption and chemical production. He or she must apply relevant scientific and engineering principles to design, construct, and operate a process in an economical, safe, and environmentally conscious manner. Improved understanding of scientific principles and the application of new materials can lead to more efficient cell designs and processes. The constant evolution of technology provides

challenging and rewarding careers to engineers and scientists in a range of disciplines. Aluminum Production: Prior to its manufacture by electrolysis, aluminum metal was extremely rare, as expensive as silver, and just as prized. Today aluminum is an inexpensive and widely available material valued for its corrosion resistant properties. The large demand for aluminum products is reflected in that aluminum production consumes more electrical power than any other electrolytic process. Chlorine and Sodium Hydroxide Production: Two common chemicals produced by

electrolysis of salt solutions are chlorine and sodium hydroxide. The principal electrode reactions that occur in the electrolysis of salt solutions are Membrane Processes : Membranes make possible an enormous variety of separation processes. Examples of membrane 81

separations include desalting of brackish water and of seawater, demineralization of food products, separation of amino acids, and recovery of resources from wastewater streams. In these processes, the key component is a membrane that permits some chemicals to go through but not others, thus separating them

The resulting overall reaction

Electro-organic Synthesis : A commercial process for producing organic chemicals that is currently practiced on a scale comparable to the inorganic chemicals and metals cited above is the electro-hydrodimerization Electrochemical Engineering: While each of the processes above use cells designed for a specific purpose, they are all bound together by fundamental principles that govern the operation. Known collectively as the principles of electrochemical engineering, these concepts include transport processes, current and potential distribution phenomena, thermodynamics, kinetics, scale-up, sensing, control, and optimization. With use of quantitative methods, many salient features of cell operations can be modeled in concise mathematical form. Thus, it has been increasingly possible to predict cell behavior without the cost of an extensive empirical (trial and error) program of preliminary study. These principles cut across all electrochemical industries and can be applied with equal success whether they are used to design a plant to produce chemicals or to design a battery or a fuel cell for use in an electric car. While these concepts are well established in the electrolytic industry, their use in other areas has blossomed in the last few years. Concepts of current and potential distribution within cells, originally conceived by electroplaters, are now being applied throughout the field. *******************************************************************

82

MODULE 6 GASEOUS STATE


The search for an understanding of the nature of the gaseous state of matter began early in the history of science and continues even today. The early work is a classic example of the deductive method of reasoning that led from the laws or habits of gases to a theory of the gaseous state the kinetic molecular theory. In its original form, the kinetic molecular theory explained the behavior of gases in terms of the kinetic energy of motion of minute spheres without internal structure. As knowledge of the internal structure of molecules increased, the theory was modified accordingly. These modifications enable us to understand how molecules hold energy. Extensive observations of gas behavior reveal that all gases have certain properties in common. These include the ability to expand or contract readily, and the ability to diffuse or to pass through other gases. These properties are of considerable theoretical and practical interest and have been studied extensively. Module 6A Boyles Law: Robert Boyle, in 1662, measured the change in volume with the change in pressure while keeping the amount of air and the temperature constant. The data are plotted in a graph. Comparison of the data showed that the volume decreases as the pressure increases. Similar data can be obtained for any kind of gas; they show that the qualitative effect of a decrease in volume when the pressure is increased is common to all gases. A further study of the data in column 3 of Table 1 reveals that the product of the pressure times volume is a constant value i.e. PV = constant value = k ---(1) (amount and temperature constant) or for a given quantity of gas at two different pressures, P1 and P2;

83

Table 1: Change in volume with change in pressure for a given amount of gas at constant temperature.
3.0

Pressure (atm) 0.200 0.500 1.000 1.500 ----(2)

Volume (Litres) 3.00 1.20 0.60 0.40

Pressure X Volume 0.600 0.600 0.600 0.600

2.5

Volume (litres)

2.0

1.5

1.0

P1V1 = k = P2V2 or V1 / V2 = P2 / P1.---------

0.5

0.0 0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

(atm) The above results may be summarized in the form of a Pressure quantitative statement known as

Boyles Law: The volume that a gaseous substance occupies is inversely proportional to the pressure under which it is measured, provided that the temperature and the amount of gas are held constant. The significance of the phrase inversely proportional may be better understood by dividing both sides of the equation (1) by P to obtain the equation in the following form: V = k x 1 / P (amount and temperature constant).----------(3) This shows in symbols that the volume is proportional to the reciprocal of the pressure, that is, inversely proportional to the pressure. It means that as P increases, V decreases and vice versa. k is the proportionality constant. The value of k however depends upon the amount and kind of gas, upon the temperature, and of course, upon the units used for P and V. Problem: 10 litres of a gas in tank at 2 atm. pressure is allowed to expand at constant temperature into an evacuated container having a volume of 50 litres. What pressure will the gas exert in this volume? Solution: Since the temperature and amount of gas remain constant, the increase in volume must be accompanied by a corresponding decrease in pressure. We can find the final pressure by multiplying the initial pressure by a ratio of the two volumes. To obtain the correct answer, 84

this ratio must be such that the final pressure is less than the initial pressure. This means that the smaller volume must be in the numerator, the larger volume in the denominator. P Final = P Initial x V Initial / V Final = 2 x 10 / 50 = 0.40 atm. Pressure is a property that determines the direction of gas (or mass) flow, just as temperature determines the direction of heat flow. Unless otherwise restrained, a gas (and liquids or solids) tends to move from a region of higher pressure to one of low pressure. In fluids, (gases and liquids), the pressure at a given point is the same in all directions. Module 6B Charles Law Experiments show that all gases expand when the temperature is raised (if the pressure is kept constant). To make this qualitative statement quantitative, experiments must be performed to show how much the volume of a given quantity of gas changes for a measured change in temperature at constant pressure. The results of four such experiments are given in Table.2. Table.2 Change in volume of gases with change in temperature, for constant mass and constant pressure. A Volume of 1g of O2 at 1500 torr (litres) 0.312 0.364 0.416 0.468 0.520 B Volume of 1g of O2 at 2500 torr (litres) 0.187 0.218 0.250 0.281 0.312 C Volume of 0.5 g of O2 at 1500 torr (litres) 0.156 0.182 0.208 0.234 0.260 0.104 0.117 0.130 D Volume of 0.5 g of SO2 at 1500 torr (litres)

Temperature (C) -33.0 +7.0 +47.0 +87.0 +127.0

By trying various mathematical operations with these data, we find that a graph of volume against temperature gives, for each case, a straight line as shown below.
A = 1g O2 at 1500 torr B = 1g O2 at 2500 torr

85

C = 0.5g O2 at 1500 torr

0.6

0.5

Volume (litres)

0.4

0.3

0.2

0.1

0.0

-200

-100

100

200

Temperature (K)

D = 0.5g O2 at 1500 torr

The slopes and intercepts of these lines differ according to the amount of gas used (A compared to C), the (constant) pressure under which the measurements are carried out (compare A with B), and the kind of gas used (C and D). the curious fact emerges, however, that if the curves are extended (extrapolated) to lower and lower temperatures, all four meet at the same point on the temperature axis

at -273C (more precisely, - 273.15C). This means that if we could lower the temperature of a gas to -273C, the gas should occupy zero volume, regardless of the kind of gas, the weight of it present, or the pressure under which it was measured. Of course, such a contraction to zero volume could never occur. Before such a low temperature was reached, the gas would have changed to a liquid or a solid. Absolute temperature, Natures temperature minimum We can take advantage of this uniformity of gas behavior by changing the zero of the temperature scale to -273C. On this new absolute temperature scale, zero of temperature corresponds to the apparent zero of gas volume. The volume of a gas is now said to be

86

directly proportional to the absolute temperature, provided the quantity of gas and its pressure remain constant. This is a statement of Charles Law. Expressed in symbols, Charles law is V = k T ----------(4) (amount and pressure constant) where T is an absolute temperature and k is a proportionality constant. Expression (4) is an equation for a straight line of zero intercept as shown in the graph. The more common absolute temperature scale, known as the Kelvin scale, maintains the size of the degree the same as the size of the Celsius degree, but changes the zero point by 273, so that 0 K = 273C; 273 K = 0C, 373 K = 100C; etc., A useful form of equation (4) for the same quantity of gas at two different temperatures, but at the same pressure, is V1 / V2 = T1 / T2--------(5) Problem: 10 litres of gas in a large balloon at 0C is heated, and the balloon is allowed to expand at constant pressure to a temperature of 200C. What will be the volume of the balloon at this temperature? Solution: Because the amount of gas and its pressure remain constant, the increase in absolute temperature must be accompanied by a corresponding increase in volume. We can find the final volume by multiplying the initial volume by a ratio of the absolute temperatures, arranged such that the final volume will be larger than the initial volume. This means that the higher absolute temperature must be in the numerator; the lower absolute temperature must be in the denominator of this ratio. i.e. V 17.3 litres. We can combine the two laws for the behavior of ideal gases into a single relationship using the three variables pressure, volume and temperature for a given amount of an ideal gas: P1V1 / T1 = P2V2 / T2 This relationship can be called the combined gas laws. It is valid only when the temperature is given in Kelvins. We can use this relationship for any calculation in which a given amount of gas undergoes a change in conditions. 87
Final

=V

Initial

xT

abs.Final

/T

abs.Initial

= 10 x 473 / 273 =

Another way to interpret the combined gas laws is to say that for a given amount of gas, PV / T is a constant. The value of this constant depends on the amount of gas in a sample. We can put this interpretation in the form of an equation. It is called the ideal gas equation and generally is written as PV = nRT where n is the usual symbol for amount in moles and R is a constant called the Universal Gas Constant. While T must be given in Kelvins and n is almost always given in moles, the units of P and V may vary. The value of R thus depends on the units used for P and V. One common value that is often used is litres as the unit of volume and atmospheres as the unit of pressure. The value of R then is 0.0821 lit.atm. mol -1K-1. The ideal gas equation provides a complete description of an ideal gas. An ideal gas is defined as a gas for which both the volume of molecules and the forces between the molecules are so small that they have no effect on the behavior of the gas. Although no such ideal gas exists, the ideal gas equation can be used to describe the behavior of a real gas. All gases are real gases. Real gases behave like ideal gases under many ordinary conditions. Only at low temperatures and high pressures, do real gases show significant nonideal behavior. For now, let us assume that gases are close to ideal and the ideal gas equation applies. Avogadros Law: The Amount Volume relationship Early in the 19th century, the Italian Chemist Amedeo Avogadro proposed a very simple but profound hypothesis relating to the volume of a gas to the number of gas particles. Although this hypothesis resolved many of the problems that puzzled scientists in those times, only decades later, did the hypothesis gain acceptance. Avogadros law states that equal volumes of gases at the same temperature and pressure contain an equal number of particles. Avogadros law contains 2 important points worth noting. First, it states that all gases show the same physical behavior. Second, the law tells us that a gas with a larger volume must consist of a greater number of particles. This is quite reasonable. As long as the pressure and temperature of a gas do not change, the only way to change the volume is by changing the number of gas particles.

88

Because n, the number of moles, is directly proportional to the number of particles, the relationship expressed by Avogadros law can be written as V = k n where n is the number of moles and k is the proportionality constant Avogadros law constant. The volume of one mole of gas is called the molar volume, whose value is 22.4 litres at STP (273 K and 1 atm). Daltons law of Partial Pressures The English Chemist John Dalton was among the first few scientists to consider mixtures of gases even though he did not have the kinetic-molecular theory of gases available to help him formulate and develop his ideas. After experimenting with gases and gas mixtures, he proposed that the particles of different gases in a mixture act independently in exerting pressures upon the walls of the container. In other words, he concluded that each gas in a mixture exerts the same pressure that it would if it were present alone at the same temperature. The pressure exerted by each component of a mixture of gases is called the partial pressure of that component. Daltons law of partial pressure states that the sum of the partial pressures of all the components in a gas mixture is equal to the total pressure of the gas mixture. PT = pa + pb + pc +.. In this equation, PT is the total pressure of a gas mixture, pa is the partial pressure of component a, pb is the partial pressure of component b and so on. The law is true only when the component gases do not react chemically with each other. A common laboratory situation that requires the use of Daltons law is encountered when a gas is collected by bubbling it through water. As each gas bubble travels upward through the water, some water evaporates into it, so by the time it escapes from the liquid, the bubble contains a mixture of the gas and water vapour. The total pressure of the mixture in the collection bottle is PT = PA + PH2O. If we wish to know the partial pressure of gas A, we will have to subtract the partial pressure of water vapour from the total pressure. P A = PT - PH2O. The partial pressure of water vapour depends on the temperature. The general formula to calculate the partial pressure of a component from a mixture of gases is given below:

89

Partial pressure of a component = mole fraction of the component x Total pressure. Mole fraction of a component = Number of moles of the component / Total number of moles of all the components in the mixture. Therefore, partial pressure of a component = Total pressure x Number of moles of the component / Total number of moles of all the components in the mixture. Module 6C Grahams Law of gaseous Diffusion All gases have the same kinetic energy at the same temperature. Therefore, from the kinetic energy equation, i.e. K E = mv2, we can see that, if we compare the velocities of the molecules of two gases, the lighter molecules will have a greater velocity than the heavier ones. For example, calculations show that the velocity of a hydrogen molecule is 4 times the velocity of an oxygen molecule. Due to their molecular motion, gases have the property of diffusion, the ability of 2 or more gases to mix spontaneously until they form a uniform mixture. Two large flasks, one containing reddish brown bromine vapours and the other dry air are connected by a side tube. When the stopcock between the flasks is opened, the bromine and air will diffuse into each other. After standing a while, both flasks will contain bromine and air. A gas expands to fill its container even if the container already has gas in it. This process is called diffusion. A similar process takes place when we make a small hole in the wall of a container that holds a gas. The gas passes through the hole by a process called effusion. The rate of both effusion and diffusion depend on the velocity of the gas molecules. For both processes, the rate increases as velocity increases. Thomas Graham, a Scottish chemist, observed that the rate of effusion / diffusion was dependant on the density of a gas. This observation led to Grahams law of effusion or diffusion. The rate of effusion or diffusion of two gases at the same temperature and pressure are inversely proportional to the square roots of their densities or molar masses.

90

Rate of diffusion of gas A / rate of diffusion of gas B = DB/DA = molar mass of B/molar mass of A. Problem: Find the relative rates of diffusion of hydrogen and oxygen gas at the same temperature and pressure. Solution: A simple way to approach this problem is to write the inverse proportionality between the rate and the square root of the molar mass, using a form that is convenient for two sets of conditions. Rate of H2 / rate of O2 = M
O2

/ M H2

Substituting the molar masses of H2 and O2 gives Rate of H2 / rate of O2 = 32 / 2 = 4. The rate of diffusion of hydrogen is 4 times faster the rate of diffusion of oxygen at the same temperature.

91

MODULE 7 ENVIRONMENTAL CHEMISTRY


Introduction Natural Resources Consumption Population Increase and the Environment Urbanization and the environment Industrialization and the Environment

All the external factors that affect an organism could be defined as environment. These factors may be other living organisms or nonliving variables, such as water, soil, climate, light, and oxygen. The environment is never static. Physical forces continuously change the surface of the earth through weather, the action of waves and natural phenomena such as volcanoes. At the same time they introduce gases, vapor and dust into the atmosphere. Living organisms also play a dynamic role through respiration, excretion and ultimately death and decay, recycling their constituent elements through the environment. Just as the familiar substances of our physical universe are divided into solids, liquids and gases, for convenience our physical environment can be divided into the atmosphere, the geosphere, the hydrosphere, the biosphere, the anthroposphere, and all the fauna and flora. Module 7A The Atmosphere The atmosphere is the gaseous envelope that surrounds the solid body of the planet. Although it has a thickness of more than 1100 km about half its mass is concentrated in the lower 5.6 km. The atmosphere is a protective blanket which nurtures life on the Earth and protects it from the hostile environment of outer space. It is the source of carbondioxide for plant photosynthesis and of oxygen for respiration.Transports water from the oceans to land, thus acting as the condenser in a vast solar powered still. Serves a vital protective function, absorbing harmful ultraviolet radiation from the sun and stabilizing Earths temperature. 92

Module 7B The Hydrosphere The hydrosphere is the layer of water that, in the form of the oceans, covers approximately 70.8 percent of the surface of the earth. Water covers about 70% of Earths surface and over 97 % of this water exists in oceans. It occurs in all spheres of the environment in the oceans as a vast reservoir of saltwater, on land as surface water in lakes and rivers, underground as groundwater, in the atmosphere as water vapor, in the polar icecaps as solid ice, and in many segments of the anthrosphere such as in boilers or municipal water distribution systems. It is an essential part of all living systems and is the medium from which life evolved and in which life exists. It carries energy and matter are through various spheres of the environment. Leaches soluble constituents from mineral matter and carries them to the ocean or leaves them as mineral deposits some distance from their sources. Carries plant nutrients from soil into the bodies of plants by way of plant roots. Absorbs solar energy in oceans and this energy is carried as latent heat and released inland when it evaporates from oceans. The accompanying release of latent heat provides a large fraction of the energy that is transported from equatorial regions toward Earths poles and powers massive storms. Module 7C The Geosphere The geosphere, is that part of the Earth upon which humans live and from which they extract most of their food, minerals, and fuels. It is divided into layers, which include the solid, ironrich inner core, molten outer core, and the lithosphere which consists of the upper mantle and the crust. Inner core, Outer core, Lower mantle, Transition zone, Upper mantle, Crust Lithosphere, Transition zone. Environmental science is most concerned with the lithosphere, which extends to depths of 100 km and comprises two shellsthe crust and upper mantle. The crust (the earths outer skin) is the layer that is accessible to humans and i s extremely thin compared to the diameter of the earth, ranging from 5 to 40 km thick.

93

Module 7D The Biosphere The Biosphere is the earths relatively thin zone of air, soil, and water that is capable of supporting life, ranging from about 10 km into the atmosphere to the deepest ocean floor. Life in this zone depends on the suns energy and on the circulation of heat and essential nutrients. The biosphere is virtually contained by the geosphere and hydrosphere in the very thin layer where these environmental spheres interface with the atmosphere. It strongly influence bodies of water, producing biomass required for life in the water and mediating oxidation-reduction reactions in the water. It is involved with weathering processes that break down rocks in the geosphere and convert rock matter to soil. Biosphere is mainly responsible for plant photosynthesis, which fixes solar energy and carbon from atmospheric CO2 in the form of high-energy biomass, represented as carbohydrates. Module 7E The Flora and Fauna The terms fauna and flora are collective names given to animals and plants respectively. There is a continuous interaction between the various sections of the environment and the flora and fauna. An assembly of mutually interacting organisms and their environment in which materials are interchanged in a largely cyclical manner is known as ecosystem. The environment in which a particular organism lives is called habitat. All parts of the environment are subjected to drastic change due to human overuse of natural resources. Module 7F Natural Resources Consumption In the last two and half century, the industrial revolution has changed the face of the planet by natural resources at an alarming rate, especially fossil fuel. Every year natural resources consumption is rising as the human population increases and standards of living rise. In the following possible environmental consequences accompanying the over consumption of the natural resources: fossil fuel, forest wood, water, land and energy by humans.

94

Fossil Fuel: Fossil Fuels, which include petroleum, coal, and natural gas, are energy-rich substances that have formed from long-buried plants and microorganisms. They provide most of the energy that powers modern industrial society. The gasoline that fuels our cars, the coal that powers many electrical plants, and the natural gas that heats our homes are all fossil fuels. Fossil fuels are largely composed of hydrocarbons which are formed from ancient living organisms that were buried under layers of sediment millions of years ago. These fuels are extracted from the earths crust, and refined into suitable fuel products, such as gasoline, heating oil, and kerosene. Some of these hydrocarbons may also be processed into plastics, chemicals, lubricants, and other non-fuel products. The most commonly used fossil fuels are petroleum, coal, and natural gas. Once extracted and processed, fossil fuel can be burned for direct uses, such as to power cars or heat homes, or it can be combusted for the generation of electrical power. Within the last century, the amount of carbon dioxide in the atmosphere has increased dramatically, largely because of the practice of burning fossil fuels. This has resulted in an increase in global temperature. The consequences of such an increase in temperature may well be dangerous. Sea levels will rise, completely inundating a number of low-lying island nations and flooding many coastal cities. Many plant and animal species may probably be forced to go into extinction, agricultural regions will be disrupted, and the frequency of droughts is likely to increase. Forest Wood: Forests are very important for maintaining ecological balance and provide many environmental benefits. In addition to timber and paper products, forests provide wildlife habitat, prevent flooding and soil erosion, help provide clean air and water, and contain tremendous biodiversity. Forests are also an important defense against global climate change. Forests produce life-giving oxygen and consume carbon dioxide, the compound most responsible for global warming through photosynthesis, thereby reducing the effects of global warming. Forests provide habitat for a wide variety of plants and animals and perform many other important functions that affect humans. The forest canopy (the treetops) and root systems provide natural filters for the water we use from lakes and rivers. When it rains the forest canopy intercepts and re-distributes precipitation that can cause flooding and erosion, the wearing away of top soil. Some of the precipitation flows down the trunks as stemflow, the rest percolates through the branches and foliage as throughfall. The canopy is also able to

95

capture fog, which it distributes into the vegetation and soil. Forests also increase the ability of the land to store water. Soil: Soil, a mixture of mineral, plant, and animal materials, is essential for most plant growth and is the basic resource for agricultural production. In the process of developing the land and clearing away the vegetation that holds water and soil in place, erosion has devastated soils worldwide. The rapid deforestation taking place in the tropics is especially damaging because the thin layer of soil that remains is fragile and quickly washes away when exposed to the heavy tropical rains. Globally, agriculture accounts for 28 percent of the nearly 2 billion hectares of soil that have been degraded by human activities; overgrazing is responsible for 34 percent; and deforestation is responsible for 29 percent. Water: Clean freshwater resources are essential for drinking, bathing, cooking, irrigation, industry, and for plant and animal survival. Due to overuse, pollution, and ecosystem degradation the sources of most freshwater suppliesgroundwater (water located below the soil surface), reservoirs, and riversare under severe and increasing environmental stress. Over 95 percent of urban sewage in developing countries is discharged untreated into surface waters such as rivers and harbors. About 65 percent of the global freshwater supply is used in agriculture and 25 percent is used in industry. Freshwater conservation therefore requires a reduction in wasteful practices like inefficient irrigation, reforms in agriculture and industry, and strict pollution controls worldwide. Population Increase and the Environment : The world population is increasing at an alarming rate. From 1930 to present it rose from 2 billion to 5.3 billion. And it is expected to rise again to over 8 billion in 2050. The demands of increasing population coupled with the desire of most people for a higher material standard of living are resulting in worldwide pollution on a massive scale. Environmental problems have led to shortages of food, clean water, materials for shelter, and other essential resources. As forests, land, air, and water are degraded, people who live directly off these natural resources suffer most from the effects. Global environmental degradation may result from a variety of factors, including overpopulation and the resulting overuse of land and other resources. Intensive farming, for instance, depletes soil fertility, thus decreasing crop yields. Environmental degradation also

96

results from pollution. Polluting industries include mining, power generation, and chemical production. Other major sources of pollution include automobiles and agricultural fertilizers. In developing countries, deforestation has had particularly devastating environmental effects. Many rural people, particularly in tropical regions, depend on forests as a source of food and other resources, and deforestation damages or eliminate these supplies. Forests also absorb many pollutants and water from extended rains; without forests, pollution increases and massive flooding further decreases the usability of the deforested areas. Poor land management and increasing population are factors that promote increased irrigation, improper cultivation or over cultivation, and increased numbers of livestock. These events alter the land and the soil, diminish the resources, and increase the chances of desertification. Over the last few years urbanization of rural areas has increased. As agriculture, more traditional local services, and small-scale industry give way to modern industry the urban and related commerce with the city drawing on the resources of an ever-widening area for its own sustenance and goods to be traded or processed into manufactures. Urbanization is among the most significant factors that aggravated environmental degradation. In the following subunit we shall briefly discuss on the impacts of urbanization on the environment. Industrialization and the Environment : The world population is increasing at an alarming rate. From 1930 to present it rose from 2 billion to 5.3 billion. And it is expected to rise again to over 8 billion in 2050. The demands of the increasing population coupled with the desire of most people for a higher material standard of living has intensified industrialization. These industrial activities, aided by modern technologies, provide the food, shelter, and goods that humans need for their well-being and survival. Industrial manufacturing processes may

consist of the synthesis of a chemical from raw materials, casting of metal or plastic parts, or any of the other things that is needed to produce a certain product. Each of these processes carries with it the potential to cause significant air and water pollution and production of hazardous wastes. The earlier in the design and development process that environmental considerations are taken into account, the more environmentally friendly a manufacturing process will be. Over the past 30 years, industrial production has been a major source of pollution in urban areas and a significant driver of intensified resource use.

97

Most air pollution comes from one human activity: burning fossil fuelsnatural gas, coal, and oilto power industrial processes and motor vehicles. This results in the emission of harmful chemical compounds such as carbon dioxide, carbon monoxide, nitrogen oxides, sulfur dioxide, and tiny solid particlesincluding lead from gasoline additivescalled particulates. Various volatile organic chemicals (VOCs), generated from incompletely burned fuels, also enter the air. Carbon dioxide is one of the green house gases which contribute significantly to global warming. Sulfur dioxide and nitrogen oxide emissions are the principal causes of acid rain in many parts of the world. Sulfur dioxide and nitrogen oxides emitted into the atmosphere, are absorbed by rain to form sulphuric acid and nitric acid. These acids are bad for the lungs and attack anything made of limestone, marble, or metal. Smog is a type of air pollution produced when sunlight acts upon motor vehicle exhaust gases to form harmful substances such as ozone (O3), aldehydes and peroxyacetylnitrate (PAN). Before the automobile age, most smog came from burning coal. Burning gasoline in motor vehicles is the main source of smog in most regions today. Powered by sunlight, oxides of nitrogen and volatile organic compounds react in the atmosphere to produce photochemical smog. Ozone in the lower atmosphere is a poison it damages vegetation, kills trees, irritates lung tissues, and attacks rubber. Smog spoils views and makes outdoor activity unpleasant. The effects of smog are even worse for the very young and the very old people who suffer from asthma or heart disease. Smog can cause breathing difficulties, headaches and dizziness. In extreme cases, smog can lead to mass illness and death, mainly from carbon monoxide poisoning. Module 7G Atmospheric Chemistry

Pollution is changing Earths atmosphere so that it lets in more harmful radiation from the Sun. The temperature increase, known as global warming, is predicted to affect world food supply, alter sea level, make weather more extreme, and increase the spread of tropical disease. As a chemistry teacher, you are expected to contribute your part to the solution of the current globally burning issue of atmospheric pollution. You should be able to describe the composition of the atmosphere, the major contributors to atmospheric pollution and the way these pollutants are accumulated in the atmosphere. In this unit, we shall discuss the chemistry

98

of the atmosphere and the major pollutants of the atmosphere, describe the way these pollutants are formed and accumulated in the atmosphere and the threat posed by the pollutants. Atmospheric chemistry: is a branch of atmospheric science in which the chemistry of the Earths atmosphere and that of other planets is studied. The composition and chemistry of the atmosphere is of importance for several reasons, but primarily because of the interactions between the atmosphere and living organisms. The composition of the Earths atmosphere has been changed by human activity and some of these changes are harmful to human health, crops and ecosystems. Examples of problems which have been addressed by atmospheric chemistry include acid rain, photochemical smog and global warming. Atmospheric chemistry seeks to understand the causes of these problems, and by obtaining a theoretical understanding of them, allow possible solutions to be tested and the effects of changes in government policy evaluated. Earths atmosphere: is a layer of gases surrounding the planet Earth and retained by the Earths gravity. It contains roughly 78% nitrogen, 21% oxygen, 0.93% argon, 0.04% carbon dioxide, and trace amounts of other gases, in addition to water vapor. This mixture of gases is commonly known as air. The atmosphere protects life on earth by absorbing solar UV radiation and reducing temperature extremes between day and night. The gases ozone, water vapor, and carbon dioxide are only minor components of the atmosphere, but they exert a huge effect on the Earth by absorbing radiation. Ozone in the upper atmosphere filters out the ultraviolet light below about 360 nm that is dangerous for living things. In the troposphere ozone is an undesirable pollutant. It is toxic to animals and plants, and it also damages materials. The atmosphere slowly becomes thinner and fades away into space. Therefore, there is no definite boundary between the atmosphere and outer space. Seventy five percent of the atmospheres mass is within 11 km of the planetary surface. Atmospheric layers: Although atmospheric pressure decreases in a regular way at higher altitudes the profile of temperature versus altitude is much more complex. The temperature of the Earths atmosphere varies with altitude and the mathematical relationship between temperature and altitude varies between the various atmospheric layers: Four regions of the

99

atmosphere, the troposphere, stratosphere, mesosphere and thermosphere, have been defined based on the temperature. The Troposphere is the region nearest the earths surface. This is the region between the surface of the earth and 7 km altitude at the poles and 17 km at the equator with some variation due to weather factors. Air temperature drops uniformly with altitude at a rate of approximately 6.5 Celsius per 1000 meters. Top is reached at an average temperature of 56.5C. In the stratosphere, temperature remains constant with height in the first 9 kilometers (called an isothermal layer) and then goes on increasing. Above the stratosphere in the region from 50 to about 80 km, the temperature again decreases in the mesosphere. The atmosphere reaches its coldest temperatures (about -90C) at the top layer of the mesosphere (a height of about 80 km). The upper atmosphere is characterized by the presence of significant levels of electrons and positive ions. Because of the rarefied conditions, these ions may exist in the upper atmosphere for long periods before recombining to form neutral species. At altitudes of approximately 50 km and up, ions are so prevalent that the region is called the ionosphere. Ultraviolet light is the primary producer of ions in the ionosphere. In darkness, the positive ions slowly recombine with free electrons. The process is more rapid in the lower regions of the ionosphere where the concentration of species is relatively high. Atmospheric temperature again increases at the thermosphere. Temperature in this layer can be as high as 1200C. The boundaries between these regions are named the tropopause, stratopause, mesopause, and thermopause. The average temperature of the atmosphere at the surface of Earth is 14 C. Passenger jets normally fly near the top of the troposphere at altitudes of 10 to 12 km, and the world altitude record for aircraft is 37.65 km roughly in the middle of the stratosphere. Atmospheric Chemical Reactions: Two constituents of utmost importance in atmospheric chemistry are radiant energy from the sun, predominantly in the ultraviolet region of the spectrum, and the hydroxyl radical, HO. The former provides a way to pump a high level of energy into a single gas molecule to start a series of atmospheric chemical reactions, and the latter is the most important reactive intermediate of daytime atmospheric chemical phenomena. Nitrogen dioxide, NO2, is one of the most photochemically active species found in a polluted atmosphere. A species such as NO2 may absorb light to produce an electronically excited molecule. An electronically excited molecule is a molecule which has 100

absorbed energetic electromagnetic radiation in the UV or visible regions of the spectrum.Electronically excited molecules, free radicals, and ions consisting of electricallycharged atoms or molecular fragments are the three relatively reactive and unstable species that are encountered in the atmosphere. They are strongly involved in atmospheric chemical processes. A) Formation of Free Radicals

Free radicals are atoms or groups of atoms with unpaired electrons. Such species may be produced by the action of energetic electromagnetic radiation on neutral atoms or molecules. The strong pairing tendencies of the unpaired electrons make free radicals highly reactive and are involved with most significant atmospheric chemical phenomena. The hydroxyl radical, HO, is the single most important reactive intermediate species in atmospheric chemical processes. It is formed by several mechanisms. At higher altitudes it is produced by photolysis of water:

In the relatively unpolluted troposphere, hydroxyl radical is produced as the result of the photolysis of ozone,

Hydroxyl radical is removed from the troposphere by reaction with methane or carbon monoxide:

The hydrogen atom produced in the second reaction reacts with O2 to produce hydroperoxyl radical which in turn may react with another hydroperoxyl or hydroxyl radical

101

or reactions that regenerate hydroxyl radical:

B)

Acid Base Reactions in the Atmosphere

The atmosphere is slightly acidic because of the presence of a low level of carbon dioxide, which dissolves in atmospheric water droplets and dissociates slightly:

In terms of pollution, however, strongly acidic HNO3 and H2SO4 formed by the atmospheric oxidation of N oxides, SO2, and H2S are much more important because they lead to the formation of damaging acid rain. Basic species are relatively less common in the atmosphere. Particulate calcium oxide, hydroxide, and carbonate can get into the atmosphere from ash and ground rock, and can react with acids such as in the following reaction:

The most important basic species in the atmosphere is gas-phase ammonia, NH3. The major source of atmospheric ammonia is the biodegradation of nitrogen containing biological matter and bacterial reduction of nitrate:

102

Ammonia is the only water soluble base present at significant levels in the atmosphere. This makes it particularly important as a base in the air. Dissolved in atmospheric water droplets, it plays a strong role in neutralizing atmospheric acids:

C)

Reactions of Atmospheric Oxygen

In addition to O2, the upper atmosphere contains oxygen atoms, O; excited oxygen molecules, O2*; and ozone, O3. Atomic oxygen, O, is stable primarily in the thermosphere, where the atmosphere is so rarefied that the three-body collisions necessary for the chemical reaction of atomic oxygen seldom occur. Atomic oxygen is produced by a photochemical reaction:

At altitudes exceeding about 80 km, the average molecular weight of air is lower than the 28.97 g/mole observed at sea level because of the high concentration of atomic oxygen. This condition has divided the atmosphere into a lower section with a uniform molecular weight (homosphere) and a higher region with a nonuniform molecular weight (heterosphere). Molecular oxygen and excited oxygen atoms (O*) are produced due to the photolysis of atmospheric ozone

or by highly energetic chemical reactions such as

103

Oxygen ion, O+, which may be produced by ultraviolet radiation acting upon oxygen atoms, is the predominant positive ion in some regions of the ionosphere. It may react with molecular oxygen or nitrogen to form other positive ions:

In intermediate regions of the ionosphere, O2+ is produced by absorption of ultraviolet radiation at wavelengths of 17-103 nm

Atmospheric ozone is produced by photochemical dissociation of molecular oxygen followed by a three body reaction

in which M is another species, such as a molecule of N2 or O2, which absorbs the excess energy given off by the reaction and enables the ozone molecule to stay together. In addition to undergoing decomposition by the action of ultraviolet radiation, stratospheric ozone reacts with atomic oxygen, hydroxyl radical, and NO: The HO radical is regenerated from HOO by the reaction,

The HO radical is regenerated from HOO by the reaction,

104

D)

Reactions of Atmospheric Nitrogen

Unlike oxygen, molecular nitrogen is not readily dissociated by ultraviolet radiation. However, at altitudes exceeding approximately 100 km, atomic nitrogen is produced by photochemical reactions:

Other reactions which may produce monatomic nitrogen are:

In the region above 105 km of the ionosphere a plausible sequence of reactions by which NO+ is formed is the following:

In the lowest region of the ionosphere, which extends from approximately 50 km in altitude to approximately 85 km, NO+ is produced directly by ionizing radiation:

E) Atmospheric Carbondioxide Although only about 0.035% (350 ppm) of air consists of carbon dioxide, it is the atmospheric nonpollutant species of most concern. Chemically and photochemically, however, it is a comparatively insignificant species because of its relatively low concentrations and low photochemical reactivity. The one significant photochemical reaction that it undergoes, and a major source of CO at higher altitudes, is the photo-dissociation of CO2 by energetic solar UV radiation in the stratosphere:

105

F) Atmospheric Water The water vapor content of the troposphere is normally within a range of 13% by volume with a global average of about 1%. However, air can contain as little as 0.1% or as much as 5% water. The percentage of water in the atmosphere decreases rapidly with increasing altitude. The cold tropopause serves as a barrier to the movement of water into the stratosphere. Thus, little water is transferred from the troposphere to the stratosphere, and the main source of water in the stratosphere is the photochemical oxidation of methane:

The water thus produced serves as a source of stratospheric hydroxyl radical as shown by the following reaction:

Module H Air Pollution Air Pollution can be defined as the addition of harmful substances to the atmosphere resulting in damage to the environment, human health, and quality of life. Air pollution causes breathing problems and promotes cancer. It harms plants, animals, and the ecosystems in which they live. Some air pollutants return to Earth in the form of acid rain and snow, which corrode statues and buildings, damage crops and forests, and make lakes and streams unsuitable for fish and other plant and animal life. Especially the pollutants that result from the use of combustion as a source of energy: oxides of sulfur, oxides of nitrogen, and carbon monoxide. Classification of Air Pollutants There are a number of ways of classifying air pollutants. Most commonly they are classified on the basis of 1) differences in their physical or chemical characteristics, 2) by their origin, 3) by the nature of the response they elicit, 4) by their legal status. 106

Based on differences in their physical or chemical characteristics Aerosols:- are tiny particles dispersed in gases and include both liquid and solid particles. Air pollution terminology relating to atmospheric aerosols includes dusts, fog, fumes, hazes, mists, particulate matter, smog, smoke, and soot. Gases and vapors:- are composed of widely separated freely moving molecules which will expand to fill a larger container and exert a pressure in all directions. A substance is a true gas if it is far removed form the liquid state (i.e. the temperature of the substance is above its critical point). A vapor is a substance in the gaseous state which is not far from being a liquid (i.e. it can be condensed to a liquid relatively easily). Major Sources of Air Pollution Human activities such as: burning coal and petroleum products (gasoline, kerosene, fuel oil etc; driving a car, and industrial activities, such as manufacturing products or generating electricity are among the major sources of air pollutants. The generation of energy through the combustion of fossil fuels produces plenty of water and carbon dioxide, which contributes to global warming. When coal, gasoline, and similar fuels are burned, the hydrocarbons and other impurities in them are oxidized. The sulfur of the pyrite that remains in coal, oxidizes to sulfur dioxide, an irritating gas with a harsh, acrid odor. The oxides formed under this condition combine with water vapor in the air to form acids, which return to the ground as acid rain. Powered by sunlight, oxides of nitrogen and volatile organic compounds react in the atmosphere to produce photochemical smog. Smog contains ozone, a form of oxygen gas made up of molecules with three oxygen atoms rather than the normal two. In the lower atmosphere Ozone is a poisonit damages vegetation, kills trees, irritates lung tissues, and attacks rubber. The severity of smog is determined by measuring the ozone level in the smog. When the ozone level is high, other pollutants, including carbon monoxide, are usually present at high levels as well. The very young, the very old, and people who suffer from asthma or heart disease, are more seriously affected by smog. Smog may cause headaches or dizziness and can cause breathing difficulties. In extreme cases, it can lead to mass illness and death, mainly from carbon monoxide poisoning. Still another pollutant, a product of the incomplete combustion of carbon or organic compounds, such as the hydrocarbons of 107

gasoline, one that we cant see and that produces no sense of irritation, is carbon monoxide, CO. This gas is known as the silent killer because it is odorless, tasteless, and invisible. Its major symptom is a drowsiness sometimes accompanied by headache, dizziness, and nausea. CO is primarily a pollutant of cities and usually fluctuates with flow of traffic. Air Pollution and Acid-Rain Rainwater which was considered to be the purest form of water available in the past, is now known to be often contaminated by pollutants in the air. In the presence of atmospheric moisture, gases such as sulfur dioxide and oxides of nitrogen, resulting from industrial emissions, turn into droplets of pure acid floating in smog, known as acid rain. These airborne acids are bad for the lungs and attack anything made of limestone, marble, or metal. Forests and lakes that are far away from industrial activities may be damaged by acid rain resulting from pollutants that may be carried by winds in the troposphere and descend in acid form, usually as rain or snow. Leaves of plants are burned and lakes will be too acidic to support fish and other living things due to acid precipitation. Air Pollution and Ozone Depletion The lower portion of the stratosphere from approximately 15 km to 3 5 km above Earths surface contains high concentration, over 90%, of the ozone (O3) in earths atmosphere. This part of the Earths atmosphere is known as the ozone layer. Nearly all, 97-99%, of the suns high frequency UV-radiation which is potentially damaging to life on Earth is absorbed in this layer. Several pollutants attack the ozone layer. However, chlorofluorocarbons (CFCs) are known to be chief among them. CFC molecules are stable, virtually indestructible until they reach the stratosphere. Here, the CFC molecules are broken apart by intense ultraviolet radiation and release the chlorine atoms they contain. These chlorine atoms react with ozone and break it down into ordinary oxygen molecules that do not absorb UV-radiation. The chlorine acts as a catalyst Chlorine takes part in several chemical reactionsyet at the end emerges unchanged and able to react again. Therefore, it acts as a catalyst. A single chlorine atom can destroy up to 100,000 ozone molecules in the stratosphere. In addition to CFCs, other pollutants, such as nitrous oxide from fertilizers and the pesticide methyl bromide, also

108

attack atmospheric ozone. Scientists are finding that under this assault the protective ozone layer in the stratosphere is thinning. Global Warming: The energy that lights and warms Earth comes from the Sun. Most of this energy comes as short-wave radiation. Earths surface, in turn, releases some of this heat as long-wave infrared radiation. Much of the emitted infrared radiation goes back out to space, but a portion remains trapped in Earths atmosphere. Certain gases in the atmosphere, including water vapor, carbon dioxide, and methane, provide the trap. Absorbing and reflecting infrared waves radiated by Earth, these gases conserve heat as the glass in a greenhouse does and are thus known as greenhouse gases. As the atmosphere becomes richer in these gases, it becomes a better insulator, retaining more of the heat provided to the planet by the Sun. The net result; more heat is received from the sun than is lost back to space, a phenomenon known as greenhouse effect. Because of this green house effect, the average surface temperature of the Earth is maintained at a relatively comfortable 15C. Was this not the case, the surface temperature would average around -18C. The problem with global warming is that man is adding to and changing the levels of the greenhouse gases and is therefore enhancing this warming. Carbon dioxide (CO2) is the gas most significantly enhancing the greenhouse effect. Plant respiration and decomposition of organic material release more than 10 times the CO 2 than released by human activities, but these have generally been in balance before the industrial revolution. Since the industrial revolution amounts have increased drastically due to combustion of fossil fuel (oil, natural gas and coal) by heavy industry and other human activities, such as transport and deforestation. Other factors slow the warming, but not to the same degree. i) The world is expected to have a more extreme weather, with more rain during wet periods, longer droughts, and more powerful storms. ii) Melting of the polar ice caps, leading to a rise in sea level. Such a rise would flood coastal cities, force people to abandon low-lying islands, and completely inundate coastal wetlands. Diseases like malaria may become more common in the regions of the globe between the tropics and the polar regions, called the

109

temperate zones. iii) Climate change may bring extinction for many of the worlds plant species, and for animal species that are not easily able to shift their territories as their habitat grows warmer. Module 7I Aquatic chemistry and Water pollution

Properties of Water Water is a vitally important substance in all parts of the environment. It covers about 70% of Earths surface and occurs in all spheres of the environment. It is an essential part of all living systems. Water carries energy and matter through various spheres of the environment. It carries plant nutrients from soil into the bodies of plants by way of plant roots. The properties of water would best be understood by considering the structure and bonding of the water molecule. A single water molecule we have two hydrogen atoms bonded covalently to an oxygen atom. The three atoms are arranged in a V-shape structure with an angle of 105. Because of its bent structure and the fact that the oxygen atom attracts electrons more strongly than hydrogen atoms, a water molecule behaves like a dipole having opposite electrical charges at either end. The water dipole may be attracted to either positively or negatively charged ions like with Na+ and Cl- during the dissolution of NaCl. Water has the ability to form hydrogen bonds. Hydrogen bond is a special type of bond that can form between the partially positively charged hydrogen atoms in one water molecule and the partially negatively changed oxygen atoms in another water molecule. Hydrogen bond holds water molecules together with strong and also help to hold some solute molecules or ions in solutions. Dissolved Gases in Water: Natural water systems contain a number of gases dissolved in them. Among these gases O2 and CO2 are vital for aquatic animals and plants. For example O2 is essential for fish and CO2 for photosynthetic algae. Some gases in water can also cause problems, such as the death of fish from bubbles of nitrogen formed in the blood. Oxygen in Water: Most of the elemental oxygen that we find dissolved in water comes from the atmosphere and also from the photosynthetic action of algae. As many kinds of aquatic organisms require oxygen for their existence, water bodies should contain appreciable level of

110

dissolved oxygen. Dissolved oxygen can decrease due to different reasons. Part of the oxygen coming from algal photosynthesis during the day for example is used up by the algae itself as part of their metabolic processes. Because of this, dissolved oxygen contribution through algal photosynthesis is not that efficient. The degradation of biomass coming from dead algae and other organic matter also consume dissolved oxygen. Therefore, the ability of a body of water to reoxygenate itself by contact with the atmosphere is an important characteristic. Carbon Dioxide in Water: Carbondioxide is present in virtually all natural waters and wastewaters and is the most important weak acid in water. The CO2 in water comes from the dissolution of atmospheric CO2 and from microbial decay of organic matter. carbon dioxide and its ionization products have extremely important influence upon the chemistry of water. Many minerals are deposited as salts of the carbonate ion. Although dissolved CO 2 is often represented as H2CO3 just a small fraction of the dissolved CO2 is actually present as H2CO3. Therefore, to make a distinction, non-ionized carbon dioxide in water is designated simply as CO2. Physical Water Quality Parameters: Physical parameters define those characteristics of water that respond to the sense of sight, touch, taste or smell. Suspended solids, turbidity, color, taste and odor, and temperature fall in this category. Suspended solids - Sources and impacts: Solids can be dispersed in water in both suspended and dissolved forms. Although some dissolved solids may be perceived by the physical sense, they fall more approximately under the category of chemical parameters. Solids suspended in water may consist of inorganic substances such as clay and silt or organic particles such as plant fibers, algal and bacterial remains. Because of the filtering capacity of the soil, suspended material is seldom a constituent of ground water. Domestic wastewater usually contains large quantities of suspended solids that are mostly organic in nature. Suspended materials in water make the water aesthetically unpleasant and provide adsorption sites for chemical and biological agents. Biological degradation of suspended organic solids results in objectionable by-products. Biologically active (live) suspended solids may include disease causing organisms as well as organisms such as toxin-producing strains of algae. Suspended solids could be divided into filterable residues and non-filterable residues. Suspended solids,

111

where such material is likely to be organic and /or biological in nature, are important parameter of wastewater. The suspended-solids parameter is used to measure the quality of the wastewater affluent, to monitor several treatment processes, and to measure the quality of the effluent. Regulators have set a maximum suspended-solids standard of 30 mg/L for most treated wastewater discharges. Turbidity: Sources and impacts: Turbidity is the measure of the extent to which light is either absorbed or scattered by suspended particles in water. Absorption and scattering are known to be influenced by both the size and surface characteristics of the suspended material. Therefore, turbidity cannot be a direct quantitative measure of suspended solids. For example, a small pebble in a glass of water would not produce any turbidity. However, if this pebble were crushed into small particles of colloidal size it produces a measurable amount of turbidity although the mass of the pebble will not change. Turbidity in surface waters results from soil erosion. Household and industrial wastewaters such as soaps, detergents and

emulsifying agents produce stable colloids that result in turbidity. Turbidity makes drinking water aesthetically displeasing and the colloidal materials associated with turbidity provide adsorption sites for chemicals that may be harmful or cause undesirable tastes and odors and for biological organisms that may be harmful to health. Color and its sources: Pure water has no color. However, due to foreign materials natural water is often colored. The tannins, humic acid, and humates taken up by water from filterable suspended organic debris such as leaves, weeds, or wood, impart yellowish-brown color to water. Non-filterable substances such as iron oxides cause reddish water. Industrial wastes from textile and dyeing operations, pulp and paper production, food processing,

chemical production, and mining, refining, and slaughterhouse operations may add substantial coloration to water in receiving streams. In general part of the water coloration coming from filterable suspended matter is said to be apparent color and that contributed by dissolved solids, which remain after removal of filterable suspended matter, is known as true color. Similar to turbid water, colored water is aesthetically unacceptable to the general public. Highly colored water is unsuitable for laundering, dyeing, papermaking, beverage manufacturing, and dairy production. Therefore, colored water is less marketable both for domestic and industrial use. 112

Taste and odor The taste of water is the flavor that water gives us when we put it into our mouth, and the quality of water that we perceive by our sense of smell is its odor. Consumers may attribute a wide variety of tastes and odors to water. Substances that produce odor in water will almost invariably impart a taste as well. However, the converse is not true, as there are many mineral substances that produce taste but not odor. Organic materials or, their biological decomposition, are known to produce both taste and odor problems in water. Principal among these are the reduced products of sulfur that imparts a rotten egg odor and taste. Also, certain species of algae secrete an oily substance that may result in both taste and odor. The combination of two or more substances neither of which would produce taste or odor by itself may sometimes result in taste or odor problems. Alkaline mineral imparts a bitter taste to water, while metallic salts may give a salty or bitter taste. Taste and odor make water aesthetically displeasing to consumers. Some of the substances that impart bad taste and odor may be carcinogenic. Temperature: Temperature is not used as a parameter to evaluate potable water or wastewater directly. It is however, one of the most important parameters in natural surface water systems. The temperature of surface waters governs to a large extent the biological species present and their rates of activity. It also influences most chemical reactions that occur in natural water system the solubility of gases in water. Generally, shallow bodies of water are more affected by ambient temperatures (temperature of the surrounding atmosphere) than are deeper bodies. Water used for the dissipation of waste heat in industry and the subsequent discharge of the heated water may result in an increasing in the temperature of receiving streams, though perhaps localized. Removal of forest canopies and irrigation return flows can also result in increased stream temperature. Lower temperatures favor slower rate of biological activity. Provided that essential nutrients are available, biological activity is doubled by an increase of approximately 10 C. With an increase in metabolic rates, organisms that are efficient at food utilization and reproduction flourish, while other species decline and are perhaps eliminated altogether. Algal growth is often accelerated in warm water and can become a problem when cells cluster into algae mats.

113

Natural secretion of oils by the algae in the mats and the decay products of dead algae cells can result in taste and odor problems. Higher-order species, such as fish, are affected dramatically by temperature and by dissolved oxygen levels, which are a function of temperature. Game fish generally require cooler temperatures and higher dissolved-oxygen levels. Temperature changes affect the reaction rates and solubility levels of chemicals. Most chemical reactions involving dissolution of solids are accelerated by an increase in temperature. The solubility of gases, on the other hand, decreases at elevated temperatures. Thus, with an increase in temperature the level of dissolved oxygen will decrease. This is undesirable situation since biological oxidation of organics in streams is dependent on adequate supply dissolved oxygen. Module 7J Soil Chemistry Soil is a mixture of mineral, plant, and animal materials that form during a long process that may take thousands of years. In general, soil is an unconsolidated, or loose, combination of inorganic and organic materials. It is necessary for most plant growth and is essential for all agricultural production. The inorganic components of soil are principally produced by the weathering of rocks and minerals. The organic materials are composed of debris from plants and from the decomposition of the many tiny life forms that inhabit the soil. The chemical composition and physical structure of soils is determined by a number of factors such as: the kinds of rocks, minerals, and other geologic materials from which the soil is originally formed. The vegetation that grow in the soil are also important. Food sources grown on soils are predominately composed of carbon, hydrogen, oxygen, phosphorous, nitrogen, potassium, sodium and calcium. Plants take up these elements from the soil and configure them into the plants we recognize as food. Each plant has unique nutritional requirements that are obtained through the roots from the soil. Nutrients are stored in soil on exchange sites of the organic and clay components. Calcium, magnesium, ammonium, potassium and the vast majority of the micronutrients are present as cations under most soil pHs. Composition of Soils: Soils comprise a mixture of inorganic and organic components: minerals, air, water, and plant and animal material. Mineral and organic particles generally compose roughly 50 percent of a soils volume. The other 50 percent consists of poresopen

114

areas of various shapes and sizes. Networks of pores hold water within the soil and also provide a means of water transport. Oxygen and other gases move through pore spaces in soil. Pores also serve as passageways for small animals and provide room for the growth of plant roots. The mineral component of soil is made up of an arrangement of particles that are less than 2.0 mm in diameter. Soil scientists divide soil particles, into three main size groups: sand, silt, and clay. According to the standard classification scheme the size designations are: sand, 0.05 to 2.00 mm; silt 0.002 to 0.05 mm; and clay, less than 0.002 mm. Depending upon the parent rock materials from which they were derived, these assorted mineral particles ultimately release the chemicals on which plants depend for survival, such as potassium, calcium, magnesium, phosphorus, sulfur, iron, and manganese. Soils also have key chemical characteristics. The surfaces of certain soil particles, particularly the clays, hold groupings of atoms known as ions. These ions carry a negative charge. Like magnets, these negative ions (called anions) attract positive ions (called cations). Cations, including those from calcium, magnesium, and potassium, then become attached to the soil particles, in a process known as cation exchange. The chemical reactions in cation exchange make it possible for calcium and the other elements to be changed into water-soluble forms that plants can use for food. Therefore, a soils cation exchange capacity is an important measure of its fertility. Organic materials constitute another essential component of soils. Some of this material comes from the residue of plantsfor example, the remains of plant roots deep within the soil, or materials that fall on the ground, such as leaves on a forest floor. These materials become part of a cycle of decomposition and decay, a cycle that provides important nutrients to the soil. In general, soil fertility depends on a high content of organic materials. Water: Soils are also characterized according to how effectively they retain and transport water. Once water enters the soil from rain or irrigation, gravity comes into play, causing water to trickle downward. Soils differ in their capacity to retain moisture against the pull exerted by gravity and by plant roots. Coarse soils, such as those consisting of mostly of sand, tend to hold less water than do soils with finer textures, such as those with a greater proportion of clays. Water also moves through soil pores by capillary action. This is the kind of movement in which water molecules move because they are more attracted to the pore walls than to one another. Such movement tends to occur from wetter to drier areas of the soil.

115

The attraction of water molecules to each other is an example of cohesion. The attraction of water molecules to other materials, such as soil or plant roots, is a type of adhesion. Soil Characteristics: Scientists can learn a lot about a soils composition and origin by examining various features of the soil. Color, texture, aggregation, porosity, ion content, and pH are all important soil characteristics. Color: Soils possess a wide range of colors. In the surface soil horizons, a dark color usually indicates the presence of organic matter. Soils with significant organic material content appear dark brown or black. The most common soil hues are in the red-to-yellow range, getting their color from iron oxide minerals coating soil particles. Red iron oxides dominate highly weathered soils. Soils frequently saturated by water appear gray, blue, or green because the minerals that give them the red and yellow colors have been leached away. Texture: A soils texture depends on its content of the three main mineral components of the soil: sand, silt, and clay. Texture is the relative percentage of each particle size in a soil. Soils with predominantly large particles tend to drain quickly and have lower fertility. Very finetextured soils may be poorly drained, tend to become waterlogged, and are therefore not wellsuited for agriculture. Soils with a medium texture and a relatively even proportion of all particle sizes are most versatile. A combination of 10 to 20 percent clay, along with sand and silt in roughly equal amounts, and a good quantity of organic materials, is considered an ideal mixture for productive soil. Aggregation: Individual soil particles tend to be bound together into larger units referred to as aggregates or soil peds. Aggregation occurs as a result of complex chemical forces acting on small soil components or when organisms and organic matter in soil act as glue binding particles together. Soil peds range in size from very fineless than 1 mm to very coarse greater than 10 mm. Porosity: The part of the soil that is not solid is made up of pores of various sizes and shapessometimes small and separate, sometimes consisting of continuous tubes. The size, number, and arrangement of soil pores is known as the soils porosity. Porosity greatly affects water movement and gas exchange. Well-aggregated soils have numerous pores, which are 116

important for organisms that live in the soil and require water and oxygen to survive. The transport of nutrients and contaminants will also be affected by soil structure and porosity. pH: Another important chemical measure is soil pH, which refers to the soils acidity or alkalinity. The pH of a soil will often determine whether certain plants can be grown successfully. Soil Erosion: For most of human history, soil has not been treated as the valuable and essentially nonrenewable resource that it is. Erosion has devastated soils worldwide as a result of overuse and misuse. In recent years, however, farmers and agricultural experts have become increasingly concerned with soil management. Erosion is the wearing away of material on the surface of the land by wind, water, or gravity. In nature, erosion occurs very slowly, as natural weathering and geologic processes remove rock, parent material, or soil from the land surface. Human activity, on the other hand, greatly increases the rate of erosion. In a cultivated field from which crops have been harvested, the soil is often left bare, without protection from the elements, particularly water. Raindrops smash into the soil, dislodging soil particles. Water then carries these particles away. This movement may take the form of broad overland flows known as sheet erosion. More often, the eroding soil is concentrated into small channels, or rills, producing so-called rill erosion. Gravity intensifies water erosion. Wind erosion occurs where soils are dry, bare, and exposed to winds. Very small soil particles can be suspended in the air and carried away with the wind. Larger particles bounce along the ground in a process called saltation. Soil Pollution: Unhealthy soil management methods have seriously degraded soil quality, caused soil pollution, and enhanced erosion. In addition to other human practices, the use of chemical fertilizers, pesticides, and fungicides has disrupted the natural processes occurring within the soil resulting in soil pollution. Soil pollution is a buildup of toxic chemical compounds, salts, pathogens, or radioactive materials that can affect plant and animal life. The concern over soil contamination stems primarily from health risks, both of direct contact and from secondary contamination of water supplies. All kinds of soil pollutants originate from a source. The source is particularly important because it is generally the logical place to eliminate pollution. After a pollutant is released from a source, it may act upon a receptor. The

117

receptor is anything that is affected by the pollutant. The following sub-unit describes some of the most common sources of soil pollution. The most common toxic soil pollutants include metals and their compounds, organic chemicals, oils and tars, pesticides, explosive and toxic gases, radioactive materials, biologically active materials, combustible materials, asbestos and other hazardous materials. These substances commonly arise from the rupture of underground storage tanks; application of chemical fertilizers, pesticides, and fungicides; percolation of contaminated surface water to subsurface strata; leaching of wastes from landfills or direct discharge of industrial wastes to the soil etc. Heavy metal soil contaminants such as cadmium, lead, chromium, copper, zinc, mercury and arsenic, are a matter of great concern. Naturally all soils contain heavy metals. However, their levels are increased by: Pesticides that are used in agricultural practices pollute the soil directly by affecting the organisms that reside in it. Organic pollutants enter the soil via atmospheric deposition, direct spreading onto land, contamination by wastewater and waste disposal. Organic contaminants include pesticides and many other components, such as oils, tars, chlorinated hydrocarbons, PCBs and dioxins. The use of pesticides may lead to: destruction of the soils micro -flora and fauna, leading to both physical and chemical deterioration. Severe yield reduction in crops and leaching of toxic chemicals into groundwater and potentially threatening drinking water resources. Soil pollution prevention requires proper land use planning and provision of environmental infrastructures. For example, industries that can cause accidental discharge of pollutants and toxic chemicals will not be allowed to be sited within water catchments. Once preventive measures are established, controls are stringently enforced to ensure that pollution control equipment are properly maintained and operated, and effluents discharged meet emission standard. ************************************************************************

118