1|Page BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIE S O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 AWESOME REVIEW SERIES OF JAMIA URDU HIND CHEMISTRY (10+2) 2|Page BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIE S O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 Preface Dear Students of Jamia Urdu Hind of past and present, We understand you don‘t need the help of anyone ………….., But we just want to take care of the way you design everything. Something we want to share with you owing to your association with JUH!!! We can't find a reason why Allah gave this idea of writing Awesome Review Series of JUH with mnemonics to us to present subjects in this review form having complete points touching all competitive exams of respective standard in the shortest form as per your need and desire based on NCERT and Madrasa Board? But that is not the question to be asked; May be…….. The question is how did Allah know that we needed a student like you. Wonderful students are carefully created by Allah, Wonderful moments are carefully planned by Allah, Wonderful innovative truth seeker like you are carefully gifted by Allah!! Always read between the line…… To educate the children of non-educated persons are tougher than that of educated persons hence Muslims are least educated minority community in the country as per Decoded Minority Report since British Imperialism. There is declining Muslim IAS Officers from 1950 (13 %) to 2000 (2.92 %) among its 14% population in India. IAS officer is the pillar of governance. Hence, more than 50000 Madarsa and 14% literacy to India are contributed by Muslims without grants from government. Madarsa has produced architecture of Taj Mahal, Lal Qila, Qutub Minar along with Abusena in medicine and Khaiyam in mathematics. Madrasa for Urdu Courses in India is like Dinosaurs with Lal Qila, Qutub Minar, Jama Masjid, Taj Mahal as remnant for scientific research. In the past, Urdu has gathered a good deal of political dust, which it must shed in the interest of its health & growth. The basic problems of a language are educational, literary or administrative and if we confine ourselves to these spheres, we will discover that solutions become easier to find. India will never be a developed nation until power practice of biased mind will be ceased and surrendered completely and voluntarily. BP Singhal, MP(RS), Ex-DG, IPS said : Could a community that ruled India for over 950 years and belonged to a privileged class even during British Raj, becomes socially handicapped. This now encounters the worst conditions (worse than SC/ST) in their own land (as per minority report) and urgently needs emergency educational support to achieve 100% literacy so as to make India a developed nation (Ref: Problems & Policy of Minority in India). We provide education through literacy campaign in the country and our positive move has empowered the most deprived class to be in the nation‘s mainstream. Education and Nation are incomplete without Urdu and like Hindi, Urdu is the thread of Bharat‘s beaded necklace where all super power of the world is quit on the united front. One can use all the superlatives about the literary work of the institution but this won't mean anything to anybody. We state the facts that are verifiable. You are served by the country as you serve the country because your leaders are exactly like you. No human society can develop in all its dimensions if it does not produce meaningful literature for its children and young readers. Therefore, the framework of a society should be established around the pillars of knowledge by converting it into a democratic force and take it into every corner of our country. There is a great hunger for knowledge in the country and our motto, therefore, should be all for knowledge and knowledge for all (President of India). People do not remember what one says but they always remember what one tries to make them feel and nothing is better than honesty and goodness in the world!!! Never expect, do not criticize, do the best you can, surely you will rise very high in your life if you have confidence, trust and hope like Einstein, Newton, Mendal, Aryabhat, Edison, Khaiyam, Abusena and Archemedes. Confidence: Once, all villagers decided to pray for rain. On prayer day, all people gathered and only one boy came with an umbrella……… that―s confidence…….. Trust: Trust should be like the feeling of a one year old baby, when you throw him in air, he laughs....because he knows you will catch him…….. That―s trust.... Hope: A human being can live for 40 days without water, 8 minutes without air, but not a single second without one thing……… That―s hope.......... -Writer’s Union of JUH 3|Page BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIE S O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 CONTENTS Some Basic Concepts of Chemistry Structure of Atom Classification of Elements and Periodicity in Properties Chemical Bonding and Molecular Structure States of Matter Thermodynamics Equilibrium Redox Reactions Hydrogen The s-Block Elements The p-Block Elements Organic Chemistry – Some Basic Principles Hydrocarbons Carbon and its compounds Environmental Chemistry The Solid State Solutions Electrochemistry Chemical Kinetics Surface Chemistry General Principles and Processes of Isolation of Elements The p-Block The d-and f-Block Elements Coordination Compounds Haloalkanes and Haloarenes Alcohols, Phenols and Ethers Aldehydes, Ketones and Carboxylic Acids Amines Biomolecules Polymers Chemistry in Everyday Life Mnemonics in Chemistry Some Basic Concepts of Chemistry Definitions of the SI Base Units Metre (m): The metre is the length of path travelled by light in vacuum during a time interval of 1/299 792 458 of a second (17th CGPM, 1983). Kilogram (kg): The kilogram is the unit of mass; it is equal to the mass of the international prototype of the kilogram (3rd CGPM, 1901). Second (s): The second is the duration of 9192631770 periods of the radiation corresponding to the transition between the two hyperfine levels of the ground state of the caesium-133 atom (13th CGPM, 1967). Ampere (A): The ampere is that constant current which, if maintained in two straight parallel conductors of infinite length, of negligible circular cross-section, and placed 1 metre apart in vacuum, would produce between these conductors a force equal to 2 10-7 Newton per metre of length (9th CGPM, 1948). 4|Page BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIE S O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 Kelvin (K): The kelvin, unit of thermodynamic temperature, is the fraction 1/273.16 of the thermodynamic temperature of the triple point of water (13th CGPM, 1967). Mole (mol): The mole is the amount of substance of a system which contains as many elementary entities as there are atoms in 0.012 kilogram of carbon-12. When the mole is used, the elementary entities must be specified and may be atoms, molecules, ions, electrons, other particles, or specified groups of such particles (14th CGPM, 1971). Candela (cd): The candela is the luminous intensity, in a given direction, of a source that emits monochromatic radiation of frequency 540 1012 hertz and that has a radiant intensity in that direction of (1/683) watt per steradian (16th CGPM, 1979). (The symbols listed here are internationally agreed and should not be changed in other languages or scripts). The study of chemistry is very important as its domain encompasses every sphere of life. Chemists study the properties and structure of substances and the changes undergone by them. All substances contain matter which can exist in three states – solid, liquid or gas. The constituent particles are held in different ways in these states of matter and they exhibit their characteristic properties. Matter can also be classified into elements, compounds or mixtures. An element contains particles of only one type which may be atoms or molecules. The compounds are formed where atoms of two or more elements combine in a fixed ratio to each other. Mixtures occur widely and many of the substances present around us are mixtures. When the properties of a substance are studied, measurement is inherent. The quantification of properties requires a system of measurement and units in which the quantities are to be expressed. Many systems of measurement exist out of which the English and the Metric Systems are widely used. The scientific community, however, has agreed to have a uniform and common system throughout the world which is abbreviated as SI units (International System of Units). Since measurements involve recording of data which are always associated with a certain amount of uncertainty, the proper handling of data obtained by measuring the quantities is very important. The measurements of quantities in chemistry are spread over a wide range of 10–31 to 10+23. Hence, a convenient system of expressing the numbers in scientific notation is used. The uncertainty is taken care of by specifying the number of significant figures in which the observations are reported. The dimensional analysis helps to express the measured quantities in different systems of units. Hence, it is possible to interconvert the results from one system of units to another. The combination of different atoms is governed by basic laws of chemical combination – these being the Law of Conservation of Mass, Law of Definite Proportions, Law of Multiple Proportions, Gay Lussac’s Law of Gaseous Volumes and Avogadro Law. All these laws led to the Dalton’s atomic theory which states that atoms are building blocks of matter. The atomic mass of an element is expressed relative to 12C isotope of carbon which has an exact value of 12u. Usually, the atomic mass used for an element is the average atomic mass obtained by taking into account the natural abundance of different isotopes of that element. The molecular mass of a molecule is obtained by taking sum of the atomic masses of different atoms present in a molecule. The molecular formula can be calculated by determining the mass per cent of different elements present in a compound and its molecular mass. The number of atoms, molecules or any other particles present in a given system are expressed in the terms of Avogadro constant (6.022 1023). This is known as 1 mol of the respective particles or entities. Chemical reactions represent the chemical changes undergone by different elements and compounds. A balanced chemical equation provides a lot of information. The coefficients indicate the molar ratios and the respective number of particles taking part in a particular reaction. The quantitative study of the reactants required or the products formed is called stoichiometry. Using stoichiometric calculations, the amounts of one or more reactant(s) required to produce a particular amount of product can be determined and vice-versa. The amount of substance present in a given volume of a solution is expressed in number of ways, e.g., mass per cent, mole fraction, molarity and molality. Structure of Atom Atoms are the building blocks of elements. They are the smallest parts of an element that chemically react. The first atomic theory, proposed by John Dalton in 1808, regarded atom as the ultimate indivisible particle of matter. Towards the end of the nineteenth century, it was proved experimentally that atoms are divisible and consist of three fundamental particles: electrons, protons and neutrons. The discovery of sub-atomic particles led to the proposal of various atomic models to explain the structure of atom. Thomson in 1898 proposed that an atom consists of uniform sphere of positive electricity with electrons embedded into it. This model in which mass of the atom is considered to be evenly spread over the atom was proved wrong by Rutherford‘s famous alpha-particle scattering experiment in 5|Page BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIE S O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 1909. Rutherford concluded that atom is made of a tiny positively charged nucleus, at its centre with electrons revolving around it in circular orbits. Rutherford model, which resembles the solar system, was no doubt an improvement over Thomson model but it could not account for the stability of the atom i.e., why the electron does not fall into the nucleus. Further, it was also silent about the electronic structure of atoms i.e., about the distribution and relative energies of electrons around the nucleus. The difficulties of the Rutherford model were overcome by Niels Bohr in 1913 in his model of the hydrogen atom. Bohr postulated that electron moves around the nucleus in circular orbits. Only certain orbits can exist and each orbit corresponds to a specific energy. Bohr calculated the energy of electron in various orbits and for each orbit predicted the distance between the electron and nucleus. Bohr model, though offering a satisfactory model for explaining the spectra of the hydrogen atom, could not explain the spectra of multi-electron atoms. The reason for this was soon discovered. In Bohr model, an electron is regarded as a charged particle moving in a well defined circular orbit about the nucleus. The wave character of the electron is ignored in Bohr‘s theory. An orbit is a clearly defined path and this path can completely be defined only if both the exact position and the exact velocity of the electron at the same time are known. This is not possible according to the Heisenberg uncertainty principle. Bohr model of the hydrogen atom, therefore, not only ignores the dual behaviour of electron but also contradicts Heisenberg uncertainty principle. Erwin Schrödinger, in 1926, proposed an equation called Schrödinger equation to describe the electron distributions in space and the allowed energy levels in atoms. This equation incorporates de Broglie‘s concept of wave-particle duality and is consistent with Heisenberg uncertainty principle. When Schrödinger equation is solved for the electron in a hydrogen atom, the solution gives the possible energy states the electron can occupy [and the corresponding wave function(s) ( ) (which in fact are the mathematical functions) of the electron associated with each energy state]. 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 Schrödinger equation. The restrictions on the values of these three quantum numbers also come naturally from this solution. The quantum mechanical model of the hydrogen atom successfully predicts all aspects of the hydrogen atom spectrum including some phenomena that could not be explained by the Bohr model. According to the quantum mechanical model of the atom, the electron distribution of an atom containing a number of electrons is divided into shells. The shells, in turn, are thought to consist of one or more subshells and subshells are assumed to be composed of one or more orbitals, which the electrons occupy. While for hydrogen and hydrogen like systems (such as He+, Li2+ etc.) all the orbitals within a given shell have same energy, the energy of the orbitals in a multi-electron atom depends upon the values of n and l: The lower the value of (n + l ) for an orbital, the lower is its energy. If two orbitals have the same (n + l ) value, the orbital with lower value of n has the lower energy. In an atom many such orbitals are possible and electrons are filled in those orbitals in order of increasing energy in accordance with Pauli exclusion principle (no two electrons in an atom can have the same set of four quantum numbers) and Hund’s rule of maximum multiplicity (pairing of electrons in the orbitals belonging to the same subshell does not take place until each orbital belonging to that subshell has got one electron each, i.e., is singly occupied). This forms the basis of the electronic structure of atoms. Classification of Elements and Periodicity in Properties In this Unit, you have studied the development of the Periodic Law and the Periodic Table. Mendeleevís Periodic Table was based on atomic masses. Modern Periodic Table arranges the elements in the order of their atomic numbers in seven horizontal rows (periods) and eighteen vertical columns (groups or families). Atomic numbers in a period are consecutive, whereas in a group they increase in a pattern. Elements of the same group have similar valence shell electronic configuration and, therefore, exhibit similar chemical properties. However, the elements of the same period have incrementally increasing number of electrons from left to right, and, therefore, have different valencies. Four types of elements can be recognized in the periodic table on the basis of their electronic configurations. These are sblock, p-block, d-block and f-block elements. Hydrogen with one electron in the 1s orbital occupies a unique position in the periodic table. Metals comprise more than seventy eight per cent of the known elements. Nonmetals, which are located at the top of the periodic table, are less than twenty in number. Elements which lie at the border line between metals and non-metals (e.g., Si, Ge, As) are called metalloids or semi-metals. Metallic character increases with increasing atomic number in a group whereas decreases from left to right in a period. The physical and chemical properties of elements vary periodically with their atomic numbers. Periodic trends are observed in atomic sizes, ionization enthalpies, electron gain enthalpies, electronegativity and valence. The atomic radii decrease while going from left to right in a period and increase with atomic number in a group. Ionization enthalpies generally increase across a period and decrease down a group. 6|Page BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIE S O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 Electronegativity also shows a similar trend. Electron gain enthalpies, in general, become more negative across a period and less negative down a group. There is some periodicity in valence, for example, among representative elements, the valence is either equal to the number of electrons in the outermost orbitals or eight minus this number. Chemical reactivity is hightest at the two extremes of a period and is lowest in the centre. The reactivity on the left extreme of a period is because of the ease of electron loss (or low ionization enthalpy). Highly reactive elements do not occur in nature in free state; they usually occur in the combined form. Oxides formed of the elements on the left are basic and of the elements on the right are acidic in nature. Oxides of elements in the centre are amphoteric or neutral. Chemical Bonding and Molecular Structure Kösselís first insight into the mechanism of formation of electropositive and electronegative ions related the process to the attainment of noble gas configurations by the respective ions. Electrostatic attraction between ions is the cause for their stability. This gives the concept of electrovalency. The first description of covalent bonding was provided by Lewis in terms of the sharing of electron pairs between atoms and he related the process to the attainment of noble gas configurations by reacting atoms as a result of sharing of electrons. The Lewis dot symbols show the number of valence electrons of the atoms of a given element and Lewis dot structures show pictorial representations of bonding in molecules. An ionic compound is pictured as a three-dimensional aggregation of positive and negative ions in an ordered arrangement called the crystal lattice. In a crystalline solid there is a charge balance between the positive and negative ions. The crystal lattice is stabilized by the enthalpy of lattice formation. While a single covalent bond is formed by sharing of an electron pair between two atoms, multiple bonds result from the sharing of two or three electron pairs. Some bonded atoms have additional pairs of electrons not involved in bonding. These are called lonepairs of electrons. A Lewis dot structure shows the arrangement of bonded pairs and lone pairs around each atom in a molecule. Important parameters, associated with chemical bonds, like: bond length, bond angle, bond enthalpy, bond order and bond polarity have significant effect on the properties of compounds. A number of molecules and polyatomic ions cannot be described accurately by a single Lewis structure and a number of descriptions (representations) based on the same skeletal structure are written and these taken together represent the molecule or ion. This is a very important and extremely useful concept called resonance. The contributing structures or canonical forms taken together constitute the resonance hybrid which represents the molecule or ion. The VSEPR model used for predicting the geometrical shapes of molecules is based on the assumption that electron pairs repel each other and, therefore, tend to remain as far apart as possible. According to this model, molecular geometry is determined by repulsions between lone pairs and lone pairs ; lone pairs and bonding pairs and bonding pairs and bonding pairs. The order of these repulsions being : lp-lp > lp-bp > bp-bp The valence bond (VB) approach to covalent bonding is basically concerned with the energetics of covalent bond formation about which the Lewis and VSEPR models are silent. Basically the VB theory discusses bond formation in terms of overlap of orbitals. For example the formation of the H2 molecule from two hydrogen atoms involves the overlap of the 1s orbitals of the two H atoms which are singly occupied. It is seen that the potential energy of the system gets lowered as the two H atoms come near to each other. At the equilibrium inter-nuclear distance (bond distance) the energy touches a minimum. Any attempt to bring the nuclei still closer results in a sudden increase in energy and consequent destabilization of the molecule. Because of orbital overlap the electron density between the nuclei increases which helps in bringing them closer. It is however seen that the actual bond enthalpy and bond length values are not obtained by overlap alone and other variables have to be taken into account. For explaining the characteristic shapes of polyatomic molecules Pauling introduced the concept of hybridisation of atomic orbitals. sp,sp2, sp3 hybridizations of atomic orbitals of Be, B,C, N and O are used to explain the formation and geometrical shapes of molecules like BeCl2, BCl3, CH4, NH3 and H2O. They also explain the formation of multiple bonds in molecules like C2H2 and C2H4. The molecular orbital (MO) theory describes bonding in terms of the combination and arrangment of atomic orbitals to form molecular orbitals that are associated with the molecule as a whole. The number of molecular orbitals are always equal to the number of atomic orbitals from which they are formed. Bonding molecular orbitals increase electron density between the nuclei and are lower in energy than the individual atomic orbitals. Antibonding molecular orbitals have a region of zero electron density between the nuclei and have more energy than the individual atomic orbitals. The electronic configuration of the molecules is written by filling electrons in the molecular orbitals in the order of increasing energy levels. As in the case of atoms, the Pauli exclusion principle and Hundís rule are applicable for the filling of molecular orbitals. Molecules are said to be stable if the number of elctrons in bonding molecular orbitals is greater than that in antibonding molecular orbitals. Hydrogen bond is formed when a hydrogen atom finds itself between two highly electronegative atoms such as F, O and N. It may be intermolecular (existing between two or more molecules of the same or different 7|Page BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIE S O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 substances) or intramolecular (present within the same molecule). Hydrogen bonds have a powerful effect on the structure and properties of many compounds. States of Matter Intermolecular forces operate between the particles of matter. These forces differ from pure electrostatic forces that exist between two oppositely charged ions. Also, these do not include forces that hold atoms of a covalent molecule together through covalent bond. Competition between thermal energy and intermolecular interactions determines the state of matter. ―Bulk‖ properties of matter such as behaviour of gases, characteristics of solids and liquids and change of state depend upon energy of constituent particles and the type of interaction between them. Chemical properties of a substance do not change with change of state, but the reactivity depends upon the physical state. Forces of interaction between gas molecules are negligible and are almost independent of their chemical nature. Interdependence of some observable properties namely pressure, volume, temperature and mass leads to different gas laws obtained from experimental studies on gases. Boyle’s law states that under isothermal condition, pressure of a fixed amount of a gas is inversely proportional to its volume. Charles’ law is a relationship between volume and absolute temperature under isobaric condition. It states that volume of a fixed amount of gas is directly proportional to its absolute temperature (V ∝ T ) . If state of a gas is represented by p1, V1 and T1 and it changes to state at p2, V2 and T2, then relationship between these two states is given by combined gas law according to which P1V1/T1=P2 V2/T2. Any one of the variables of this gas can be found out if other five variables are known. Avogadro law states that equal volumes of all gases under same conditions of temperature and pressure contain equal number of molecules. Dalton’s law of partial pressure states that total pressure exerted by a mixture of non-reacting gases is equal to the sum of partial pressures exerted by them. Thus p = p1+p2+p3+ ... . Relationship between pressure, volume, temperature and number of moles of a gas describes its state and is called equation of state of the gas. Equation of state for ideal gas is PV=nRT, where R is a gas constant and its value depends upon units chosen for pressure, volume and temperature. At high pressure and low temperature intermolecular forces start operating strongly between the molecules of gases because they come close to each other. Under suitable temperature and pressure conditions gases can be liquified. Liquids may be considered as continuation of gas phase into a region of small volume and very strong molecular attractions. Some properties of liquids e.g., surface tension and viscosity are due to strong intermolecular attractive forces. Thermodynamics Thermodynamics deals with energy changes in chemical or physical processes and enables us to study these changes quantitatively and to make useful predictions. For these purposes, we divide the universe into the system and the surroundings. Chemical or physical processes lead to evolution or absorption of heat (q), part of which may be converted into work (w). These quantities are related through the first law of thermodynamics via U = q + w. U, change in internal energy, depends on initial and final states only and is a state function, whereas q and w depend on the path and are not the state functions. We follow sign conventions of q and w by giving the positive sign to these quantities when these are added to the system. We can measure the transfer of heat from one system to another which causes the change in temperature. The magnitude of rise in temperature depends on the heat capacity (C) of a substance. Therefore, heat absorbed or evolved is q = CT. Work can be measured by w = ñpexV, in case of expansion of gases. Under reversible process, we can put pex = p for infinitesimal changes in the volume making wrev = ñ p dV. In this condition, we can use gas equation, pV = nRT. At constant volume, w = 0, then U = qV , heat transfer at constant volume. But in study of chemical reactions, we usually have constant pressure. We define another state function enthalpy. Enthalpy change, H = U + ngRT, can be found directly from the heat changes at constant pressure, H= qp. There are varieties of enthalpy changes. Changes of phase such as melting, vaporization and sublimation usually occur at constant temperature and can be characterized by enthalpy changes which are always positive. Enthalpy of formation, combustion and other enthalpy changes can be calculated using Hess’s law. First law of thermodynamics does not guide us about the direction of chemical reactions i.e., what is the driving force of a chemical reaction. For isolated systems, we define another state function, S, entropy for this purpose. Entropy is a measure of disorder or randomness. For a spontaneous change, total entropy change is positive. Chemical reactions are generally carried at constant pressure, so we define another state function Gibbs energy, G, which is related to entropy and enthalpy changes of the system by the equation: G nS. Temperature is an important factor in the equation. Many reactions which are non-spontaneous at low temperature, are made spontaneous at high temperature for systems having positive entropy of reaction. 8|Page BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIE S O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 Equilibrium When the number of molecules leaving the liquid to vapour equals the number of molecules returning to the liquid from vapour, equilibrium is said to be attained and is dynamic in nature. Equilibrium can be established for both physical and chemical processes and at this stage rate of forward and reverse reactions are equal. Equilibrium constant, Kc is expressed as the concentration of products divided by reactants, each term raised to the stoichiometric coefficient. For reaction, a A + b B � c C +d D Kc = [C]c[D]d/[A]a[B]b. Equilibrium constant has constant value at a fixed temperature and at this stage all the macroscopic properties such as concentration, pressure, etc. become constant. For a gaseous reaction equilibrium constant is expressed as Kp and is written by replacing concentration terms by partial pressures in Kc expression. The direction of reaction can be predicted by reaction quotient Qc which is equal to Kc at equilibrium. Le Chatelier’s principle states that the change in any factor such as temperature, pressure, concentration, etc. will cause the equilibrium to shift in such a direction so as to reduce or counteract the effect of the change. It can be used to study the effect of various factors such as temperature, concentration, pressure, catalyst and inert gases on the direction of equilibrium and to control the yield of products by controlling these factors. Catalyst does not effect the equilibrium composition of a reaction mixture but increases the rate of chemical reaction by making available a new lower energy pathway for conversion of reactants to products and vice-versa. All substances that conduct electricity in aqueous solutions are called electrolytes. Acids, bases and salts are electrolytes and the conduction of electricity by their aqueous solutions is due to anions and cations produced by the dissociation or ionization of electrolytes in aqueous solution. The strong electrolytes are completely dissociated. In weak electrolytes there is equilibrium between the ions and the unionized electrolyte molecules. According to Arrhenius, acids give hydrogen ions while bases produce hydroxyl ions in their aqueous solutions. Brönsted-Lowry on the other hand, defined an acid as a proton donor and a base as a proton acceptor. When a Brönsted-Lowry acid reacts with a base, it produces its conjugate base and a conjugate acid corresponding to the base with which it reacts. Thus a conjugate pair of acid-base differs only by one proton. Lewis further generalised the definition of an acid as an electron pair acceptor and a base as an electron pair donor. The expressions for ionization (equilibrium) constants of weak acids (Ka) and weak bases (Kb) are developed using Arrhenius definition. The degree of ionization and its dependence on concentration and common ion are discussed. The pH scale (pH = -log[H+]) for the hydrogen ion concentration (activity) has been introduced and extended to other quantities (pOH = – log[OH–]) ; pKa = –log[Ka] ; pKb = –log[Kb]; and pKw = –log[Kw] etc.). The ionization of water has been considered and we note that the equation: pH + pOH = pKw is always satisfied. The salts of strong acid and weak base, weak acid and strong base, and weak acid and weak base undergo hydrolysis in aqueous solution.The definition of buffer solutions, and their importance are discussed briefly. The solubility equilibrium of sparingly soluble salts is discussed and the equilibrium constant is introduced as solubility product constant (Ksp). Its relationship with solubility of the salt is established. The conditions of precipitation of the salt from their solutions or their dissolution in water are worked out. The role of common ion and the solubility of sparingly soluble salts is also discussed. Redox Reactions Redox reactions form an important class of reactions in which oxidation and reduction occur simultaneously. Three tier conceptualisation viz, classical, electronic and oxidation number, which is usually available in the texts, has been presented in detail. Oxidation, reduction, oxidising agent (oxidant) and reducing agent (reductant) have been viewed according to each conceptualisation. Oxidation numbers are assigned in accordance with a consistent set of rules. Oxidation number and ion-electron method both are useful means in writing equations for the redox reactions. Redox reactions are classified into four categories: combination, decomposition displacement and disproportionation reactions. The concept of redox couple and electrode processes is introduced here. The redox reactions find wide applications in the study of electrode processes and cells. Hydrogen Hydrogen is the lightest atom with only one electron. Loss of this electron results in an elementary particle, the proton. Thus, it is unique in character. It has three isotopes, namely : protium, deuterium and tritium. Amongst these three, only tritium is radioactive. Inspite of its resemblance both with alkali metals and halogens, it occupies a separate position in the periodic table because of its unique properties. Hydrogen is the most abundant element in the universe. In the free state it is almost not found in the earth‘s atmosphere. However, in the combined state, it is the third most abundant element on the earth‘s surface. Dihydrogen on the industrial scale is prepared by the water-gas shift reaction from petrochemicals. It is obtained as a byproduct by the electrolysis of brine. The H–H bond 9|Page BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIE S O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 dissociation enthalpy of dihydrogen (435.88 kJ mol–1) is the highest for a single bond between two atoms of any elements. This property is made use of in the atomic hydrogen torch which generates a temperature of ~4000K and is ideal for welding of high melting metals. Though dihydrogen is rather inactive at room temperature because of very high negative dissociation enthalpy, it combines with almost all the elements under appropriate conditions to form hydrides. All the type of hydrides can be classified into three categories: ionic or saline hydrides, covalent or molecular hydrides and metallic or non-stoichiometric hydrides. Alkali metal hydrides are good reagents for preparing other hydride compounds. Molecular hydrides (e.g., B2H6, CH4, NH3, H2O) are of great importance in day-to-day life. Metallic hydrides are useful for ultrapurification of dihydrogen and as dihydrogen storage media. Among the other chemical reactions of dihydrogen, reducing reactions leading to the formation hydrogen halides, water, ammonia, methanol, vanaspati ghee, etc. are of great importance. In metallurgical process, it is used to reduce metal oxides. In space programmes, it is used as a rocket fuel. In fact, it has promising potential for use as a non-polluting fuel of the near future (Hydrogen Economy). Water is the most common and abundantly available substance. It is of a great chemical and biological significance. The ease with which water is transformed from liquid to solid and to gaseous state allows it to play a vital role in the biosphere. The water molecule is highly polar in nature due to its bent structure. This property leads to hydrogen bonding which is the maximum in ice and least in water vapour. The polar nature of water makes it: (a) a very good solvent for ionic and partially ionic compounds; (b) to act as an amphoteric (acid as well as base) substance; and (c) to form hydrates of different types. Its property to dissolve many salts, particularly in large quantity, makes it hard and hazardous for industrial use. Both temporary and permanent hardness can be removed by the use of zeolites, and synthetic ion-exchangers. Heavy water, D2O is another important compound which is manufactured by the electrolytic enrichment of normal water. It is essentially used as a moderator in nuclear reactors. Hydrogen peroxide, H2O2 has an interesting non-polar structure and is widely used as an industrial bleach and in pharmaceutical and pollution control treatment of industrial and domestic effluents. The s-Block Elements The s-Block of the periodic table constitutes Group1 (alkali metals) and Group 2 (alkaline earth metals). They are so called because their oxides and hydroxides are alkaline in nature. The alkali metals are characterised by one s-electron and the alkaline earth metals by two s-electrons in the valence shell of their atoms. These are highly reactive metals forming monopositive (M+) and dipositve (M2+) ions respectively. There is a regular trend in the physical and chemical properties of the alkali metal with increasing atomic numbers. The atomic and ionic sizes increase and the ionization enthalpies decrease systematically down the group. Somewhat similar trends are observed among the properties of the alkaline earth metals. The first element in each of these groups, lithium in Group 1 and beryllium in Group 2 shows similarities in properties to the second member of the next group. Such similarities are termed as the ‘diagonal relationship’ in the periodic table. As such these elements are anomalous as far as their group characteristics are concerned. The alkali metals are silvery white, soft and low melting. They are highly reactive. The compounds of alkali metals are predominantly ionic. Their oxides and hydroxides are soluble in water forming strong alkalies. Important compounds of sodium includes sodium carbonate, sodium chloride, sodium hydroxide and sodium hydrogencarbonate. Sodium hydroxide is manufactured by Castner-Kellner process and sodium carbonate by Solvay process. The chemistry of alkaline earth metals is very much like that of the alkali metals. However, some differences arise because of reduced atomic and ionic sizes and increased cationic charges in case of alkaline earth metals. Their oxides and hydroxides are less basic than the alkali metal oxides and hydroxides. Industrially important compounds of calcium include calcium oxide (lime), calcium hydroxide (slaked lime), calcium sulphate (Plaster of Paris), calcium carbonate (limestone) and cement. Portland cement is an important constructional material. It is manufactured by heating a pulverised mixture of limestone and clay in a rotary kiln. The clinker thus obtained is mixed with some gypsum (2-3%) to give a fine powder of cement. All these substances find variety of uses in different areas. Monovalent sodium and potassium ions and divalent magnesium and calcium ions are found in large proportions in biological fluids. These ions perform important biological functions such as maintenance of ion balance and nerve impulse conduction. The p-Block Elements p-Block of the periodic table is unique in terms of having all types of elements – metals, non-metals and metalloids. There are six groups of p-block elements in the periodic table numbering from 13 to 18. Their valence shell electronic configuration is ns2np1–6 (except for He). Differences in the inner core of their electronic configuration greatly influence their physical and chemical properties. As a consequence of this, a lot of variation in properties among these elements is observed. In addition to the group oxidation state, these elements show other oxidation states differing from the total number of valence electrons by unit of two. While the group oxidation state is the most stable for the 10 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 lighter elements of the group, lower oxidation states become progressively more stable for the heavier elements. The combined effect of size and availability of d orbitals considerably influences the ability of these elements to form bonds. While the lighter elements form p –p bonds, the heavier ones form d–p or d–d bonds. Absence of d orbital in second period elements limits their maximum covalence to 4 while heavier ones can exceed this limit. Boron is a typical non-metal and the other members are metals. The availability of 3 valence electrons (2s22p1) for covalent bond formation using four orbitals (2s, 2px, 2py and 2pz) leads to the so called electron deficiency in boron compounds. This deficiency makes them good electron acceptor and thus boron compounds behave as Lewis acids. Boron forms covalent molecular compounds with dihydrogen as boranes, the simplest of which is diborane, B2H6. Diborane contains two bridging hydrogen atoms between two boron atoms; these bridge bonds are considered to be three-centre twoelectron bonds. The important compounds of boron with dioxygen are boric acid and borax. Boric acid, B(OH)3 is a weak monobasic acid; it acts as a Lewis acid by accepting electrons from hydroxyl ion. Borax is a white crystalline solid of formula Na2[B4O5(OH)4]·8H2O. The borax bead test gives characteristic colours of transition metals. Aluminium exhibits +3 oxidation state. With heavier elements +1 oxidation state gets progressively stabilised on going down the group. This is a consequence of the so called inert pair effect. Carbon is a typical non-metal forming covalent bonds employing all its four valence electrons (2s22p2). It shows the property of catenation, the ability to form chains or rings, not only with C–C single bonds but also with multiple bonds (C=C or C≡C). The tendency to catenation decreases as C>>Si>Ge ~ Sn > Pb. Carbon provides one of the best examples of allotropy. Three important allotropes of carbon are diamond, graphite and fullerenes. The members of the carbon family mainly exhibit +4 and +2 oxidation states; compouds in +4 oxidation states are generally covalent in nature. The tendency to show +2 oxidation state increases among heavier elements. Lead in +2 state is stable whereas in +4 oxidation state it is a strong oxidising agent. Carbon also exhibits negative oxidation states. It forms two important oxides: CO and CO2. Carbon monoxide is neutral whereas CO2 is acidic in nature. Carbon monoxide having lone pair of electrons on C forms metal carbonyls. It is deadly poisonous due to higher stability of its haemoglobin complex as compared to that of oxyhaemoglobin complex. Carbon dioxide as such is not toxic. However, increased content of CO2 in atmosphere due to combustion of fossil fuels and decomposition of limestone is feared to cause increase in ‗green house effect‘. This, in turn, raises the temperature of the atmosphere and causes serious complications. Silica, silicates and silicones are important class of compounds and find applications in industry and technology. Organic Chemistry – Some Basic Principles In this unit, we have learnt some basic concepts in structure and reactivity of organic compounds, which are formed due to covalent bonding. The nature of the covalent bonding in organic compounds can be described in terms of orbitals hybridisation concept, according to which carbon can have sp3, sp2 and sp hybridised orbitals. The sp3, sp2 and sp hybridized carbons are found in compounds like methane, ethene and ethyne respectively. The tetrahedral shape of methane, planar shape of ethene and linear shape of ethyne can be understood on the basis of this concept. A sp3 hybrid orbital can overlap with 1s orbital of hydrogen to give a carbon - hydrogen (C–H) single bond (sigma, bond). Overlap of a sp2 orbital of one carbon with sp2 orbital of another results in the formation of a carbon–carbon bond. The unhybridised p orbitals on two adjacent carbons can undergo lateral (side-byside) overlap to give a pi ( ) bond. Organic compounds can be represented by various structural formulas. The three dimensional representation of organic compounds on paper can be drawn by wedge and dash formula. Organic compounds can be classified on the basis of their structure or the functional groups they contain. A functional group is an atom or group of atoms bonded together in a unique fashion and which determines the physical and chemical properties of the compounds. The naming of the organic compounds is carried out by following a set of rules laid down by the International Union of Pure and Applied Chemistry (IUPAC). In IUPAC nomenclature, the names are correlated with the structure in such a way that the reader can deduce the structure from the name. Organic reaction mechanism concepts are based on the structure of the substrate molecule, fission of a covalent bond, the attacking reagents, the electron displacement effects and the conditions of the reaction. These organic reactions involve breaking and making of covalent bonds. A covalent bond may be cleaved in heterolytic or homolytic fashion. A heterolytic cleavage yields carbocations or carbanions, while a homolytic cleavage gives free radicals as reactive intermediate. Reactions proceeding through heterolytic cleavage involve the complimentary pairs of reactive species. These are electron pair donor known as nucleophile and an electron pair acceptor known as electrophile. The inductive, resonance, electromeric and hyperconjugation effects may help in the polarisation of a bond making certain carbon atom or other atom positions as places of low or high electron densities. Organic reactions can be broadly classified into following types; substitution, addition, elimination and rearrangement reactions. Purification, qualitative and quantitative analysis of organic compounds are carried out 11 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 for determining their structures. The methods of purification namely : sublimation, distillation and differential extraction are based on the difference in one or more physical properties. Chromatography is a useful technique of separation, identification and purification of compounds. It is classified into two categories : adsorption and partition chromatography. Adsorption chromatography is based on differential adsorption of various components of a mixture on an adsorbent. Partition chromatography involves continuous partitioning of the components of a mixture between stationary and mobile phases. After getting the compound in a pure form, its qualitative analysis is carried out for detection of elements present in it. Nitrogen, sulphur, halogens and phosphorus are detected by Lassaigne’s test. Carbon and hydrogen are estimated by determining the amounts of carbon dioxide and water produced. Nitrogen is estimated by Dumas or Kjeldahl’s method and halogens by Carius method. Sulphur and phosphorus are estimated by oxidising them to sulphuric and phosphoric acids respectively. The percentage of oxygen is usually determined by difference between the total percentage (100) and the sum of percentages of all other elements present. Hydrocarbons Hydrocarbons are the compounds of carbon and hydrogen only. Hydrocarbons are mainly obtained from coal and petroleum, which are the major sources of energy. Petrochemicals are the prominent starting materials used for the manufacture of a large number of commercially important products. LPG (liquefied petroleum gas) and CNG (compressed natural gas), the main sources of energy for domestic fuels and the automobile industry, are obtained from petroleum. Hydrocarbons are classified as open chain saturated (alkanes) and unsaturated (alkenes and alkynes), cyclic (alicyclic) and aromatic, according to their structure. The important reactions of alkanes are free radical substitution, combustion, oxidation and aromatization. Alkenes and alkynes undergo addition reactions, which are mainly electrophilic additions. Aromatic hydrocarbons, despite having unsaturation, undergo mainly electrophilic substitution reactions. These undergo addition reactions only under special conditions. Alkanes show conformational isomerism due to free rotation along the C–C sigma bonds. Out of staggered and the eclipsed conformations of ethane, staggered conformation is more stable as hydrogen atoms are farthest apart. Alkenes exhibit geometrical (cis-trans) isomerism due to restricted rotation around the carbon–carbon double bond. Benzene and benzenoid compounds show aromatic character. Aromaticity, the property of being aromatic is possessed by compounds having specific electronic structure characterised by Hückel (4n+2) electron rule. The nature of groups or substituents attached to benzene ring is responsible for activation or deactivation of the benzene ring towards further electrophilic substitution and also for orientation of the incoming group. Some of the polynuclear hydrocarbons having fused benzene ring system have carcinogenic property. TRY CARBerlearning.com 2 Carbon and its compounds 1. A covalent bond is a bond formed by sharing of electrons between atoms. In a covalent bond, the shared pair of electrons belongs to the valence shell of both the atoms. 2. Properties of covalent compounds i. Physical states: They are generally liquids or gases. Some covalent compounds may exist as solids. ii. Solubility: They are generally insoluble in water and other polar solvents but soluble in organic solvents such as benzene, toluene etc. iii. Melting and boiling points: They generally have low melting and boiling points. iv. Electrical conductivity: They do not conduct electrical current. 3. Electronegativity is the ability of an atom to attract a shared pair of electrons towards itself. 4. Polar covalent bond: If the atoms forming a covalent bond have different electronegativities, the atom with higher electronegativity pulls the shared pair of electrons towards itself. Thus, the atom with the higher electronegativity develops a partial negative charge and the atom with the lower electronegativity develops a partial positive charge. This covalent bond with some polarity is called a polar covalent bond. 5. Carbon is an element that always forms covalent bonds. All the living things, plants and animals are made up of carbon-based compounds called organic compounds. 6. Carbon forms a large number of compounds because of two unique properties: i. Tetravalency ii. Catenation 7. Tetravalency of carbon: Carbon has atomic number 6 and has 4 electrons in its outermost shell. It needs 4 electrons to attain the noble gas configuration. Thus, its valency is 4. In other words, carbon has the ability to form four bonds with carbon or atoms of other monovalent elements. 12 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 8. Catenation: Carbon has the unique ability to form bonds with other atoms of carbon, giving rise to a large number of carbon compounds. This property is called catenation. 9. Allotropes of carbon i. Diamond: It is a colourless transparent substance. It is extremely hard and does not conduct electricity. It has a tetrahedral arrangement of carbon atoms in its structure. ii. Graphite: It is a greyish black opaque substance. It is soft and slippery and conducts electricity. A graphite crystal consists of layers of carbon atoms or sheets of carbon atoms. iii. Buckminsterfullerene: It is an allotrope of carbon containing clusters of 60 carbon atoms joined together to form spherical molecules. It is a football-shaped spherical molecule. 10. Hydrocarbons: A compound made up of only hydrogen and carbon is called a hydrocarbon. 11. Aliphatic or open chain hydrocarbons: These are the carbon compounds which have carbon– carbon long open chains. They are classified as i. Saturated hydrocarbons: These hydrocarbons have all carbon–carbon single bonds and are called alkanes. General formula: CnH2n+2 ii. Unsaturated hydrocarbons: These hydrocarbons have at least one carbon–carbon double or triple bond. a. Hydrocarbons with at least one carbon–carbon double bond are called alkenes. General formula = CnH2n, where n = number of carbon atoms b. Hydrocarbons with at least one carbon–carbon triple bond are called alkynes. General formula = CnH2n-2, where n = number of carbon atoms 12. Cyclic or closed chain hydrocarbons: These are hydrocarbons which have a carbon–carbon closed chain. They are classified as i. Alicyclic hydrocarbons: These are hydrocarbons which do not have a benzene ring in their structure. ii. Aromatic hydrocarbons: These are hydrocarbons which have a benzene ring in their structure. When hydrogen bonded to carbon of benzene is substituted with halogens, radicals or other functional groups, the derivatives are called aromatic compounds. 13. Benzene: It is an aromatic hydrocarbon which has the molecular formula C6H6. It has alternating carbon–carbon single and double bonds. Benzene can also be represented as 14. Types of formulae for writing hydrocarbons a. Molecular formula: The actual number of each type of atom present in the compound. b. Structural formula: The actual arrangement of atoms is written. c. Condensed formula: It is the shortened form of the structural formula. 15. Isomers: The organic compounds with the same molecular formula but different structures are called isomers. 16. Conditions for isomerism a. Only alkanes with more than three carbon atoms can have isomers. b. The side chains cannot be present on the terminal carbons. 17. Homologous series: A series of organic compounds in which every succeeding member differs from the previous one by a -CH2 group or a difference of 14 u in the molecular mass is called a homologous series. The molecular formula of all the members of a homologous series can be derived from a general formula. 18. Properties of a homologous series: As the molecular mass increases in a series, the physical properties of compounds show variation, but the chemical properties, which are determined by a functional group, remain the same within a series. 19. Homologous series of alkanes: General formula: CnH2n+2, where n = number of carbon atoms. 20. Homologous series of alkenes: General formula: CnH2n, where n = number of carbon atoms. 21. Homologous series of alkynes: General formula: CnH2n-2, where n = number of carbon atoms. 22. Functional group: An atom or a group of atoms which when present in a compound gives specific properties to it, irrespective of the length and nature of the carbon chain is called a functional group. 23. Some functional groups in carbon compounds Heteroatom Functional group Formula of the functional group Prefix/suffix Cl/Br Halo- 13 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 Chloro -Cl Bromo-Br Named as prefix Alcohol -OH -ol Aldehyde-al Ketone-one Carboxylic acid-oic acid 24. IUPAC naming of organic compounds i. Select the parent carbon chain. 1. Select the longest carbon chain as the parent chain. 2. If a double or a triple bond is present in the carbon chain, it should be included in the parent chain. 3. If a functional group is present, the carbon chain should include the functional group. ii. Number the parent carbon chain from that carbon end such that the functional group, double bond,triple bond or side chain gets the lowest number. Remember here that the aldehyde and carboxylic acid functional groups are present on the terminal carbon atom. iii. Identify the name and position of the functional group, double bond, triple bond or side chain. iv. The name of the functional group is written with either a prefix or a suffix as given in the above table. v. If the name of the functional group is to be given as a suffix, the name of the carbon chain ismodified by deleting the final ‗e‘ and adding the appropriate suffix. For example, a three-carbon chainwith a ketone group would be named in the following manner: Propane − ‗e‘ = propan + ‗one‘ =propanone. vi. Remember that in compounds which have carbon-containing functional groups, the name of the word root includes the functional group carbon atom also. vii. If the carbon chain is unsaturated, then the final ‗ane‘ in the name of the carbon chain issubstituted by ‗ene‘ or ‗yne‘ as given in the table above. For example, a three-carbon chain with adouble bond would be called propene, and if it has a triple bond, it would be called propyne. 25. Chemical properties of carbon compounds i. Combustion: The process of burning of a carbon compound in air to give carbon dioxide, water, heatand light is called combustion. Saturated hydrocarbons burn in air to produce a blue, non-sooty flame,whereas unsaturated hydrocarbons burn in air with a yellow, sooty flame. iii. Substitution reaction: The reaction in which one or more hydrogen atoms of a hydrocarbon are replaced by some other atoms is called a substitution reaction. Saturated hydrocarbons undergo substitution reactions. iv. Addition reaction: The reaction in which an unsaturated hydrocarbon combines with another substance to give a single product is called an addition reaction. These reactions are given by all unsaturated hydrocarbons. 26. Hydrogenation of oils: When a vegetable oil is heated with hydrogen in the presence of finely divided nickel as catalyst, then a saturated fat called vegetable ghee is formed. This is calledhydrogenation of oils. 27. All unsaturated compounds (alkenes or alkynes) decolourise bromine water but saturated hydrocarbons, i.e. alkanes do not decolourise bromine water. 28. Ethanol (C2H5OH): The common name is ethyl alcohol. It is a colourless liquid soluble in water. Ithas no effect on any litmus solution. 29. Reactions of ethanol Burning: CH3CH2OH - 3O2 2CO2 3H2O Heat Light - 2CH3CH2OH + 2Na 2CH3CH2ONa + H2 - Hot conc. H2SO4 3 2 o 2 2 2 170 C - CH CH OH CH =CH + H O. Alkaline KMnO4 Heat- 3 2 Or acidifiedK2Cr2O7 Heat 3 2 - CH CH OH+2[O] CH COOH+H O 30. Denatured alcohol: It is ethyl alcohol which has been made unfit for drinking purposes by adding small amounts of poisonous substances such as methanol etc. 31. Ethanoic acid (CH3COOH): It is a colourless liquid soluble in water having smell of vinegar. It turns blue litmus solution red. 32. Reactions of ethanoic acid CH COOH +NaOH CH COONa H O- 2CH COOH +Na CO 2CH COONa H O CO- CH COOH +NaHCO CH COONa H O CO 14 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 33. Esterification: Ethanoic acid reacts with alcohols in the presence of a little concentrated sulphuric acid to form esters. CH COOH +CH CH OH CH COOCH CH Hydrolysis of esters CH COOC H NaOH CH COONa+ C H OH 34. Soaps: These are sodium or potassium salts of long chain carboxylic acids. 35. Structure of soap molecule: The structure of soap molecule consists of a long hydrocarbon tail at one end which is hydrophobic in nature. The other end is the ionic part which is hydrophilic in nature. 36. Cleansing action of soap: When soap is at the surface of water, the ionic end of soap orientsitself towards water and the hydrocarbon ‗tail‘ aligns itself along the dirt. Thus, clusters ofmolecules are formed in which the hydrophobic tails are in the interior of the cluster and the ionicends are on the surface of the cluster. This formation is called a micelle.Soap in the form of a micelle is able to clean because the oily dirt will be collected in the centre ofthe micelle. The micelles stay in solution as a colloid and will not come together to precipitate because of ion–ion repulsion. Now, when water is agitated, the dirt suspended in the micelles is also easily rinsed away. 37. Detergents: These are generally sodium salts of long chain benzene sulphonic acids or long chainalkyl hydrogen sulphates. Detergents do not form scum with hard water. This is because the charged ends of these compounds do not form insoluble precipitates with the calcium and magnesium ions in hard water. Thus, they remain effective in hard water. 39. Differences between soaps and detergents Soaps are sodium or potassiumsalts of long chain carboxylic acids. Detergents are generally ammonium or sulphonate salts of long chain carboxylic acids. Soaps are not effective for cleaning in hard water. Detergents are effective for cleaning in hard and soft water. Soaps are biodegradable. Detergents are non-biodegradable. Environmental Chemistry Environmental chemistry plays a major role in environment. Chemical species present in the environment are either naturally occurring or generated by human activities. Environmental pollution is the effect of undesirable changes in the surrounding that have harmful effects on plants, animals and human beings. Pollutants exist in all the three states of matter. We have discussed only those pollutants, which are due to human activities, and can be controlled. Atmospheric pollution is generally studied as tropospheric and stratospheric pollution. Troposphere is the lowest region of the atmosphere (~10 km) in which man along with other organisms including plants exist. Whereas stratosphere extends above troposphere up to 50 km above sea level. Ozone layer is one of the important constituents of stratosphere. Tropospheric pollution is basically due to various oxides of sulphur, nitrogen, carbon, halogens and also due to particulate pollutants. The gaseous pollutants come down to the earth in the form of acid rain. 75% of the solar energy reaching earth is absorbed by the earth surface and rest is radiated back to the atmosphere. These gases mentioned above trap the heat which result into global warming. It is important to realise that these very gases are also responsible for the life on the earth as they trap the requisite amount of solar energy for the sustainance of life. The increase in the greenhouse gases is raising the temperature of the earth‘s atmosphere which, if not checked, may eventually result in melting of polar ice caps and consequently may submerge the costal land mass. Many human activities are producing chemicals, which are responsible for the depletion of ozone layer in the stratosphere, leading to the formation of ozone hole. Through the ozone hole, ultraviolet radiations can penetrate into the earth‘s atmosphere causing mutation of genes. Water is the elixir of life but the same water, if polluted by pathogens, organic wastes, toxic heavy metals, pesticides etc., will turn into poison. Therefore, one should take care to follow international standards to maintain purity levels of drinking water. Industrial wastes and excessive use of pesticides, result into pollution of land mass and water bodies. Judicious use of chemicals required for agricultural practices can lead to sustainable development. Strategies for controlling environmental pollution can be: (i) waste management i.e., reduction of the waste and proper disposal, also recycling of materials and energy, (ii) adopting methods in dayto-day life, which results in the reduction of environmental pollution. The second method is a new branch of chemistry, which is in its infancy known as green chemistry. It utilizes the existing knowledge and practices so as to bring about reduction in the production of pollutants. The Solid State Solids have definite mass, volume and shape. This is due to the fixed position of their constituent particles, short distances and strong interactions between them. In amorphous solids, the arrangement of constituent particles has only short range order and consequently they behave like super cooled liquids, do not have sharp melting points and 15 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 are isotropic in nature. In crystalline solids there is long range order in the arrangement of their constituent particles. They have sharp melting points, are anisotropic in nature and their particles have characteristic shapes. Properties of crystalline solids depend upon the nature of interactions between their constituent particles. On this basis, they can be divided into four categories, namely: molecular, ionic, metallic and covalent solids. They differ widely in their properties. The constituent particles in crystalline solids are arranged in a regular pattern which extends throughout the crystal. This arrangement is often depicted in the form of a three dimensional array of points which is called crystal lattice. Each lattice point gives the location of one particle in space. In all, fourteen different types of lattices are possible which are called Bravais lattices. Each lattice can be generated by repeating its small characteristic portion called unit cell. A unit cell is characterised by its edge lengths and three angles between these edges. Unit cells can be either primitive which have particles only at their corner positions or centred. The centred unit cells have additional particles at their body centre (bodycentred), at the centre of each face (face-centred) or at the centre of two opposite faces (endcentred). There are seven types of primitive unit cells. Taking centred unit cells also into account, there are fourteen types of unit cells in all, which result in fourteen Bravais lattices. Close-packing of particles result in two highly efficient lattices, hexagonal close-packed (hcp) and cubic close-packed (ccp). The latter is also called facecentred cubic (fcc) lattice. In both of these packings 74% space is filled. The remaining space is present in the form of two types of voids-octahedral voids and tetrahedral voids. Other types of packing are not close-packings and have less efficient packing of particles. While in body-centred cubic lattice (bcc) 68% space is filled, in simple cubic lattice only 52.4 % space is filled. Solids are not perfect in structure. There are different types of imperfections or defects in them. Point defects and line defects are common types of defects. Point defects are of three types - stoichiometric defects, impurity defects and non-stoichiometric defects. Vacancy defects and interstitial defects are the two basic types of stoichiometric point defects. In ionic solids, these defects are present as Frenkel and Schottky defects. Impurity defects are caused by the presence of an impurity in the crystal. In ionic solids, when the ionic impurity has a different valence than the main compound, some vacancies are created. Nonstoichiometric defects are of metal excess type and metal deficient type. Sometimes calculated amounts of impurities are introduced by doping in semiconductors that change their electrical properties. Such materials are widely used in electronics industry. Solids show many types of magnetic properties like paramagnetism, diamagnetism, ferromagnetism, antiferromagnetism and ferrimagnetism. These properties are used in audio, video and other recording devices. All these properties can be correlated with their electronic configurations or structures. Solutions A solution is a homogeneous mixture of two or more substances. Solutions are classified as solid, liquid and gaseous solutions. The concentration of a solution is expressed in terms of mole fraction, molarity, molality and in percentages. The dissolution of a gas in a liquid is governed by Henry’s law, according to which, at a given temperature, the solubility of a gas in a liquid is directly proportional to the partial pressure of the gas. The vapour pressure of the solvent is lowered by the presence of a non-volatile solute in the solution and this lowering of vapour pressure of the solvent is governed by Raoult‘s law, according to which the relative lowering of vapour pressure of the solvent over a solution is equal to the mole fraction of a non-volatile solute present in the solution. However, in a binary liquid solution, if both the components of the solution are volatile then another form of Raoult‘s law is used. Solutions which obey Raoult’s law over the entire range of concentration are called ideal solutions. Two types of deviations from Raoult‘s law, called positive and negative deviations are observed. Azeotropes arise due to very large deviations from Raoult‘s law. The properties of solutions which depend on the number of solute particles and are independent of their chemical identity are called colligative properties. These are lowering of vapour pressure, elevation of boiling point, depression of freezing point and osmotic pressure. The process of osmosis can be reversed if a pressure higher than the osmotic pressure is applied to the solution. Colligative properties have been used to determine the molar mass of solutes. Solutes which dissociate in solution exhibit molar mass lower than the actual molar mass and those which associate show higher molar mass than their actual values. Quantitatively, the extent to which a solute is dissociated or associated can be expressed by van‘t Hoff factor i. This factor has been defined as ratio of normal molar mass to experimentally determined molar mass or as the ratio of observed colligative property to the calculated colligative property. Electrochemistry The Hydrogen Economy 16 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 At present the main source of energy that is driving our economy is fossil fuels such as coal, oil and gas. As more people on the planet aspire to improve their standard of living, their energy requirement will increase. In fact, the per capita consumption of energy used is a measure of development. Of course, it is assumed that energy is used for productive purpose and not merely wasted. We are already aware that carbon dioxide produced by the combustion of fossil fuels is resulting in the ‗Greenhouse Effect‘. This is leading to a rise in the temperature of the Earth‘s surface, causing polar ice to melt and ocean levels to rise. This will flood low-lying areas along the coast and some island nations such as Maldives face total submergence. In order to avoid such a catastrope, we need to limit our use of carbonaceous fuels. Hydrogen provides an ideal alternative as its combustion results in water only. Hydrogen production must come from splitting water using solar energy. Therefore, hydrogen can be used as a renewable and non polluting source of energy. This is the vision of the Hydrogen Economy. Both the production of hydrogen by electrolysis of water and hydrogen combustion in a fuel cell will be important in the future. And both these technologies are based on electrochemical principles. An electrochemical cell consists of two metallic electrodes dipping in electrolytic solution(s). Thus an important component of the electrochemical cell is the ionic conductor or electrolyte. Electrochemical cells are of two types. In galvanic cell, the chemical energy of a spontaneous redox reaction is converted into electrical work, whereas in an electrolytic cell, electrical energy is used to carry out a nonspontaneous redox reaction. The standard electrode potential for any electrode dipping in an appropriate solution is defined with respect to standard electrode potential of hydrogen electrode taken as zero. The standard potential of the cell can be obtained by taking the difference of the standard potentials of cathode and anode. The standard potential of the cells are related to standard Gibbs energy.(V = – RT ln K) of the reaction taking place in the cell. Concentration dependence of the potentials of the electrodes and the cells are given by Nernst equation. The conductivity, , of an electrolytic solution depends on the concentration of the electrolyte, nature of solvent and temperature. Molar conductivity, Ëm, is defined by = /c where c is the concentration. Conductivity decreases but molar conductivity increases with decrease in concentration. It increases slowly with decrease in concentration for strong electrolytes while the increase is very steep for weak electrolytes in very dilute solutions. Kohlrausch found that molar conductivity at infinite dilution, for an electrolyte is sum of the contribution of the molar conductivity of the ions in which it dissociates. It is known as law of independent migration of ions and has many applications. Ions conduct electricity through the solution but oxidation and reduction of the ions take place at the electrodes in an electrochemical cell. Batteries and fuel cells are very useful forms of galvanic cell. Corrosion of metals is essentially an electrochemical phenomenon. Electrochemical principles are relevant to the Hydrogen Economy. Chemical Kinetics Chemical kinetics is the study of chemical reactions with respect to reaction rates, effect of various variables, rearrangement of atoms and formation of intermediates. The rate of a reaction is concerned with decrease in concentration of reactants or increase in the concentration of products per unit time. It can be expressed as instantaneous rate at a particular instant of time and average rate over a large interval of time. A number of factors such as temperature, concentration of reactants, catalyst, affect the rate of a reaction. Mathematical representation of rate of a reaction is given by rate law. It has to be determined experimentally and cannot be predicted. Order of a reaction with respect to a reactant is the power of its concentration which appears in the rate law equation. The order of a reaction is the sum of all such powers of concentration of terms for different reactants. Rate constant is the proportionality factor in the rate law. Rate constant and order of a reaction can be determined from rate law or its integrated rate equation. Molecularity is defined only for an elementary reaction. Its values are limited from 1 to 3 whereas order can be 0, 1, 2, 3 or even a fraction. Molecularity and order of an elementary reaction are same. Temperature dependence of rate constants is described by Arrhenius equation (k = Ae–Ea/RT). Ea corresponds to the activation energy and is given by the energy difference between activated complex and the reactant molecules, and A (Arrhenius factor or pre-exponential factor) corresponds to the collision frequency. The equation clearly shows that increase of temperature or lowering of Ea will lead to an increase in the rate of reaction and presence of a catalyst lowers the activation energy by providing an alternate path for the reaction. According to collision theory, another factor P called steric factor which refers to the orientation of molecules which collide, is important and contributes to effective collisions. Surface Chemistry Adsorption is the phenomenon of attracting and retaining the molecules of a substance on the surface of a solid resulting into a higher concentration on the surface than in the bulk. The substance adsorbed is known as adsorbate and the substance on which adsorption takes place is called adsorbent. In physisorption, adsorbate is held to the adsorbent by weak van der Waals forces, and in chemisorption, adsorbate is held to the adsorbent by strong chemical 17 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 bond. Almost all solids adsorb gases. The extent of adsorption of a gas on a solid depends upon nature of gas, nature of solid, surface area of the solid, pressure of gas and temperature of gas. The relationship between the extent of adsorption (x/m) and pressure of the gas at constant temperature is known as adsorption isotherm. A catalyst is a substance which enhances the rate of a chemical reaction without itself getting used up in the reaction. The phenomenon using catalyst is known as catalysis. In homogeneous catalysis, the catalyst is in the same phase as are the reactants, and in heterogeneous catalysis the catalyst is in a different phase from that of the reactants. Colloidal solutions are intermediate between true solutions and suspensions. The size of the colloidal particles range from 1 to 1000 nm. A colloidal system consists of two phases - the dispersed phase and the dispersion medium. Colloidal systems are classified in three ways depending upon (i) physical states of the dispersed phase and dispersion medium (ii) nature of interaction between the dispersed phase and dispersion medium and (iii) nature of particles of dispersed phase. The colloidal systems show interesting optical, mechanical and electrical properties. The process of changing the colloidal particles in a sol into the insoluble precipitate by addition of some suitable electrolytes is known as coagulation. Emulsions are colloidal systems in which both dispersed phase and dispersion medium are liquids. These can be of: (i) oil in water type and (ii) water in oil type. The process of making emulsion is known as emulsification. To stabilise an emulsion, an emulsifying agent or emulsifier is added. Soaps and detergents are most frequently used as emulsifiers. Colloids find several applications in industry as well as in daily life. General Principles and Processes of Isolation of Elements Uses of Aluminium, Copper, Zinc and Iron: Aluminium foils are used as wrappers for chocolates. The fine dust of the metal is used in paints and lacquers. Aluminium, being highly reactive, is also used in the extraction of chromium and manganese from their oxides. Wires of aluminium are used as electricity conductors. Alloys containing aluminium, being light, are very useful. Copper is used for making wires used in electrical industry and for water and steam pipes. It is also used in several alloys that are rather tougher than the metal itself, e.g., brass (with zinc), bronze (with tin) and coinage alloy (with nickel). Zinc is used for galvanising iron. It is also used in large quantities in batteries, as a constituent of many alloys, e.g., brass, (Cu 60%, Zn 40%) and german silver (Cu 25-30%, Zn 25-30%, Ni 40–50%). Zinc dust is used as a reducing agent in the manufacture of dye-stuffs, paints, etc. Cast iron, which is the most important form of iron, is used for casting stoves, railway sleepers, gutter pipes , toys, etc. It is used in the manufacture of wrought iron and steel. Wrought iron is used in making anchors, wires, bolts, chains and agricultural implements. Steel finds a number of uses. Alloy steel is obtained when other metals are added to it. Nickel steel is used for making cables, automobiles and aeroplane parts, pendulum, measuring tapes, chrome steel for cutting tools and crushing machines, and stainless steel for cycles, automobiles, utensils, etc. Metals are required for a variety of purposes. For this, we need their extraction from the minerals in which they are present and from which their extraction is commercially feasible.These minerals are known as ores. Ores of the metal are associated with many impurities. Removal of these impurities to certain extent is achieved in concentration steps. The concentrated ore is then treated chemically for obtaining the metal. Usually the metal compounds (e.g., oxides, sulphides) are reduced to the metal. The reducing agents used are carbon, CO or even some metals. In these reduction processes, the thermodynamic and electrochemical concepts are given due consideration. The metal oxide reacts with a reducing agent; the oxide is reduced to the metal and the reducing agent is oxidised. In the two reactions, the net Gibbs energy change is negative, which becomes more negative on raising the temperature. Conversion of the physical states from solid to liquid or to gas, and formation of gaseous states favours decrease in the Gibbs energy for the entire system. This concept is graphically displayed in plots of G0 vs T (Ellingham diagram) for such oxidation/reduction reactions at different temperatures. The concept of electrode potential is useful in the isolation of metals (e.g., Al, Ag, Au) where the sum of the two redox couples is +ve so that the Gibbs energy change is negative. The metals obtained by usual methods still contain minor impurities. Getting pure metals require refining. Refining process depends upon the differences in properties of the metal and the impurities. Extraction of aluminium is usually carried out from its bauxite ore by leaching it with NaOH. Sodium aluminate, thus formed, is separated and then neutralised to give back the hydrated oxide, which is then electrolysed using cryolite as a flux. Extraction of iron is done by reduction of its oxide ore in blast furnace. Copper is extracted by smelting and heating in a reverberatory furnace. Extraction of zinc from zinc oxides is done using coke. Several methods are employed in refining the metal. Metals, in general, are very widely used and have contributed significantly in the development of a variety of industries. Aluminium Iron Copper Zinc 18 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 1. Bauxite, Al2O3. x H2O 2. Cryolite, Na3AlF6 1. Haematite, Fe2O3 2. Magnetite, Fe3O4 1. Copper pyrites, CuFeS2 2. Copper glance, Cu2S 3. Malachite, CuCO3.Cu(OH)2 4. Cuprite, Cu2O 1. Zinc blende or Sphalerite, ZnS 2. Calamine, ZnCO3 3. Zincite, ZnO The p-Block Helium Helium is a non-inflammable and light gas. Hence, it is used in filling balloons for meteorological observations. It is also used in gas-cooled nuclear reactors. Liquid helium (b.p. 4.2 K) finds use as cryogenic agent for carrying out various experiments at low temperatures. It is used to produce and sustain powerful superconducting magnets which form an essential part of modern NMR spectrometers and Magnetic Resonance Imaging (MRI) systems for clinical diagnosis. It is used as a diluent for oxygen in modern diving apparatus because of its very low solubility in blood. Neon is used in discharge tubes and fluorescent bulbs for advertisement display purposes. Neon bulbs are used in botanical gardens and in green houses. Argon is used mainly to provide an inert atmosphere in high temperature metallurgical processes (arc welding of metals or alloys) and for filling electric bulbs. It is also used in the laboratory for handling substances that are air-sensitive. There are no significant uses of Xenon and Krypton. They are used in light bulbs designed for special purposes. Groups 13 to 18 of the periodic table consist of p-block elements with their valence shell electronic configuration ns2np1–6. Groups 13 and 14 were dealt with in Class XI. In this Unit remaining groups of the p-block have been discussed. Group 15 consists of five elements namely, N, P, As, Sb and Bi which have general electronic configuration ns2np3. Nitrogen differs from other elements of this group due to small size, formation of p–p multiple bonds with itself and with highly electronegative atom like O or C and non-availability of d orbitals to expand its valence shell. Elements of group 15 show gradation in properties. They react with oxygen, hydrogen and halogens. They exhibit two important oxidation states, + 3 and + 5 but +3 oxidation is favoured by heavier elements due to ‗inert pair effect‘. Dinitrogen can be prepared in laboratory as well as on industrial scale. It forms oxides in various oxidation states as N2O, NO, N2O3, NO2, N2O4 and N2O5. These oxides have resonating structures and have multiple bonds. Ammonia can be prepared on large scale by Haber‘s process. HNO3 is an important industrial chemical. It is a strong monobasic acid and is a powerful oxidising agent. Metals and non-metals react with HNO3 under different conditions to give NO or NO2. Phosphorus exists as P4 in elemental form. It exists in several allotropic forms. It forms hydride, PH3 which is a highly poisonous gas. It forms two types of halides as PX3 and PX5. PCl3 is prepared by the reaction of white phosphorus with dry chlorine while PCl5 is prepared by the reaction of phosphorus with SO2Cl2. Phosphorus forms a number of oxoacids. Depending upon the number of P–OH groups, their basicity varies. The oxoacids which have P–H bonds are good reducing agents. The Group 16 elements have general electronic configuration ns2np4. They show maximum oxidation state, +6. Gradation in physical and chemical properties is observed in the group 16 elements. In laboratory, dioxygen is prepared by heating KClO3 in presence of MnO2. It forms a number of oxides with metals. Allotropic form of oxygen is O3 which is a highly oxidising agent. Sulphur forms a number of allotropes. Sulphur combines with oxygen to give oxides such as SO2 and SO3. SO2 is prepared by the direct union of sulphur with oxygen. SO2 is used in the manufacture of H2SO4. Sulphur forms a number of oxoacids. Amongst them, the most important is H2SO4. It is prepared by contact process. It is a dehydrating and oxidising agent. It is used in the manufacture of several compounds. Group 17 of the periodic table consists of the following elements F, Cl, Br, I and At.These elements are extremely reactive and as such they are found in the combined state only. The common oxidation state of these elements is –1. However, highest oxidation state can be +7. They show regular gradation in physical and chemical properties. They form oxides, hydrogen halides, interhalogen compounds and oxoacids. Chlorine is conveniently obtained by the 19 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 reaction of HCl with KMnO4. HCl is prepared by heating NaCl with concentrated H2SO4. Halogens combine with one another to form interhalogen compounds of the type XX1 n (n = 1, 3, 5, 7) where X1 is lighter than X. A number of oxoacids of halogens are known. In the structures of these oxoacids, halogen is the central atom which is bonded in each case with one OH bond as X–OH. In some cases X = 0 bonds are also found. Group 18 of the periodic table consists of noble gases. They have ns2 np6 valence shell electronic configuration except He which has 1s2. All the gases except Rn occur in atmosphere. Rn is obtained as the decay product of 226Ra. Due to complete octet of outermost shell, they have less tendency to form compounds. The best characterised compounds are those of xenon with fluorine and oxygen only under certain conditions. These gases have several uses. Argon is used to provide inert atmosphere, helium is used in filling balloons for meteorological observations, neon is used in discharge tubes and fluorescent bulbs. The d-and f-Block Elements Iron and steels are the most important construction materials. Their production is based on the reduction of iron oxides, the removal of impurities and the addition of carbon and alloying metals such as Cr, Mn and Ni. Some compounds are manufactured for special purposes such as TiO for the pigment industry and MnO2 for use in dry battery cells. The battery industry also requires Zn and Ni/Cd. The elements of Group 11 are still worthy of being called the coinage metals, although Ag and Au 233 The d- and f- Block Elements are restricted to collection items and the contemporary UK ‗copper‘ coins are copper-coated steel. The ‗silver‘ UK coins are a Cu/Ni alloy. Many of the metals and/or their compounds are essential catalysts in the chemical industry. V2O5 catalyses the oxidation of SO2 in the manufacture of sulphuric acid. TiCl4 with A1(CH3)3 forms the basis of the Ziegler catalysts used to manufacture polyethylene (polythene). Iron catalysts are used in the Haber process for the production of ammonia from N2/H2 mixtures. Nickel catalysts enable the hydrogenation of fats to proceed. In the Wacker process the oxidation of ethyne to ethanal is catalysed by PdCl2. Nickel complexes are useful in the polymerisation of alkynes and other organic compounds such as benzene. The photographic industry relies on the special light-sensitive properties of AgBr. The d-block consisting of Groups 3-12 occupies the large middle section of the periodic table. In these elements the inner d orbitals are progressively filled. The f-block is placed outside at the bottom of the periodic table and in the elements of this block, 4f and 5f orbitals are progressively filled. Corresponding to the filling of 3d, 4d and 5d orbitals, three series of transition elements are well recognised. All the transition elements exhibit typical metallic properties such as –high tensile strength, ductility, malleability, thermal and electrical conductivity and metallic character. Their melting and boiling points are high which are attributed to the involvement of (n–1) d electrons resulting into strong interatomic bonding. In many of these properties, the maxima occur at about the middle of each series which indicates that one unpaired electron per d orbital is particularly a favourable configuration for strong interatomic interaction. Successive ionisation enthalpies do not increase as steeply as in the main group elements with increasing atomic number. Hence, the loss of variable number of electrons from (n –1) d orbitals is not energetically unfavourable. The involvement of (n–1) d electrons in the behaviour of transition elements impart certain distinct characteristics to these elements. Thus, in addition to variable oxidation states, they exhibit paramagnetic behaviour, catalytic properties and tendency for the formation of coloured ions, interstitial compounds and complexes. The transition elements vary widely in their chemical behaviour. Many of them are sufficiently electropositive to dissolve in mineral acids, although a few are ‗noble‘. Of the first series, with the exception of copper, all the metals are relatively reactive. The transition metals react with a number of non-metals like oxygen, nitrogen, sulphur and halogens to form binary compounds. The first series transition metal oxides are generally formed from the reaction of metals with oxygen at high temperatures. These oxides dissolve in acids and bases to form oxometallic salts. Potassium dichromate and potassium permanganate are common examples. Potassium dichromate is prepared from the chromite ore by fusion with alkali in presence of air and acidifying the extract. Pyrolusite ore (MnO2) is used for the preparation of potassium permanganate. Both the dichromate and the permanganate ions are strong oxidising agents. The two series of inner transition elements, lanthanoids and actinoids constitute the f-block of the periodic table. With the successive filling of the inner orbitals, 4f, there is a gradual decrease in the atomic and ionic sizes of these metals along the series (lanthanoid contraction). This has far reaching consequences in the chemistry of the elements succeeding them. Lanthanum and all the lanthanoids are rather soft white metals. They react easily with water to give solutions giving +3 ions. The principal oxidation state is +3, although +4 and +2 oxidation states are also exhibited by some occasionally. The chemistry of the actinoids is more complex in view of their ability to exist in different oxidation states. Furthermore, many of the actinoid elements are radioactive which make the study of these elements rather difficult. 20 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 There are many useful applications of the d- and f-block elements and their compounds, notable among them being in varieties of steels, catalysts, complexes, organic syntheses, etc. Coordination Compounds The coordination compounds are of great importance. These compounds are widely present in the mineral, plant and animal worlds and are known to play many important functions in the area of analytical chemistry, metallurgy, biological systems, industry and medicine. These are described below: • Coordination compounds find use in many qualitative and quantitative chemical analysis. The familiar colour reactions given by metal ions with a number of ligands (especially chelating ligands), as a result of formation of coordination entities, form the basis for their detection and estimation by classical and instrumental methods of analysis. Examples of such reagents include EDTA, DMG (dimethylglyoxime), –nitroso––naphthol, cupron, etc. • Hardness of water is estimated by simple titration with Na2EDTA. The Ca2+ and Mg2+ ions form stable complexes with EDTA. The selective estimation of these ions can be done due to difference in the stability constants of calcium and magnesium complexes. • Some important extraction processes of metals, like those of silver and gold, make use of complex formation. Gold, for example, combines with cyanide in the presence of oxygen and water to form the coordination entity [Au(CN)2]– in aqueous solution. Gold can be separated in metallic form from this solution by the addition of zinc (Unit 6). • Similarly, purification of metals can be achieved through formation and subsequent decomposition of their coordination compounds. For example, impure nickel is converted to [Ni(CO)4], which is decomposed to yield pure nickel. • Coordination compounds are of great importance in biological systems. The pigment responsible for photosynthesis, chlorophyll, is a coordination compound of magnesium. Haemoglobin, the red pigment of blood which acts as oxygen carrier is a coordination compound of iron. Vitamin B12, cyanocobalamine, the anti–pernicious anaemia factor, is a coordination compound of cobalt. Among the other compounds of biological importance with coordinated metal ions are the enzymes like, carboxypeptidase A and carbonic anhydrase (catalysts of biological systems). • Coordination compounds are used as catalysts for many industrial processes. Examples include rhodium complex, [(Ph3P)3RhCl], a Wilkinson catalyst, is used for the hydrogenation of alkenes. • Articles can be electroplated with silver and gold much more smoothly and evenly from solutions of the complexes, [Ag(CN)2]– and [Au(CN)2]– than from a solution of simple metal ions. • In black and white photography, the developed film is fixed by washing with hypo solution which dissolves the undecomposed AgBr to form a complex ion, [Ag(S2O3)2]3–. • There is growing interest in the use of chelate therapy in medicinal chemistry. An example is the treatment of problems caused by the presence of metals in toxic proportions in plant/animal systems. Thus, excess of copper and iron are removed by the chelating ligands D–penicillamine and desferrioxime B via the formation of coordination compounds. EDTA is used in the treatment of lead poisoning. Some coordination compounds of platinum effectively inhibit the growth of tumours. Examples are: cis–platin and related compounds. The chemistry of coordination compounds is an important and challenging area of modern inorganic chemistry. During the last fifty years, advances in this area, have provided development of new concepts and models of bonding and molecular structure, novel breakthroughs in chemical industry and vital insights into the functioning of critical components of biological systems. The first systematic attempt at explaining the formation, reactions, structure and bonding of a coordination compound was made by A. Werner. His theory postulated the use of two types of linkages (primary and secondary) by a metal atom/ion in a coordination compound. In the modern language of chemistry these linkages are recognised as the ionisable (ionic) and non-ionisable (covalent) bonds, respectively. Using the property of isomerism, Werner predicted the geometrical shapes of a large number of coordination entities. The Valence Bond Theory (VBT) explains with reasonable success, the formation, magnetic behaviour and geometrical shapes of coordination compounds. It, however, fails to provide a quantitative interpretation of magnetic behavior and has nothing to say about the optical properties of these compounds. The Crystal Field Theory (CFT) to coordination compounds is based on the effect of different crystal fields (provided by the ligands taken as point charges), on the degeneracy of d orbital energies of the central metal atom/ion. The splitting of the d orbitals provides different electronic arrangements in strong and weak crystal fields. The treatment provides for quantitative estimations of orbital separation energies, magnetic moments and spectral and stability parameters. However, the assumption that ligands consititute point charges creates many theoretical difficulties. The metal–carbon bond in metal carbonyls 21 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 possesses both and character. This unique synergic bonding provides stability to metal carbonyls. The stability of coordination compounds is measured in terms of stepwise stability (or formation) constant (K) or overall stability constant (). The stabilisation of coordination compound due to chelation is called the chelate effect. The stability of coordination compounds is related to Gibbs energy, enthalpy and entropy terms. Coordination compounds are of great importance. These compounds provide critical insights into the functioning and structures of vital components of biological systems. Coordination compounds also find extensive applications in metallurgical processes, analytical and medicinal chemistry. Haloalkanes and Haloarenes Polyhalogen Compounds Carbon compounds containing more than one halogen atom are usually referred to as polyhalogen compounds. Many of these compounds are useful in industry and agriculture. Some polyhalogen compounds are described in this section. Dichloromethane (Methylene chloride) : Dichloromethane is widely used as a solvent as a paint remover, as a propellant in aerosols, and as a process solvent in the manufacture of drugs. It is also used as a metal cleaning and finishing solvent. Methylene chloride harms the human central nervous system. Exposure to lower levels of methylene chloride in air can lead to slightly impaired hearing and vision. Higher levels of methylene chloride in air cause dizziness, nausea, tingling and numbness in the fingers and toes. In humans, direct skin contact with methylene chloride causes intense burning and mild redness of the skin. Direct contact with the eyes can burn the cornea. Trichloromethane(Chloroform): Chemically, chloroform is employed as a solvent for fats, alkaloids, iodine and other substances. The major use of chloroform today is in the production of the freon refrigerant R-22. It was once used as a general anaesthetic in surgery but has been replaced by less toxic, safer anaesthetics, such as ether. As might be expected from its use as an anaesthetic, inhaling chloroform vapours depresses the central nervous system. Breathing about 900 parts of chloroform per million parts of air (900 parts per million) for a short time can cause dizziness, fatigue, and headache. Chronic chloroform exposure may cause damage to the liver (where chloroform is metabolised to phosgene) and to the kidneys, and some people develop sores when the skin is immersed in chloroform. Chloroform is slowly oxidised by air in the presence of light to an extremely poisonous gas, carbonyl chloride, also known as phosgene. It is therefore stored in closed dark coloured bottles completely filled so that air is kept out. Triiodomethane (Iodoform): It was used earlier as an antiseptic but the antiseptic properties are due to the liberation of free iodine and not due to iodoform itself. Due to its objectionable smell, it has been replaced by other formulations containing iodine. Tetrachloromethane (Carbon tetrachloride): It is produced in large quantities for use in the manufacture of refrigerants and propellants for aerosol cans. It is also used as feedstock in the synthesis of chlorofluorocarbons and other chemicals, pharmaceutical manufacturing, and general solvent use. Until the mid 1960s, it was also widely used as a cleaning fluid, both in industry, as a degreasing agent, and in the home, as a spot remover and as fire extinguisher. There is some evidence that exposure to carbon tetrachloride causes liver cancer in humans. The most common effects are dizziness, light headedness, nausea and vomiting, which can cause permanent damage to nerve cells. In severe cases, these effects can lead rapidly to stupor, coma, unconsciousness or death. Exposure to CCl4 can make the heart beat irregularly or stop. The chemical may irritate the eyes on contact. When carbon tetrachloride is released into the air, it rises to the atmosphere and depletes the ozone layer. Depletion of the ozone layer is believed to increase human exposure to ultraviolet rays, leading to increased skin cancer, eye diseases and disorders, and possible disruption of the immune system. Freons: The chlorofluorocarbon compounds of methane and ethane are collectively known as freons. They are extremely stable, unreactive, non-toxic, non-corrosive and easily liquefiable gases. Freon 12 (CCl2F2) is one of the most common freons in industrial use. It is manufactured from tetrachloromethane by Swarts reaction. These are usually produced for aerosol propellants, refrigeration and air conditioning purposes. By 1974, total freon production in the world was about 2 billion pounds annually. Most freon, even that used in refrigeration, eventually makes its way 22 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 into the atmosphere where it diffuses unchanged into the stratosphere. In stratosphere, freon is able to initiate radical chain reactions that can upset the natural ozone balance p,p’-Dichlorodiphenyltrichloroethane( DDT): DDT, the first chlorinated organic insecticides, was originally prepared in 1873, but it was not until 1939 that Paul Muller of Geigy Pharmaceuticals in Switzerland discovered the effectiveness of DDT as an insecticide. Paul Muller was awarded the Nobel Prize in Medicine and Physiology in 1948 for this discovery. The use of DDT increased enormously on a worldwide basis after World War II, primarily because of its effectiveness against the mosquito that spreads malaria and lice that carry typhus. However, problems related to extensive use of DDT began to appear in the late 1940s. Many species of insects developed resistance to DDT, and it was also discovered to have a high toxicity towards fish. The chemical stability of DDT and its fat solubility compounded the problem. DDT is not metabolised very rapidly by animals; instead, it is deposited and stored in the fatty tissues. If ingestion continues at a steady rate, DDT builds up within the animal over time. The use of DDT was banned in the United States in 1973, although it is still in use in some other parts of the world. Alkyl/ Aryl halides: Alkyl/ Aryl halides may be classified as mono, di, or polyhalogen (tri-, tetra-, etc.) compounds depending on whether they contain one, two or more halogen atoms in their structures. Since halogen atoms are more electronegative than carbon, the carbonhalogen bond of alkyl halide is polarised; the carbon atom bears a partial positive charge, and the halogen atom bears a partial negative charge. Alkyl halides are prepared by the free radical halogenation of alkanes, addition of halogen acids to alkenes, replacement of –OH group of alcohols with halogens using phosphorus halides, thionyl chloride or halogen acids. Aryl halides are prepared by electrophilic substitution to arenes. Fluorides and iodides are best prepared by halogen exchange method. The boiling points of organohalogen compounds are comparatively higher than the corresponding hydrocarbons because of strong dipole-dipole and van der Waals forces of attraction. These are slightly soluble in water but completely soluble in organic solvents. The polarity of carbon-halogen bond of alkyl halides is responsible for their nucleophilic substitution, elimination and their reaction with metal atoms to form organometallic compounds. Nucleophilic substitution reactions are categorised into SN1 and SN2 on the basis of their kinetic properties. Chirality has a profound role in understanding the reaction mechanisms of SN1 and SN2 reactions. SN2 reactions of chiral alkyl halides are characterised by the inversion of configuration while SN1 reactions are characterised by racemisation. A number of polyhalogen compounds e.g., dichloromethane, chloroform, iodoform, carbon tetrachloride, freon and DDT have many industrial applications. However, some of these compounds cannot be easily decomposed and even cause depletion of ozone layer and are proving environmental hazards. Alcohols, Phenols and Ethers Alcohols and phenols are classified (i) on the basis of the number of hydroxyl groups and (ii) according to the hybridisation of the carbon atom, sp3 or sp2 to which the –OH group is attached. Ethers are classified on the basis of groups attached to the oxygen atom. Alcohols may be prepared (1) by hydration of alkenes (i) in presence of an acid and (ii) by hydroboration-oxidation reaction (2) from carbonyl compounds by (i) catalytic reduction and (ii) the action of Grignard reagents. Phenols may be prepared by (1) substitution of (i) halogen atom in haloarenes and (ii) sulphonic acid group in aryl sulphonic acids, by –OH group (2) by hydrolysis of diazonium salts and (3) industrially from cumene. Alcohols are higher boiling than other classes of compounds, namely hydrocarbons, ethers and haloalkanes of comparable molecular masses. The ability of alcohols, phenols and ethers to form intermolecular hydrogen bonding with water makes them soluble in it. Alcohols and phenols are acidic in nature. Electron withdrawing groups in phenol increase its acidic strength and electron releasing groups decrease it. Alcohols undergo nucleophilic substitution with hydrogen halides to yield alkyl halides. Dehydration of alcohols gives alkenes. On oxidation, primary alcohols yield aldehydes with mild oxidising agents and carboxylic acids with strong oxidising agents while secondary alcohols yield ketones. Tertiary alcohols are resistant to oxidation. The presence of –OH group in phenols activates the aromatic ring towards electrophilic substitution and directs the incoming group to ortho and para positions due to resonance effect. Reimer-Tiemann reaction of phenol yields salicylaldehyde. In presence of sodium hydroxide, phenol generates phenoxide ion which is even more reactive than phenol. Thus, in alkaline medium, phenol undergoes Kolbe‘s reaction. Ethers may be prepared by (i) dehydration of alcohols and (ii) Williamson synthesis. The boiling points of ethers resemble those of alkanes while their solubility is comparable to those of alcohols having same molecular mass. The C–O bond in ethers can be cleaved by hydrogen halides. In electrophilic substitution, the alkoxy group activates the aromatic ring and directs the incoming group to ortho and para positions. 23 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 Aldehydes, Ketones and Carboxylic Acids Aldehydes, ketones and carboxylic acids are some of the important classes of organic compounds containing carbonyl group. These are highly polar molecules. Therefore, they boil at higher temperatures than the hydrocarbons and weakly polar compounds such as ethers of comparable molecular masses. The lower members are more soluble in water because they form hydrogen bonds with water. The higher members, because of large size of hydrophobic chain of carbon atoms, are insoluble in water but soluble in common organic solvents. Aldehydes are prepared by dehydrogenation or controlled oxidation of primary alcohols and controlled or selective reduction of acyl halides. Aromatic aldehydes may also be prepared by oxidation of (i) methylbenzene with chromyl chloride or CrO3 in the presence of acetic anhydride, (ii) formylation of arenes with carbon monoxide and hydrochloric acid in the presence of anhydrous aluminium chloride, and (iii) cuprous chloride or by hydrolysis of benzal chloride. Ketones are prepared by oxidation of secondary alcohols and hydration of alkynes. Ketones are also prepared by reaction of acyl chloride with dialkylcadmium. A good method for the preparation of aromatic ketones is the Friedel-Crafts acylation of aromatic hydrocarbons with acyl chlorides or anhydrides. Both aldehydes and ketones can be prepared by ozonolysis of alkenes. Aldehydes and ketones undergo nucleophilic addition reactions onto the carbonyl group with a number of nucleophiles such as, HCN, NaHSO3, alcohols (or diols), ammonia derivatives, and Grignard reagents. The -hydrogens in aldehydes and ketones are acidic. Therefore, aldehydes and ketones having at least one -hydrogen, undergo Aldol condensation in the presence of a base to give -hydroxyaldehydes (aldol) and -hydroxyketones(ketol), respectively. Aldehydes having no -hydrogen undergo Cannizzaro reaction in the presence of concentrated alkali. Aldehydes and ketones are reduced to alcohols with NaBH4, LiAlH4, or by catalytic hydrogenation. The carbonyl group of aldehydes and ketones can be reduced to a methylene group by Clemmensen reduction or Wolff-Kishner reduction. Aldehydes are easily oxidised to carboxylic acids by mild oxidising reagents such as Tollens’ reagent and Fehling’s reagent. These oxidation reactions are used to distinguish aldehydes from ketones. Carboxylic acids are prepared by the oxidation of primary alcohols, aldehydes and alkenes by hydrolysis of nitriles, and by treatment of Grignard reagents with carbon dioxide. Aromatic carboxylic acids are also prepared by side-chain oxidation of alkylbenzenes. Carboxylic acids are considerably more acidic than alcohols and most of simple phenols. Carboxylic acids are reduced to primary alcohols with LiAlH4, or better with diborane in ether solution and also undergo -halogenation with Cl2 and Br2 in the presence of red phosphorus (Hell-Volhard Zelinsky reaction). Methanal, ethanal, propanone, benzaldehyde, formic acid, acetic acid and benzoic acid are highly useful compounds in industry. Amines Amines can be considered as derivatives of ammonia obtained by replacement of hydrogen atoms with alkyl or aryl groups. Replacement of one hydrogen atom of ammonia gives rise to structure of the type R-NH2, known as primary amine. Secondary amines are characterised by the structure R2NH or R-NHR′and tertiary amines by R3N, RNR′R′′ or R2NR′ Secondary and tertiary amines are known as simple amines if the alkyl or aryl groups are the same and mixed amines if the groups are different. Like ammonia, all the three types of amines have one unshared electron pair on nitrogen atom due to which they behave as Lewis bases. Amines are usually formed from nitro compounds, halides, amides, imides, etc. They exhibit hydrogen bonding which influence their physical properties. In alkylamines, a combination of electron releasing, steric and H-bonding factors influence the stability of the substituted ammonium cations in protic polar solvents and thus affect the basic nature of amines. Alkyl amines are found to be stronger bases than ammonia. In aromatic amines, electron releasing and withdrawing groups, respectively increase and decrease their basic character. Aniline is a weaker base than ammonia. Reactions of amines are governed by availability of the unshared pair of electrons on nitrogen. Influence of the number of hydrogen atoms at nitrogen atom on the type of reactions and nature of products is responsible for identification and distinction between primary, secondary and tertiary amines. p-Toluenesulphonyl chloride is used for the identification of primary, secondary and tertiary amines. Presence of amino group in aromatic ring enhances reactivity of the aromatic amines. Reactivity of aromatic amines can be controlled by acylation process, i.e., by treating with acetyl chloride or acetic anhydride. Tertiary amines like trimethylamine are used as insect attractants. Aryldiazonium salts, usually obtained from arylamines, undergo replacement of the diazonium group with a variety of nucleophiles to provide advantageous methods for producing aryl halides, cyanides, phenols and arenes by reductive removal of the diazo group. Coupling reaction of aryldiazonium salts with phenols or arylamines give rise to the formation of azo dyes. Biomolecules 24 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 Carbohydrates are optically active polyhydroxy aldehydes or ketones or molecules which provide such units on hydrolysis. They are broadly classified into three groups — monosaccharides, disaccharides and polysaccharides. Glucose, the most important source of energy for mammals, is obtained by the digestion of starch. Monosaccharides are held together by glycosidic linkages to form disaccharides or polysaccharides. Proteins are the polymers of about twenty different -amino acids which are linked by peptide bonds. Ten amino acids are called essential amino acids because they cannot be synthesised by our body, hence must be provided through diet. Proteins perform various structural and dynamic functions in the organisms. Proteins which contain only -amino acids are called simple proteins. The secondary or tertiary structure of proteins get disturbed on change of pH or temperature and they are not able to perform their functions. This is called denaturation of proteins. Enzymes are biocatalysts which speed up the reactions in biosystems. They are very specific and selective in their action and chemically all enzymes are proteins. Vitamins are accessory food factors required in the diet. They are classified as fat soluble (A, D, E and K) and water soluble ( group and C). Deficiency of vitamins leads to many diseases. Nucleic acids are the polymers of nucleotides which in turn consist of a base, a pentose sugar and phosphate moiety. Nucleic acids are responsible for the transfer of characters from parents to offsprings. There are two types of nucleic acids — DNA and RNA. DNA contains a five carbon sugar molecule called 2-deoxyribose whereas RNA contains ribose. Both DNA and RNA contain adenine, guanine and cytosine. The fourth base is thymine in DNA and uracil in RNA. The structure of DNA is a double strand whereas RNA is a single strand molecule. DNA is the chemical basis of heredity and have the coded message for proteins to be synthesized in the cell. There are three types of RNA — mRNA, rRNA and tRNA which actually carry out the protein synthesis in the cell. Polymers Polymers are defined as high molecular mass macromolecules, which consist of repeating structural units derived from the corresponding monomers. These polymers may be of natural or synthetic origin and are classified in a number of ways. In the presence of an organic peroxide initiator, the alkenes and their derivatives undergo addition polymerisation or chain growth polymerisation through a free radical mechanism. Polythene, teflon, orlon, etc. are formed by addition polymerization of an appropriate alkene or its derivative. Condensation polymerisation reactions are shown by the interaction of bi – or poly functional monomers containing – NH2, – OH and – COOH groups. This type of polymerisation proceeds through the elimination of certain simple molecules as H2O, CH3OH, etc. Formaldehyde reacts with phenol and melamine to form the corresponding condensation polymer products. The condensation polymerisation progresses through step by step and is also called as step growth polymerisation. Nylon, bakelite and dacron are some of the important examples of condensation polymers. However, a mixture of two unsaturated monomers exhibits copolymerisation and forms a co-polymer containing multiple units of each monomer. Natural rubber is a cis 1, 4-polyisoprene and can be made more tough by the process of vulcanisation with sulphur. Synthetic rubbers are usually obtained by copolymerization of alkene and 1, 3 butadiene derivatives. In view of the potential environmental hazards of synthetic polymeric wastes, certain biodegradable polymers such as PHBV and Nylon-2- Nylon-6 are developed as alternatives. Chemistry in Everyday Life Chemistry is essentially the study of materials and the development of new materials for the betterment of humanity. A drug is a chemical agent, which affects human metabolism and provides cure from ailment. If taken in doses higher than recommended, these may have poisonous effect. Use of chemicals for therapeutic effect is called chemotherapy. Drugs usually interact with biological macromolecules such as carbohydrates, proteins, lipids and nucleic acids. These are called target molecules. Drugs are designed to interact with specific targets so that these have the least chance of affecting other targets. This minimises the side effects and localises the action of the drug. Drug chemistry centres around arresting microbes/destroying microbes, preventing the body from various infectious diseases, releasing mental stress, etc. Thus, drugs like analgesics, antibiotics, antiseptics, disinfectants, antacids and tranquilizers are used for specific purpose. To check the population explosion, antifertility drugs have also become prominent in our life. Food additives such as preservatives, sweetening agents, flavours, antioxidants, edible colours and nutritional supplements are added to the food to make it attractive, palatable and add nutritive value. Preservatives are added to the food to prevent spoilage due to microbial growth. Artificial sweeteners are used by those who need to check the calorie intake or are diabetic and want to avoid taking sucrose. These days, detergents are much in vogue and get preference over soaps because they work even in hard water. Synthetic detergents are classified into three main categories, namely: anionic, cationic and non-ionic, and each category has its specific uses. Detergents with straight chain of hydrocarbons are preferred over branched chain as the latter are non-biodegradable and consequently cause environmental pollution. 25 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 26 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 MUSCLE RELAXATION POTENTIATING AGENTS: Aminoglycosides…………………. “ATP” Tetracycline………………………. “ABC” Polypeptide antibiotic Antiarrhythmic Beta blocker Calcium channel blocker Toxic value for most commonly monitored drugs (Magic of 2) : Digitalis (0.5 – 1.5) =Toxicity (2) Dilantin/Phenytoin (10 – 20) =Toxicity (20) Lithium (0.6 – 1.2) =Toxicity (2) Jogger/stimulant drugs (Theophylline) (10 20)=Toxicity (20) ―Dilwali Dulhenia Le Jayenge=DDLJ” Drugs Name. Approved name Brand name Chemical and code name…………. “ABC ORPHAN DRUGS: Baclofen Acetyl cysteine…………. “BAD Drug” Desmopressin Digoxin Ab Fab DRUG INTERACTIONS (IA):……………………….. “3P” 1. Pharmacokinetic IA: occurs during drug movements. 2. Pharmacodynamic IA: occurs at the receptor/between various drug actions. 3. Pharmaceutical IA: occurs during formulation/mixing. PharmacodynaMics means Mechanism of action. Targets for drug action are Receptors, Ion channel, Carrier molecule, Enzyme…… ―RICE” MECHANISM OF DRUG ACTIONS Physical action: It may be: 1. Radioactivity (131I). 2. 3. 4. Osmotic (mannitol). Adsorptive (charcoal). Radioopacity (contrast media such as BaSO4, urogram)……… “ROAR” Competitive inhibition in Vmax. NOncompetitive inhibition Vmax decreases = Km increases, no change = NO change in Km, UNcompetitive inhibition = Km & Vmax decrease (Under Normal) RECEPTORS: Receptor with intrinsic ion channel Enzymatic receptor Coupled with G-protein Expression through gene regulation Proteins usually Transduction into response on substance combination On the membrane/inside cytoplasm or nucleus Radiological studies for their identification Specifically bind with ligand First 4 are types of receptors. G-protein-linked second messengers: Except D1, all receptors of type ONe causes cONtractility. Classification of ADR:…………………….. “ABCDE” 1. Type A (80%)/ Augmented: Occurs in every case, is predictable and dose-related, e.g. BP. 2. Type B (20%)/ Bizarre: Occurs in some people and is not dose- related, it is unpredictable and is due to hereditary. It has most drug fatalities, e.g. allergy. Types A and B are main types of ADR. 3. Type C/ Continuous: Is due to long-term use. 4. Type D/ Delayed, e.g. carcinogenesis. 5. Type E/ (Ending of use) rxn, e.g. rebound adrenocortical insufficiency. Amide linked LA : “AmiDe LA has "Double i" in name” 1. Long-acting : Etidocaine, Bupivacaine, Ropivacaine, Dibucaine (Longest-acting LA) 2. Intermediate-acting : Lidocaine, Mepivacaine, Prilocaine Cardioselective(1): Biso-prolol, Celi-prolol, Meto-prolol, Atenolol, Acebutolol, Betaxolol, Esmolol…………….. “A to M = B CAME” blockers with : Shortest t½ — Esmolol (10 min) 27 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 Longest t½ — Nadolol (14-24 hrs) Highest bioavailability Pindolol (90%) Lowest bioavailability Alprenolol (10%) Maximum LA property Propranolol. — — — ANTIPSYCHOTIC DRUGS: “BOAT in Pond” 1. 2. Butyrophenones Droperidol. Haloperidol. Penfluridol. Trifluperidol…………..“DTPH = Dil To Pagal Hai” Others Molindone, Reserpine, Pimozide, Sulpiride, Loxapine…………. “MRP — Six Lacs” 3. Atypical Clozapine, Olanzapine, REsperidone………………..“CORE” 3. Thioxanthenes Chlorprothixene, Flupenthixol, Thiothixene……………….. “CFT = Complement Fixation Test” 5. Phenothiazines Aliphatic side chain: Chlorpromazine, Triflupromazine……………. “CAT” PiperiDine side chain: ThioriDazine. PiPERAZINE side chain: TrifluoPERAZINE, ThioproPERAZINE and Fluphenazine. “Fertilization of Two ova in Two different cycles (superfeTation)” ANTIVIRAL DRUGS 1. Antiherpes virus (CMV, HSV) : Ganciclovir Idoxuridine Foscarnet Trifluridine Famciclovir>>>>>>>>>>>>> ―GIFT For Antiherpes Virus‖ Acyclovir Vidarabine New antiherpes agents — Penciclovir, Valacyclovir>>>>>>>>>>> ―PCV” Cidofavir. 2. Anti-Retrovirus A. Protease inhibitors : Ritonavir (PI) Nelfinavir (PI) Atazanavir (PI) Fosamprenavir (PI) Amprenavir (PI) Indinavir (PI) Lopinavir (PI) Saquinavir (PI)>>>>>>>>>>>>>>“RNA FAILS (to be formed)” B. Reverse transcriptase infection)/RTI (a) Nucleoside RTI: Lamivudine (NRTI) Emtricitabine (NRTI) Tenofovir (Nucleotide RTI) Abacavir (NRTI) Didanosine (NRTI) Zalcitabine (NRTI) Zidovudine (NRTI) Stavudine (NRTI) inhibitor (b) Nonnucleoside RTI: Efavirenz (NNRTI) Nevirapine (NNRTI) Delavirdine (NNRTI)>>>>>>>>>>>>>>>>>>>>>“LET ADZZS(AIDS) END” (c) FUsion Inhibitor: EnFUvirtide 3. Anti-influenza virus : Amantadine Rimantadine (HIV 28 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 4. Nonselective : Interferon Ribavirin and Lamivudine. Stage of EXCITEMENT EXcitation and well being Concentration and confidenc decreased; lack of self-control. Inhibition is low. Time for reaction(Reaction Time) impaired; prolonged intercourse without ejaculation. Motor coordination, cognition function and sensory function are decreased. Emotion, action, speech, are less restrained. Nystagmus(alcohol gaze nystagmus means jerky movement in gaze direction) Time and space perception is altered. Stage of incoordination Loss of inhibition and blurring of consonant STAGE OF COMA Sensory and motor cells deeply affected. Temperature is subnormal. Asphyxia leads to death. Gut is disturbed. Eye: Miosis is changed into mydriasis(Mc Evans Sign) Oxidation and excretion of alcohol leads to low level in coma. >Five hours of coma means worst prognosis. Recovery leads to irritation, depression and headache(hangover) Consciousness is lost during urination(micturition syncope) Overactivity of muscles causes muscle paralysis. Munich Beer Heart (cardiac depression, hypertorphy) After irreversible damage to vital centre, death occurs. (A) Acute alcoholic intoxication: Causes hypoglycaemia hence glucose is given. Treatment Of Acute Case:………………….ABCDEFGH Alkaline solution to wash bowel. Breathing supported by oxygen. Caffeine and strychnine for nerve stimulation. Coramine 5 ml. Drip(fructose+insulin)-most patients are recovered. Electrolyte balance, ECG monitoring, 100 mg thiamine. Fluid-1 L NS with 10% glucose. Gastric lavage by NaHCO3 2gm/250 ml water. Haemodialysis. (B) Chronic alcoholism: Develops tolerance and dependence (physical and psychic), nutritional deficiencies (due to malabsorption and neglected food), neuropathy (polyneuropathy, pellegra, seizure, tremors, Korsakoff's Psychosis, Wernick’s encephalopathy), cirrhosis, HTN, myopathy (skeletal and cardiac), CHF, arrhythmia, immunity, withdrawal syndrome (anxiety, sweating, confusion, hallucination, delirium), convulsion and collapse. Peripheral neuropathy (commonest). Treatment of chronic cases:………………..ABCD Acamprosate 2 mg/day or naltrexone 100 mg/day. BZD: 1 mg lorazepam; vitamin B1 100 mg. Clonidine 100 mg IV/hour; CPZ 50 mg QID; chlormethiazole. Conditioned reflex treatment: Alcohol+drug increases ADR leading to abstinancy. Disulfiram 250 mg/day then 100 mg/day. Delirium Tremens Delirium TREMENS is due to temporary excess/sudden withdrawal. It typically begins 3-4 days after last drink. Clinical features of Delirium TREMENS Disorientation to time, place and persons. Tremors Restlessness. Enhanced HR, BP and temperature. Memory loss. Excess fear. No control on violence. Suicidal tendency; visual and auditory hallucination(death in 5-15 %) . 29 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 DISULFIRAM Mech: Inhibits aldehyde (acetaldehyde) dehydrogenase irreversibly, enhances acetaldehyde conc. in the body, causes aldehyde syndrome which reinforces not to drink. It also inhibits alcohol dehydrogenase, DA hydroxylase, CYP 450 isoenzymes, and prolongs t½ of many drugs. ADR of DISULFIRAM: Dangerous due to CVS collapse. Increased pulse and hyperventilation. Sweating. Upset(abdominal). Loss of vision. Flushing; Fainting. Increased throbbing headache. Rashes. Anxiety. Metallic taste and mailase. Hence, the patients dislike drinking due to the ADR of increased acetaldehyde. Signs and symptoms of “ANGEL DUST”: Analgesia like opioid, amphetamine like at high doses Numbness, Nystagmus and feeling of dissociation Generalized seizures, sweating, salivation, dystonia. Euphoria, miosis, visual hallucination Low sugar level Distorted perception and body image, Diaphoresis Urine(feature of ARF) Similar to ketamine, catatonic syndrome(violent, bizarre, nudism) Treatment of angel dust:…………..“ABCD” Acidify urine, NH4Cl 3 mEq/kg Breathing stabilization by oxygen C vitamin 2 mg IV Diazepam, Diaphenhydramine LSD (LYSERGIC ACID DIETHYLAMIDE) Signs and symptoms of LSD:...................................“HALLUCINOGENS” HTN,Hyperthermia. Acute mania, Arrhythmia. LSD effect, re-experienced without exposure(flashbacks). Limb aplasia,anophthalmia,cerebral malformation in pregnancy. Under UV light, it shows blue fluorescence. Changed mood and perception(colour heard and music palpated). Increased temperature(cotton fever)and bad trip(most common). No abstinence syndrome but psychic dependence present. Orally taken usually,myositis ossificans due to repeated puncture Erection of hair;Eye-mydriasis Nausea Syndrome(body packer and body stuffer syndrome); Slow passage of time; Salivation Signs and symptoms of “CANNABIS INDICA” CNS-higher centre depression with loss of perception of time and space Anaesthetic effects Numness and tingling Nasea and dizziness Aphrodisiac,talkativeness and rarely Running Amok Breathing paralysis causes death Inceased appetite with intake of food with great relish but weight loss occurs Signs and symptoms similar to alcohol(excitement to necrosis) Impotence(decreased sperm count and DHT), Irresistable desire to destroy life and property Nude beautiful women dancing before abuser is perception Dilated pupil Insomnia,hashish insanity, mood deterioration Confusion Anorexia Treatment of Cannabis indica toxicity:…………………“ABCDEFGH” Airway maintenance by intubation 30 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 Breathing maintenance by oxygen Circulation maintenance by RL/NS/D5W IV Drugs-Diazepam 10 mg IV; naloxone 2 mg; thiamine 100 mg IV;strychnine hypodermic injection. ECG monitoring. Fluid with 100 ml of 50% glucose. Give strong tea and coffee orally. Haloperidol for psychosis. Stage of excitement of COCAINE Cortex and medulla stimulation, Convulsion, Cord degeneration Ocular-mydriasis Cyanosis; Colour of skin-pallor Absence of fatigue and depression Increased heart rate, respiratory rate, temperature, physical activity and energy and hypotension Numbness of extremities, nose and throat; Nausea Excited, restless and talkative Stage of depression of “WHITE LADY” Within an hour Heart failure, respiratory depression and vascular collapse. Irritability Tactile hallucination(cocaine bugs), Tachycardia and Tachypnoea Eye-mydriasis Loss of interest in family, food and sex Abnormal behaviour(paranoid, mania and depression) Dysphoria(depression and insomnia) Young of upper class more effected due to high cost. Treatment of cocaine poisoning:…………………….“ABCDEFGHI” Airway maintenance by intubation Breathing maintenance by oxygen Circulation maintenance by NS/RL Drugs-Diazepam/chloroform for convulsion; barbiturate for stimulation; naloxone 2 mg IV; thiamine 100 mg IV; ice bath for hyperthermia. Ensure ligature above the part if injected 1. 2. 1. 2. 3. For chronic case-amphetamine,lithium and bromocriptine. Gastric lavage by warm water containing charcoal,KMnO4 and tannic acid. Wash out nose and throat with water. Haloperidol for psychosis. Inhalational amylnitrate is antidote. CIGARETTES Cigarettes give nicotine (active substance) which causes : CNS stimulation (arousal, relaxation and mild euphoria). Stimulation of sympathetic nervous system vasoconstriction BP. Tars and CO inhaled enhance COPD, cancer and heart disease. Physical and psychological dependence occurs. Abstinence leads to anxiety, insomnia and appetite loss. Approaches to abstaining from cigarettes: Bupropion (TCA). Behavioural modification. Nicotine available in gum, patch and inhaler. Treatment of acute poisoning: Airway, breathing and circulation maintenance. Wash With Warm Water (4W) containing charcoal, tannin and KI. Urine acidification, BZD. Gastric lavage by KMnO4. Mecamylamine (specific antagonist). NaSO4, atropine and hexamethonium (50 mg s.c.) along with symptomatic treatment. Clonidine 30 mg/day (weans away from addiction), buspirone, 5-HT uptake inhibitor, doxepin, Vit. C. The smoker PUTS down 4 diseases (these favour non-smokers): Pre-eclampsia, Ulcerative colitis, Tremor agitans (parkinsonism), Sarcoidosis. “Cigarette is a roll of tobacco with a flame at one end and a fool at the other end” BARBITURATES (ACIDIC DRUG) “Barbiturates facilitate GABA action by increased DURATION of Cl – channel opening. barbiDURATe = DURATion”. Signs and symptoms of “BARBITURATES” 31 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 BP is decreased due to medullary and myocardial depression. Arrhythmia causes death. Peripheral blood pooling occurs. Respiratory, CVS and CNS depression. Renal BZD depression due to hypotension. BZD and alcohol are cumulative and Intensify toxicity. Tone of muscle is lost. Unsteady gait,Unconsciousness, Urine and stool incontinence. Rapid toxicity due to unstable angina(a few second to minute). Ataxia, Absent reflex(planter and flexor), Babinskis sign positive. Temperature is decreased. Eye-miosis thereafter mydriasis. Somnolence; Skin cold, camy and cyanotic.Barbiturate blister. Treatment of barbiturate poisoning:…………………… “ABCDEFGH” Airway Breathing and Circulation stabilization by oxygen, NS, RL and Scandinavian method(antishock measure) by NA 2 mg/DA. Do not revive CNS/respiratory depression with analeptics(amphetamine 20 mg IV, cardiazol 5 mg IV, amiphenazole 15 mg IV, picrotoxin, nikethamide) due to increased oxygen demand, increased temperature and increased seizures.Drugs: vasodepressor (DA) and forced alkaline diuresis with Mannitol and NaHCO3 . Exteremly hard concretion in stomach(stomach wash upto 8 hours must be done). Forced alkaline diuresis in case of LA by mannitol(most useful)200 ml of 25% then 500 ml of 5 % in next 3 hours then 5% dextrose in 1 day for 10-20 L urine excretion must be done. Gastirc lavage with activated charcoal(1 mg/kg), KMnO4,tannic acid, MgSO4 for purgation. Gradual withdrawal in chronic use with symptomatic treatment due to physical and psychological dependence. No specific antidote. Hemodialysis and haemoperfusion. Mechanism of BZD: They act as GABA agonist. Overall action of all BZD is the same. ―BZD Facilitates GABA action by Frequency of Cl- channel opening.” Signs And Symptoms Of BZD Toxicity 1.Acute:……………. “DIAZEPAM” Diplopia,Dysarthria Increased reaction time Ataxia diZziness Epigastric pain Paradoxical CNS stimulation Abuse liability due to dependence Memory loss 2. Chronic:Anxiety, intolerance, tremor, muscle spasm Treatment:………………….. “ABCDEF” Airway, Breathing and Circulation maintenance by oxygen, intubation etc. Diazepam 5 mg IV for withdrawal reaction then tapered off. Electrolyte balance by NS/RL Flumazenil 5 mg IV at the rate of 0.1 mg/minute Diazepam is DOC :………………………………“The SPASM” Delirium Tremens Status epilepticus (I.V.) Postoperative delirium Alcohol withdrawal syndrome. Febrile Seizures. Preanaesthetic Medication. in 32 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 Alprazolam is BZD of choice in :………………………….. “APE” Agoraphobia (fear of being alone or in open space). Panic disorder Elderly individual Uses of DIAZEPAM: Delirium tremens (in alcohol withdrawal), Insomnia and neurosis, Anxiety, before cardiac catheteriZation, sedation surgery, Epilepsy, Preanaesthetic medication, I.V. anaesthesia, As Adjuvant with Antiemetics, Muscle relaxation. PARALDEHYDE before Therapeutic effects of DIAZEPAM: Drowsiness, Increased reaction time, Ataxia, diZziness (hangover), Epigastric distress, Paradoxical CNS stimulation, Abuse liability (due to dependence), Memory loss (=amnesia). It is called "Knockout drops" due to its rapid action for the purpose of rape/robbery. Mickey Finn = Alcohol + chloral hydrate. Signs and symptoms of “CHLORAL” hydrate Convulion,mental retardation Habitual use-tolerance and physical dependence Like barbiturates, it manifests Ocular-pinpoint pupil before death Retrosternal burning sensation,urticaria,scarlet rash Albuminuria Loss of life due to paralysis of respiratory centre. Treatment of chloralhydrate:………ABCDEF Airway intubation Breathing maintenance by oxygen Cardiac stimulation It is potent hypnotic with sharp and short lasting actions. Uses are: Delirium To calm down Agitated patients Tetanus Eclampsia…………….. ―DATES” Convulsion of Status epilepticus. Drugs with increased absorption with food are: Diazepam, Thiazides, Propranolol, Halofantrine, Lithium and Griseofulvin……………………… ―DTPH & Love Guru‖ SEIZURES They are paroxysmal event due to uncontrolled excessive hypersynchronous discharges from an aggregate CNS neurones. CHLORALHYDRATE (PRODRUG) Drugs-flumazenil 0.1 mg(maximum 3 mg) ,diazepam. Electrolytes(glucose,NS/RL IV) Forced alkaline diuresis Major types : 1. Focal/partial (local brain part) : a. Simple (SPS) cortical lobe epilepsy : Lasts 1 min., involves a group of ms., no loss of consciousness. b. Complex (CPS)/psychomotor/temporal lobe epilepsy : Lasts 1-2 min., Bizarre behaviour (staring, roaming). It is associated with attention in consciousness coupled with automation (chewing, aimless walking, etc.). 2. Generalised (large part of the body):………… “I AM FAST” Infantile spasm : Intermittent ms. spasm with mental retardation. 33 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 Atonic seizures (Akinetic epilepsy) : Unconsciousness without relaxation of all muscles due to excessive inhibitory discharge. Myoclonic : Momentary ms. contraction. Febrile seizures (6 months to 6 yrs) : Due to >101.8° F temp. Absence/Petitmal : Brief impairment of consciousness, involves mainly children, lasts ½ min., EEG 3 cps (spike and wave pattern). Status epilepticus : Continuous clinical menifestations of epileptic disease without intermission. Tonic-clonic /grandmal /major epilepsy : commonest, lasts 1-2 min. Oedema (peripheral), Appetite increased, Tremor, Enzyme inducer (liver). Drugs causing fatty liver are :…………………. “SMART” Sod. valporate, Mtx, Amiodarone, aspaRaginase, Tetracycline PHENYTOIN/DIPHENYL HYDANTOIN Mechanism of phenytoin: use dependent blockade of Na+channel. Mechanism of action of antiepileptics: Inhibition of GABA—Transaminase by vigabatrin and valproic acid. VIGABATRIN = GABA TRansaminase INhibition (irreversible). GABA release in brain by GABApentin (not act as GABAA R agonist). Facilitation of GABA mediated Cl- channel opening by BZD, barbiturates, valproate, vigabatrin, gabapentin. Induction of T type Ca++ current by valproate, trimethadione and ethosuximide. Prolongation of Na+ channel inactivation by phenytoin, valproate, carbamazepine and lamotrigine. ADR of PHENYTOIN: P – 450 interaction, Hirsutism, Enlarged gum, Nystagmus, Yellow-brown skin, Teratogenic, Osteomalacia, Interference with B12 metabolism leading to anemia, Neuropathy (vertigo, ataxia, headache). VALPROIC ACID ADR of “VALPROATE” : Vomiting, Alopecia, Liver toxicity, Pancytopenia/pancreatitis, Retention of fat (weight gain), CHLORPROMAZINE (CPZ) (AS PROTOTYPE) Chlorpromazine is the prototype ―ANTIPSYCHOTIC”. Its actions are: Antipsychotic effect in psychotic patients (therapeutic effect). Neuroleptic syndrome in normal persons (unpleasant). Temperature control is disturbed. Increased chances of epileptic fits due to decreased seizure threshold. Prolactin release increases – glactorrhoea and gynecomastia. Side effects – Extrapyramidal, e.g. Parkinsonism, dystonias, akathisia, dyskinesia. Yellowness, i.e. cholestatic jaundice. Cholinergic antagonism leading to dry mouth, etc. Hypotension. Obesity. Tolerance to some effects like sedation. Inhibition of gonadotropin secretion and D2 R mainly. Certain spastic conditions are relieved. ADR of neuroleptics: A. Hypersensitivity rxn (not dose related) : Skin rashes, urticaria, contact dermatitis, photosensitivity = 5%. Cholestatic jaundice = 4%. Agranulocytosis (common with clozapine) = 0.8%. B. Dose related :…………………………….. “ACE Blockade‖ Anticholinergic (dry mouth, constipation, urinary hesitency, blurred vision). CNS (confusion, drowsiness, tolerance and appetite). 34 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 Endocrine (amenorrhoea, infertility, gynaecomastia due to protactin and gonadotropin) . Extrapyramidal disturbances (least with clozapine, risperidone, thioridazine, and more with potent drugs). Blockade of alpha rceptors (postural hypotension, palpitation, inhibition of ejaculation). Blue pigmentation of exposed skin and retinal degeneration. Extrapyramidal ADR: 4 hours 4 days 4 weeks 4 months Time of Evolution of ADR Acute dystonia Akinesia Akathisia Tardive dyskinesia Extrapyramidal ADR Syndrome (Malignant neuroleptic syndrome) Muscular dystonia Akathisia ……………………… “SMART Person‖ Rabbit tremor Tardive dyskinesia Parkinsonism Neuroleptics are for rapid control of mania and for shortterm basis to control organic brain syndrome. Max. therapeutic effect in chronic schizophrenia occurs in 2-4 months therapy. TCA: IMIPRAMINE (PROTOTYPE) Imipramine forms desipramine (Active metabolite). Amitriptyline forms nortriptyline (Active metabolite). ADR of SSRI: Serotonin syndrome (causes HARM = Hyperthermia, Autonomic instability, Rigidity, Myoclonus), Stimulates CNS, Reproductive dysfunction in male, Insomnia. ADR of TCAs: Thrombocytopenia, Cardiac (MI, stroke), coma, convulsion, Anticholinergic, Seizures. Signs and symptoms of “ANTIDEPRESSANTS” toxicity Agitation NA blockade causes hypertension Toxic to heart by unknown mechanism Increased heart rate Dilated pupil Extension of planter reflex Pulmonary system depression Retention of urine due to anticholinergic side effects Eye-blurred vision Seizure(myoclonic jerk) Suppression of BP Acidosis(metabolic) NA and 5-HT inhibition causes mood elevation Tremor Serotonin syndrome causes HARMHyperthermia,Autonomic instability,Rigidity,Myoclonus Treatment of antidepressants:…………….. “ABCD” Adequate oxygen,Activated charcoal,Antidote(physiostigmine 2 mg IV for 5 minutes), watch out SLUD(Salivation, Lacrimation, Urination, Defecation),Central effects are present. Bicarbonate(NaHCO3) 50 mEq IV.Lidocaine/phenytoin may be used Correction of hypotension and acidosis Diazepam for convulsion IA : Phenytoin, Phenylbutazone, CPZ and Aspirin displace TCA from protein binding sites and cause toxicity. Where there is sins (PAPZ), there is toxicity (to TCA). Limitation of TCA: Limited efficacy, Low therapeutic margin……………………. “3L CAN” Lag time of 2-4 wk.before response, ADR (Cardiovascular, Anticholinergic and Neurological). VENLAFAXINE : It is a novel antidepressant. Sedation absent. 35 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 Mech: 5 - HT and NA reuptake inhibitor but does not interact with cholinergic, adrenergic and histaminergic R. It enhances BP. ADR: Raised BP, Anxiety, Impotence, inhibitor of CYP 450, Sweating, Enhanced nasal secretion (nausea), Dizziness…………………………. ―RAISED BP” AMINEPTINE Antidepressant action is due to increased serotonin uptake (similar to tianeptine). ADR: Postural hypotension, Anticholinergic ADR, Conductive disturbance of the diseased heart, Tachycardia………………………………………. ―PACT‖ Li2CO3/MOOD STABILISER/ANTIMANIC DRUG ADR of “LITHIUM‖ Leukocyte Increased, Tremor, Hypothyroidism, Increased Urine, Moms alerted due to teratogenicity. MORPHINE “Morphine is for for More Pain” Opium poppy: 10% opium Morphine 1% opium Codeine. They are phenanthrene derivative of P. somniferum. Pure active morphine was isolated from opium by Serturner. Morphine is called God's Own Medicine by Sir William Osler. Morphine and pethidine are anodyne hypnotics. Actions of receptors(spinal and supraspinal): Mu: Hormone change. Analgesia. Respiratory depression. DA release. ACh release. Reinforcement euphoria. Motility of gut is enhanced. Cough and appetite suppression………. HARD ARMS Kappa: Decreased dysphoria, GI motility, appetite and respiration; analgesia, psychosis, sedation, diuresis. Sigma: Hormone change, DA release and decreased appetite. Delta: Cardiac stimulation. Hallucination. Dysphoria……………..CHD Mechanism of action of opioid : It causes hyperpolarisation of nerve cell, inhibition of nerve firing and presynaptic inhibition of transmitter release. Effects of ―MORPHINES” Miosis, Orthostatic hypotension, Respiratory depression, Pain suppression, Histamine release and Hormonal alteration, Increased ICP, Nausea, Euphoria, Sedation. ADR : 1. Sedation, lethargy, idiosyncrasy and allergy. Allergy and idiosyncrasy (local rxn due to histamine release, swelling of lips, urticaria). 2. Apnoea in newborn due to drug intake by mother during pregnancy (more attainment of drug by foetus in brain). Naloxone 10 g/kg injected in cord is DOC. 3. Acute morphine poisoning : Lethal dose — 250 mg. Manifestations - coma, cyanosis, flaccidity, BP, pinpoint pupil, death due to respiratory failure. Excitement stupor coma. Treatment :…………………………………….. “ABCDEFG” 36 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 Airway, Breathing and Circulation maintenance.Amphenazole 30 mg IV.Coma cocktail(100 ml of 50 % glucose and 100 mg thiamine) Drugs (vosoconstrictor) and 0.6 mg/i.v. naloxone (DOC).Methadone(long action).Nalmefene 1 mg/kg IV.Physiostigmine 0.04 mg/kg IV. Ephedrine. Caffeine. Amphetamine. ECG monitoring and Fluid balance. Gastric lavage with KMnO4 , NaSO4 and charcoal. Chronic poisoning of OPIUM: Opium addicts tolerate upto 6 gm/day. Pleasurable feeling of relief and well being then depression. Irritation; Insomnia; Impotance; Intellectual deterioration. Ultimate result to foetus is life threatening. Miosis; Mental fatigue; Moral deterioration; Memory loss. 4. Tolerance and dependence (psychological and physical) present. Tolerance is partly pharmacokinetic (rate of metabolism) but mainly pharmacodynamic (cellular tolerance). Crosstolerance present. Effects of morphine for which high degree of tolerance develops are : Sedation, Mental clouding, Euphoria and dysphoria, Analgesia and antidiuresis, Respiratory depression………………. ―SMEAR” Effect of morphine for which minimal or no tolerance develops are : Constipation, Antagonistic action, convuLsion and Miosis………………………………. ―CALM” METHADONE 1 mg of oral methadone = 4 mg of morphine = 2 mg of heroin = 20 mg of pethidine. U :……………………………………………. “MADS” 1. Maintenance therapy in opioid addicts : methadone in sufficient dose given orally to produce high degree of tolerance so that subjects give up the habit in the absence of pleasurable effects of I.V. doses of heroin and morphine. 2. Analgesia in labour and biliary colic. 3. Detoxification of morphine addicts methadone (DOC). Nonaddicting drug used in opioid withdrawal syndrome clonidine. 4. Substitution therapy in opioid dependence. 1 mg oral methadone subsituated for 2 mg Heroin…………..―HMP—2, 4, 20‖ 4 mg Morphine. 20 mg Pethidine. Uses of morphine: Cardiac Asthma (Acute LVF) Balanced anaesthesia and neurolept analgesia Cough Diarrhoea Analgesic Preanaesthetic Medication Pulmonary edema Epidural anaesthesia………………………………. “ABC DAMPEN” Neurogenic shock NALOXONE It is a competitive antagonist on all types of opioid R. and is a N-alylnor-oxymorphone. NArcotic ANtagonists are NAloxone and NAltrexone. ADR of “ASPIRIN” : Asthma, Salicylism, Premature closure of PDA/Platelet disaggregation/Phosphorylation – oxidation uncoupling, Intestinal bleeding due to peptic ulcer, Reye’s syndrome, Idiosyncracy, Noise (tinnitus). Order of toxicity: Tinnitus uncoupling of oxidative phosphorylation ( CO2 respiration) (medullary stimulation HCO3- loss and respiratory alkalosis) 37 | P a g e BE ST SEL L INGB OOK S: AWE SO ME RE VIEW SE RIES O F JAMIA URDU H INDPUB L ISH E D B Y JUH PRESSO F FAL AH -E -H IND L IB RARY. ISB N006527278 acidosis (HCO3- loss, fluid and electrolyte loss, respiratory depression). Manifestations: Nausea and vomiting Acidotic Breathing Coma and Convulsion Dehydration and Delirium Electrolyte imbalance Death due to respiratory Failure + cardiovascular collapse Giddiness Hallucination and Hyperpyrexia Restlessness ………………………….. ―ABCDEFGH” Treatment: 1. Airway Breathing and Circulation maintenance 2. Forced alkaline Diuresis and Hemodialysis to remove absorbed drug. 3. Electrolyte balance by I.V. Fluid with Na+, K+, HCO3and Glucose and External cooling (Most important). 4. Gastric lavage to remove unabsorbed drug. 5. Blood transfusion&Vitamin K….. “ABCDEFGH”
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