Pharmaceutical Inorganic Chemistry

Index

Part - I

Theoretical Pharmaceutical Inorganic Chemistry

CHAPTER 1 : Introduction

1.1 Inorganic Chemistry

The inorganic chemistry was originally meant for non-living chemistry. It was the part of chemistry that has arisen from the arts and recipes which deals with minerals and ores. This chemistry began with finding naturally occurring substances that had useful properties for e.g., flint (~5 × 10⁵ years ago). The research continues in various fields of sciences like mineralogy, geology and later in other fields like pharmaceutical, bioinorganic enzymes, high temp-super conductors, metals etc. First chemical reaction was the discovery of fire, the most important early reactions were the reductions of metal oxides, carbonates and sulfides to metals. This chemistry mainly deals with the changes that can be effected in materials. There is a need to distinguish between superficial resemblances for e.g., between fool’s gold (iron pyrites, FeS2) and the element gold. Now we can see how far inorganic chemistry has developed from the days when it was meant for non-living to various other fields including living.

1.2 Inorganic Nomenclature

The complexity of inorganic compounds increases, there is difficulty in describing these compounds with simple names. The rules were issued by the International Commission on the Nomenclature of Inorganic Chemistry.

1.2 (a) Formulas and Names of Compounds

(i)   In formulas the cation (electropositive constituent) will be placed first in the binary compounds.

NaCl, MgSO4, AlCl3 etc.

(ii)   In the formulas of binary compounds between non-metals, the constituent that occurs in the sequence i.e., heavier non-metal first followed by the lower.

IF7, NH3, Cl2O, OF2 etc.

SOr -sulphate, NO" -nitrate,

SO3²- -sulphite, NO2 -nitrite,

SO2 -sulphur dioxide, NO -nitric oxide etc.

(vi)   Some of the polyatomic compounds have central atom or characteristic atom. The atoms, radicals or molecules attached to central atom. Such polyatomic group is named as complex and the atom, radicals or molecules bound to the central atom are called ligands.

(vii)   The molecular hydrides naming is naming the element followed by suffix -ane

PbH4 -plumbane, GeH4 -germane

SiH4 -silane, B2H6 -diborane etc.

(viii)   There are exceptions to these rules.

PH3 -phosphine, AsH3 -arsine,

sbH3 -stilbine, BiH3 -bismuthane

1.2 (b) Name for Ions and Radicals

Radical is a group of atoms which occurs repeatedly in a number of different compounds. (i) For mono atomic cations

Cu+ Copper (I) ion, Fe2+ iron (II) ion

I+ Iodine (I) cation (ii) For poly atomic cations

NO+ nitrayl cation, NO +2 nitryl cation

(iii)   For polyatomic cations derived by the addition of more photons end in-onium.

PH+4 - Phosphonium, As H+4 - Arsonium

NH+4 - Ammonium is exception for this.

(iv)   Substituted ammonium ions derived form nitrogen bases with names ending in-amine to - ammonium.

NH2-CH2-CH2-NH2 -ethylene diamine.

OH NH3+ -hydroxyl ammonium

(v)   The naming of monoatomic anions -end in - ide

H– - hydride ion Cl– - chloride ion

N3– - azide ion O²– - oxide ion

S²– - sulphide ion

(vi) The names of certain polyatomic anions -end in - ideOH– - hydroxide ion, NH²– - imide ion

(vii)   The names of oxygen containing anions

(viii)   The names of certain neutral and cationic radicals containing oxygen or other chalcogens end in - yl.

1.2 (c) Acids

(i)   Binary or psuedobinary compounds of hydrogen end in - ide

HCl - hydrogen chloride

HCN- hydrogen cyanide

H2S - hydrogen sulphide

(ii)   The oxo-acids name end with - ous or - ic.

H2N2O2 - hyponitrous acid

H4P2O6 - hypophosphic acid

HOBr - hypobromous acid

Prefix hypo - is used to denote lower oxidation state and per – used to denote higher oxidation state.

HClO4 - perchloric acid

HIO4 - periodic acid

Prefix ortho -, meta -, para - are used to distinguish acids differing in the ‘content of water’.

The names of other oxo acids:

2 (d) Elements, Atoms and Group of Atoms

(i)   Identification of mass, charge and atomic number using indexes. Mass, ionic charge, atomic numbers are indicated by means of:

(ii)   Isotopes: Atomic number in same but mass number different

isotopes of hydrogen - ¹H, ²H, ³H named as portium, deuterium and tritium respectively.

The cations ¹H+, ²H+, ³H+ named as proton, deuteron triton respectively.

(iii)   Name of an element or elementary substance of definite molecular structure or formula.

O2 - oxygen, O3 - ozone, P4 - white phosphorous,

S8 - a - sulphur, p - sulphur etc.

1.2 (e) Salts

(i)    salts: A salt is a chemical compound consisting of a combination of cations and anions. H3O+ is normally called as acid (both salt and acid character)

(ii)    Binary compound can be defined as that it contains only one kind of cation and one kind of anion and is still considered as salt.

NaCl - sodium chloride, LiH - lithium hydride

For polyatomic cations and / or anions enclosing marks should be used.

TlII3 - thallium (I) triiodide

TlIIII3 - thallium (III) triiodide

For salts containing acid hydrogen: Salts containing both a hydron which is replaceable and one or more metal cations are called acid salts

NaHCO3 - sodium hydrogen carbonate

LiH2PO4 - lithium dihodrogen phosphate

K2HPO4 - dipotassium hydrogen phosphate

NaHSO3 - sodium bisulphite

1.2 (f) Prefixes or Affixes used in Nomenclature

(i)    Multiplying affixes

These are used by direct joining without hyphens (-).

Other nomenclature used is:

bis (2), tris (3), tetrakis (4), pentakis (5) etc., also by direct joining without hyphens but usually with enclosing marks each whole expression to which prefix applies.

(ii)   structural affixes

These affixes are italicized ad separated from the rest of the name by hyphens.

(iii)   Substitutional Affixes:

An affix such as ‘ferra’, ‘nickela’, ‘sila’, metalla’ etc., can be used to indicate the formal substitution of a heteroatom in a hydrocarbon.

silabenzene-one silicon is substituted in place of carbon in benzene.

Ferra cyclopropane (metalla cycle)

1.2 (g) Nomenclature of Complexes

To name the variety of coordination compounds in a more uniform fashion, Nomenclature committee of the International Union of Pure and Applied Chemistry (IUPAC) suggested the rules (1989).

(i)   If a complex contains ions, the full name of the positive ion is given first followed by the full name of the negative ion. The central atom is named last though it is written first in the formula

[Fe(H2O)6] ²+ - Hexaaquairon (II) ion

K2[PtCl6] - Potassium hexachloroplatinate (II)

[Co(NH3)6]Cl3 - Hexammine cobalt (III) chloride

If the complex is neutral it is given one word name

[Pt(NH3)2Cl2] – Diammine dichloroplatinum (II)

(ii)   In a complex ion, the order of presentation is – ligands, metal with oxidation state in Roman numerical.

K3 [Cr(CN)6] - potassium hexa cyano chromate (III)

[Cr(H2O)6]Cl3 - Hexaaquachlornium (III) chloride

(iii)   In writing the name of the complex: The ligands are quoted in alphabetical order, regardless of their charge (followed by metal).

All negative (- ve) ligands end in - O

Neutral ligands have no special endings.

Organic ligands are usually given their common names

(iv)   In writing the formula of the complex: The complex ion should be enclosed by square brackets. The metal is written first, then the ligands in the order – negative ligands, neutral ligands, and positive ligands (alphabetically according to first symbol within each group)

[Co Cl2(NH3)4] Cl – Tetraamminedichlorocobralt (III) chloride

K2 [Os Cl5 N] – potassium petachloro nitridoosmate (IV)

(v)   In a complex ion – for the same ligands the prefixes di, tetra, penta, etc., are used and for the multidentate ligands (groups with complicated structure) the prefixes bis, tris, tetrakis, pentakis etc., and the ligand is enclosed in parentheses.

K2 [Cr (CN)2 O2 (O2) NH3] – potassium ammine dicyanodioxoperoxochromate (IV)

[Co Cl2 (CH)2] Cl - Dichlorobis (ethylene diammine) cobalt (III) chloride

K3 [Fe (ox)3]- Potassium tris (oxalato) ferrate (III)

(vi)   For Ambidentate ligands (ligands are attached by more than one atom): The attached atom is specified.

[Co (ONO) (NH3)5] Cl2 pentaammine nitro-O cobalt (III) chloride

[Co (NO2) (NH3)5] Cl2 pentaammine nitro-N cobalt (III) chloride

The other ambidenatate ligands are: –

(vii)   Bridged ligands are denoted by »

μ - amido bis (pentammine cobalt (III) nitrate

[(NH3)5 CoNH2Co (NH3)5] (NO3)5

(viii)   For metal to metal bonds, prefix bi - is used

sym-dichloro octakis (methylamine) biplatinum (II) chloride For more than two metals

D-[Co(en)3]³+ D-[ Co(l – pn)3 ]³+ D [ Co(d - pn)3]³+

AlK(SO4)2. 12H2O

Aluminum potassium sulphate 12 water

Fe(NH4)2 (SO4)2. 6H2O

Ferrous ammonium sulphate 6 water

1.2 (h) Chemical Reaction

A chemical reaction is a change of bonding between atoms. Bonding changes occur because of rearrangement or transfer of outer electrons about atoms. Chemical reactions are often accompanied by a change in energy.

Symbols used in chemical equation are:

1.3 Analytical Chemistry

Analytical chemistry is a measurement of science consisting of powerful ideas and methods that are useful in all fields of science and medicine. Analysis is:

Analytical chemistry is applied throughout industry, medicine and in all the sciences. The relationship between analytical chemistry and other branches of chemistry and sciences is shown in Fig 1.1

Fig. 1.1

1.4 Pharmaceutical Chemistry

1.4.1 Introduction

Chemistry is the defining science of pharmacy. To understand anything about a drug – the synthesis, the determination of its purity, the formulation into a medicine, the dose given, the absorption and distribution around the body, the molecular interaction of drug with its receptor, the metabolism of the drug and finally, the elimination of drug from the body - requires a thorough and comprehensive understanding of the chemical structure of the drug and how this chemical structure influences the properties and behavior of the drug in the body. For these reasons, chemistry is the most important of all the scientific disciplines contributing to the understanding of drugs and their actions in the body. A good understanding of the chemistry of drugs will allow the study of advanced topics such as drug design and medicinal chemistry, molecular pharmacology and novel drug delivery systems that are usually encountered in the later stages of a pharmacy or pharmaceutical science degree.

Pharmaceutical chemistry is a science that makes use of the general laws of chemistry to study drugs, i.e., their preparation, chemical nature, composition, structure, influence on an organism studies, the physical and chemical properties of drugs, quality control methods and their usage conditions etc.

Inorganic chemicals have been used in pharmacy and medicine for many reasons, ranging from therapeutic agents to nutritional supplements to pharmaceutical necessities. Inorganic pharmaceutical chemistry is a science that makes use of laws of chemistry to study inorganic substances as drugs. Inorganic drugs are majorly obtained from the natural source such as minerals. Examples include waters, inorganic chemicals, calcined inorganics, heavy metals etc. Although many inorganic chemicals are rarely used today, yet few inorganic chemicals are being still used in modern medicine.

1.4.2 Pharmacopeia

The word ‘pharmacopoeia’ is derived from the Greek words ‘pharmakon’ means drug or medicine and ‘poeia’ means to make. Pharmacopoeia, in its modern technical sense, is a book containing directions for the identification of samples and the preparation of compound medicines, and published by the authority of a government or a medical or pharmaceutical society. In a broader sense it is a reference work for pharmaceutical drug specifications. Most of the advanced countries have their own pharmacopoeia.

1.4.3 History of Pharmacopeia

In olden times, physicians used to prepare their own prescriptions. As the complexity of medical formulae increased, physicians delegated this laborious work to their assistants, called apothecaries. These apothecaries gradually become independent. They looked for guidance and knowledge to the books written by individuals who had achieved fame in medicine. The first known dated work of this kind published under civic authority appears to have been that of Nuremberg in 1542; a student named Valerius Cordus showed a collection of medical receipts, which he had selected from the writings of the most eminent medical authorities, to the physicians of the town, who urged him to print it for the benefit of the apothecaries, and obtained for his work the sanction of the senatus. The term Pharmacopoeia first appears as a distinct title in a work published at Basel in 1561 by Dr A. Foes, but does not appear to have come into general use until the beginning of the 17th century. The credit for producing the first national pharmacopoeia goes to England. Until 1617 such drugs and medicines as were in common use were sold in England by the apothecaries and grocers. In that year the apothecaries obtained a separate charter and it was enacted that no grocer should keep an apothecary’s shop. The preparation of physicians’ prescriptions was thus confined to the apothecaries, upon whom pressure was brought to bear to make them dispense accurately.

By the issue of a First Pharmacopoeia in May 1618 by the College of Physicians, and the wardens of the apothecaries received the powers to destroy all the compounds which they found unfaithfully prepared. Thus, the first authorized London Pharmacopoeia, was selected chiefly from the works of Mezue and Nicolaus de Salerno, but it was found to be so full of errors that the whole edition was cancelled, and a fresh edition was published in the following December. At this period the compounds employed in medicine were often heterogeneous mixtures, some of which contained from 20 to 70, or more, ingredients, while a large number of samples were used in consequence of the same substance being supposed to possess different qualities according to the source from which it was derived. During the 17th and 18th centuries more than 50 regional pharmacopoeias appeared.

1.4.4 Indian Pharmacopoeia

The pharmacopoeia originated as the Bengal Pharmacopoeia and General Conspectus of Medicinal Plants, 1844 and was known as the Bengal Pharmacopoeia. Its main focus was on indigenous drugs although it included some products imported from Europe. The first pharmacopoeia was published in 1868 under the authority of the Secretary of State for India in Council by a committee constituted in 1865. It contained standards for drugs official in the British Pharmacopoeia (BP) 1867 and a few selected indigenous drugs. A Supplement to the British pharmacopoeia came out in 1869 and remained in use till around 1885. With the publication of the British Pharmacopoeia in 1885 the then Government made this the sole authority on all matters relating to pharmacy. In 1900 the Indian and Colonial Addendum to the BP 1898 was published and an Indian edition of it with minor modifications came out in 1901. Until 1955 the British Pharmacopoeia remained our official guide on drugs standards. There started a move for a separate Indian Pharmacopoeia right after the publication of British Pharmacopoeia in 1914.

The BP Commission made provision for publication of Supplements to take care of local needs. In 1946 the Indian Pharmacopoeial List was prepared to serve as an Indian Supplement to BP 1932. After Independence an Indian Pharmacopoeia Committee, a permanent body was constituted in 1948 and it prepared the Pharmacopoeia of India (The Indian Pharmacopoeia) 1955. Subsequent editions were brought out.

The First Edition of the IP was published in 1955. It had laid down standards mainly for imported drug products and locally manufactured herbal products. In 1954 the original IP Committee had been reconstituted to bring out the second edition but managed to publish only a Supplement to the first edition in 1960.

In the meantime the country had made substantial progress in the manufacture of drug products and a few drug substances from imported intermediates.

The IP Committee was reconstituted again in 1962 with only one representative from the industry. It brought out the Second edition in 1967 with 885 monographs.

The revision of this edition was overdue and it was decided to bring out a Supplement with the help of a reconstituted Committee in 1972 which had representatives from different disciplines in the industry and the government. The Supplement came out in 1975. Simultaneously, work on the third edition had been initiated by the committee which had a wider representation. It had eminent physicians, pharmacologists, representatives of professional bodies, the regulatory agencies, the industry and independent professionals. It brought out the third edition in 1985. It had several changes in the contents and in the manner of presentation. It also published addenda to this edition in 1989 and 1991. A reconstituted committee published the fourth edition in 1996.

The latest edition of the Indian Pharmacopoeia entitled Indian Pharmacopoeia 2007 has been prepared by the Indian Pharmacopoeia Commission (IPC) in accordance with a plan and completed through the untiring efforts of its members and its Secretariat over a period of about two years. This is the fifth edition of the Indian Pharmacopoeia after independence. It supersedes the 1996 edition but any monograph of the earlier edition that does not figure in this edition continues to be official as stipulated in the second schedule of the drugs and Cosmetics Act, 1940. The Indian Pharmacopoeia 2007 is presented in three volumes. Volume I contains the general notices, preface, the structure of the IPC, acknowledgements, introduction, and the general chapters. Volume 2 deals with the general monographs on drug substances, dosage forms and pharmaceutical aids (A to M). Volume 3 Contains Monographs on drug substances, dosage forms and pharmaceutical aids (N to Z) followed by monographs on vaccines and immunizers for human use, herbs and herbal products, blood and blood related products, biotechnology products and veterinary products. The scope of the pharmacopoeia has been extended to include products of biotechnology, indigenous herbs and herbal products, viral vaccines and additional antiretroviral drugs and formulations, inclusive of commonly used fixed-dose combinations. To assure the health care professional’s patients and consumers of the standards of drug in India the Secretary, Ministry of Health & Family Welfare, Shri Naresh Dayal who is also the Chairman of Indian Pharmacopoeia Commission released the Addendum 2008 to the Indian Pharmacopoeia (IP) 2007. The Addendum contains amendments to IP 2007 and adds 73 new monographs on different therapeutic groups representing synthetic, herbals and biological drugs. While the amendments to the IP 2007 will come into force with immediate effect, the new monographs will become effective from 1st July 2009. A monograph in I.P. includes the following features:

Main title: Name of the substance.

1.   Synonyms: The common names, if any.

2.   Chemical Formula: Gives chemical structure of molecule

3.   Molecular Weight: Calculated from molecular formula using standard atomic weights.

4.   Category: It indicates drug’s pharmacological activity.

5.   Doses: Gives the average dose for adults.

6.   Description: Statements on colour, odour and taste.

7.   Solubility: Terms used to indicate different degrees of solubility are

8.   Standards: I.P. prescribes standards of purity and strength in the monograph of almost all the official substances.

9.   Identification: This includes some specific and some non-specific tests for identify of the substance.

10.   Test for purity: I.P. prescribes for purity of almost all the official substances. These tests include melting point, boiling point, weight per ml, limit tests for chloride, sulphates, iron, heavy metals, lead and arsenic, specific optical rotation, sulphated ash, loss on drying, pH pf the solution, etc., as may applicable for the substance.

11.   Assay: An assay gives in detail the analytical method for the substance in order to determine the % content of a particular chemical in the given test sample.

12.   Storage: The substances and preparations of I.P. are to be stored under conditions that prevent contamination and deterioration.

Terms used for indicating different temperature conditions are-

1.4.5 United States Pharmacopeia

The United States Pharmacopeia (USP) is the official pharmacopeia of the United States, published dually with the National Formulary as the USP-NF. In 1817, Dr.Lyman Spadling of New York proposed a plan to the Medical society of the country at Newyork for publishing a National Pharmacopeia. The first edition of United States Pharmacopeia was compiled, edited and published on 15th December 1820 which was having 217 drugs in about 272 pages. On July 5, 1975, unification of USP and NF was announced. Convention, the N.F. has been published with U.S.P. in a single volume since 1980. Though U.S.P and N.F. were combined with in a single volume, they continued as two distinct official compendia. To set up the standards for all the drugs, the scope of both U.S.P and N.F. was changed drastically. The U.S.P was limited to drug substances and dosage forms and N.F. was limited to pharmaceutical ingredients. When a compound is both a drug and a pharmaceutical ingredient, it was included in the U.S.P with a cross reference from the N.F. to that U.S.P. monograph. In the single U.S.P-N.F. volume, a large amount of duplication of text was eliminated.

The edition of 1995 is U.S.P.23-N.F.18. This indicates that this is the 23rd edition of U.S.P and 18th edition of N.F. This new volume contains a total of 3410 monographs and 147 general chapters. There are 336 new monographs-320 in U.S.P and 16 in N.F., and 15 general chapters. The publication of U.S.P-N.F. is now undertaken by the United States Pharmacopoeial Convention, Inc. Today the U.S.P-N.F. is recognized and used as a source of official drug standards by several countries throughout the world. The U.S.P.24-N.F.19 has been published in 1999 and gives drug standards that are official from January 2000.

The United States Pharmacopeial Convention (usually also called the USP) is the nonprofit organization that owns the trademark and copyright to the USP-NF and publishes it every year. Prescription and over-the-counter medicines and other health care products sold in the United States are required to follow the standards in the USP-NF. USP also sets standards for food ingredients and dietary supplements.

USP establishes written (documentary) and physical (reference) standards for medicines, food ingredients, dietary supplement products and ingredients. These standards are used by regulatory agencies and manufacturers to help to ensure that these products are of the appropriate identity, as well as strength, quality, purity, and consistency.

Prescription and over- the-counter medicines available in the United States must, by federal law, meet USP-NF public standards, where such standards exist. Many other countries use the USP-NF instead of issuing their own pharmacopeia, or to supplement their government pharmacopeia.

USP standards for food ingredients can be found in its Food Chemicals Codex (FCC). The FCC is a compendium of standards used internationally for the quality and purity of food ingredients like preservatives, flavorings, colorings and nutrients. While the FCC is recognized in law in countries like Australia, Canada and New Zealand, it currently does not have broad legal recognition in the United States. USP obtained the FCC from the Institute of Medicine in 2006. The IOM had published the first five editions of the FCC.

USP also conducts verification programs for dietary supplement products and ingredients. These are testing and audit programs. Products that meet the requirements of the program can display the USP Verified Dietary Supplement Mark on their labels. This is different from seeing the letters USP alone on a dietary supplement label, which means that the manufacturer is claiming to adhere to USP standards. USP does not test such products as it does with USP Verified products.

1.4.6 The British Pharmacopoeia

The British Pharmacopoeia (BP) is the official collection of standards for UK medicinal products and pharmaceutical substances. Produced by the British Pharmacopoeia Commission Secretariat of the Medicines and Healthcare products Regulatory Agency, the BP makes a valuable contribution to public health by setting publicly available standards for the quality of medicines.

The current edition of the British Pharmacopoeia comprises six volumes which contain nearly 3,000 monographs for drug substances, excipients and formulated preparation, together with supporting General Notices, Appendices (test methods, reagents etc) and Reference Spectra used in the practice of medicine, all comprehensively indexed and cross-referenced for easy reference. Items used exclusively in veterinary medicine in the UK are included in the BP (Veterinary). Volumes I and II

•   Medicinal Substances

Volume III

•   Formulated Preparations

•   Blood related Preparations

•   Immunological Products

•   Radiopharmaceutical Preparations

•   Surgical Materials

•   Homeopathic Preparations

Volume IV

•   Appendices

•   Infrared Reference Spectra

•   Index

Volume V

•   British Pharmacopoeia (Veterinary)

Volume VI

(CD-ROM version)

•   British Pharmacopoeia

•   British Pharmacopoeia (Veterinary)

•   British Approved Names

The BP is available as a printed volume and electronically in both on-line and CD-ROM versions, the electronic products use sophisticated search techniques to locate information quickly. For example, pharmacists referring to a monograph can immediately link to other related substances and appendices referenced in the content by using 130,000+ hypertext links within the text.

CHAPTER 2 : Atomic and Molecular Structures / Complexes

2.1 Introduction

The gradual development of modern atomic theory is one of the most fascinating stories in the history of scientific discovery. The idea of atom was originally developed by Leukippos with his atomic hypothesis around 500 B.C. and it was extended by Demokritos.

The hypothesis is "The matter is made up of small, unalterable particles called atoms."

After 25 centuries later, John Dalton in 1803 postulated that:

(a)   Matter is made up of extremely small particles called atoms,

(b)   By chemical reaction atoms are indivisible and can neither be created nor destroyed,

(c)   In an element all the atoms have same weight, size, shape, structure (different element atoms have different properties),

(d)   Chemical combination between two or more atoms in stoichiometric ratios gives compounds.

The atoms are chemically indivisible particles of an element, can not exist freely and applies to elements only.

Berzelious stated that equal volume of all gases under the same conditions of temperature and pressure, contain equal number of atoms.

2.2 Subatomic Particles

Atom possesses a complex structure consisting of fundamental particles (subatomic particles) like.

(a)   Electron: This was the first subatomic particle recognized as a constituent of all atoms. J.J. Thomson is 1880 discovered in his experiment. From his experiment, he explains that the electrons are negatively (0.0005486 on physical scale) charged and the electron mass is 9.106 × 10²⁸ g or 1836 times less than the proton mass. The symbol is e negatively charged and the electron mass is 9.106 × 10 -²⁸ g (0.0005486 on physical scale) or 1836 times less than p-ray and charge is -1.

(b)   Proton: The name proton (Greek meaning first) suggested by Ernest Ruther ford in 1920. It is having positive charge and its mass is 1.6725 × 10²⁴ g (1.008142 on physical scale). Symbol is H¹ or P¹ and charge is +1.

(c)   Neutron: Rutherford postulated that a proton might combine with an electron inside the nucleus to form a particle which would carry no charge but have some mass as that of proton and named it as neutrono.

For e.g. : Neutron was emitted in the reactions

The symbol of neutron is on¹ and charge is zero. The mass is 1.008982 on physical scale.

(d)   Positron: Positive electron was predicted by PA.M Disac and from the study of cosmic rays CO. Anderson discovered positron. The symbol is e+ and charge is +1 and mass is 0.0005486 (on physical scale).

(e)   Neutrono: It is a theoretical particle postulated by W.Pauli in 1931 to preserve the conservation of energy and angular momentum is beta decay.

The symbol is v, charge is zero and mass is nearly zero (< 0.00002 on physical scale).

(f)   Measons: These are the particles required for the exchange of protons and neutrons into one another.

The symbol is n, charge is +1, and -1 and mass is 0.151 on physical scale.

2.3 Models of Atoms

(a)   Thomson’s Model (1904): The atom is a sphere of positive electricity in whichelectrons are embedded like raisins in bread pudding. The repulsion betweenelectrons was balanced by attraction towards the centre of sphere.

Thompson explained the observed spectra of elements by assuming that electrons in an atom are not at rest but are vibrating about equilibrium position. Thus a vibrating electron would emit radiation. But this model could not explain the spectral lines obtained even in the simplest cases and only one spectral line is possible for H2 in U.V. region.

(b)   Rutherford Model (1912): The atom consists of central nucleus of smalldimension (diameter 10–8 cm) surrounded by electrons which are not at rest butare revolving round the nucleus in a closed path like the planets revolving roundthe Sun.

Atomic nucleus consists of protons (+ve charge) and most of the mass (neutrons). The model is shown in Fig. 2.1.

Fig. 2.1 Rutherford model of atom.

Drawback of this model is - when electron revolves around the nucleus, it will radiate out energy resulting in the loss of energy. This loss of energy makes the electrons to move slowly and consequently it will be moving in a spiral path and fall inside the nucleus and ultimately the atom collapse.

(c)   Bohr’s Model (1913): Bohr applied the Planck’s Theory i.e., the energy must be emitted or absorbed only in discrete amounts.

The Postulates of the Model are

(i)   In the atom an electron can move, in certain specific (Fig. 2.2) orbits, without radiating any energy, around the nucleus

This orbital motion/rotation without emitting energy follows the Newtonian’s law i.e., the force of attraction is equal to centrifugal force of attraction.

Fig. 2.2 Bohr atomic model.

(ii)   The total angular momentum of the revolving electron is quantized which is an integral multiple of h/2 n, where h is Planck’s constant. Angular momentum is given by

Where n = principal quantum number which is an integer 1, 2, 3 …..etc.,

This angular momentum limits the number of permissible orbits.

(iii)   The energy is only radiated out when an electrons jumps from one stationary orbit to another. The frequency, v of this radiation is given by the difference in energy between the initial and final orbits.

Where

E1 = energy of initial orbit

E2 = energy of final orbit

h = Planck’s constant

v = frequency

The energy of the revolving electron is negative because the electron is bound to the nucleus by attractive forces to that energy must be supplied to electron in order to separate it completely from the nucleus. The inner most orbital electron (n = 1) has the most negative value and decreases for n = 2, n = 3 … so on.

Where m = mass of electron

e = charge of the electron z = atomic number of atom n = quantum number

if n = 1, and z = 1 for H atom

E1 = Z.18 × 10–11 ergs

So

Since

is constant which is known as Reidberg constant R,

then eq. 2.12 can be written as

where R = 109737.707 cm–1

Draw backs

•   It cannot explain the spectra of other atoms except H atom.

•    Each spectral line of hydrogen atom under high resolution consists of many closed lines.

•   It failed to explain Zeeman effect (magnetic field) and Stark effect (electric field) i.e., the splitting of spectral lines.

•   It failed to explain the distribution and arrangement of electrons in atoms.

•    It used two theories namely the Planck’s quantum theory and the laws of chemical mechanics which are opposed to each other.

Hydrogen atom emission spectrum consists five series namely - Lyman series (n2 = 1), Balmer series (n2 = 2), Paschen series (n2 = 3), Brackette series (n2 = 4) and Pfund series (n2 = 5).

Later Sommerfied (1915) introduced the concept that the electrons are revolving around the nucleus in elliptical orbits to explain the multiplicity of spectral lines. These models gave four quantum numbers.

(d)   Vector Atom Model (1925): This model of atom is extension of Bohr-Sommerfield model. Two concepts of this model are:

(i)   Spinning Electron Hypothesis: Uhlenbeck and Goudsmith (1925) stated that the electron not only rotates about the nucleus but also about its own axis somewhat like the motion of planet is solar system i.e., earth moves around the sun and also about its own axis.

This concept give two angular momenta i.e., orbital angular momentum and spin angular momentum. Since the changed particle (electron) on rotation also gives orbital magnetic momentum and spin magnetic momentum.

The interaction between two angular momenta account for multiplicity of spectral lines and the interaction between two magnetic moments account for the fine structure.

(ii)   Space Quantiration: In general the motion of electron in an atom is three dimensional so there are three degrees of freedom. The additional quantum number or third quantum number condition quantizes the orientation of elliptical orbit in three dimensional space and does not alter the size and shape of the orbits.

This atom model gives seven quantum numbers altogether

(e)   Quantum Mechanical Atom Model:

Failure of Quantum theory is on the basis of

–   Wave-particle dualistic nature of radiation.

–   One quantum number does not cater the needs

–   Introduction of new quantum number wherever it is necessary to explain the observation of spectrum.

The new Mathematical concept was introduced by taking into consideration the DeBroghe’s Hypothesis y= h/p and Heisenberg’s uncertainty principle in Quantum Mechanics to cover the draw backs arised in quantum theory.

The Quantum Mechanical Model of Atom can be explained by the following points.

(i)    Electron moment represented by wave function is called as an orbital or the region of finding the electron is termed as an orbital.

(ii)   Electron spends maximum time in its own orbit

(iii)   Electron moment is in a haphazard (irregular) manner as shown in Fig. 2.3 i.e., like the insect moves around the electric bulb.

Fig. 2.3 Electron moment in a haphazard manner.

(iv)   Electron is having penetration effect i.e., it spends sometime in the other orbits i.e., right from the nucleus, whereas in quantum theory it revolves only one circular orbit.

(v)   In between orbits there are nodal surfaces i.e., zero electron density.

(vi)   If electron moment is photographed, it looks like a cloud (Fig. 2.4).

Fig. 2.4 Photograph of electron moment.

(vii)   The Probability of finding the electron in atom is always real. Exact position of electron is not known so we can mention probability of the electron is an atom.

This Model is completely different from Bohr Model, where the electron is restricted to revolve around the nucleus in a fixed circular orbit. The Quantum Mechanical model is in accordance with Heisenberg’s uncertainty principle (it is impossible to determine position and momentum of any particle/electron precisely and simultaneously).

Orbit and Orbital

The orbit is the circle around the nucleus with particular principal quantum number in which the electron revolves around the nucleus. The energies are different for different n values.

The orbital describes the electron moment represented by the wave function y or the region in space around the nucleus where there is high probability of finding the electron.

2.4 Quantum Numbers

The term quantum number is used to identify the various energy levels that are available to an electron. To know the position of the electron in an atom, four quantum numbers are required as per quantum theory.

(i)   Principal Quantum Number, n: This is an integer from 1, 2, 3 …., n is never zero. It describes the size of the orbital depending on n value, the different shells K, L, M, N for n = 1, 2, 3, 4 respectively. The no of electrons present in each n is given by the formula 2n². For e.g. n = 3 then 2 × (3)² = 18.

(ii)   Azimuthal Quantum Number, l: This is an integer right from 0, 1, 2, ….n - 1. It describes the shape of the orbital i.e.,

1 = 0 S orbital

l = 1 P orbital

1= 2 d orbital

1 = 3 f orbital The relation with n is

l = n - 1 values including zero

if n = 3 then/ = 0, 1, 2

The number of values of n is equal to/.

(iii)   Magnetic Quantum Number, m: It describes the orientation of orbitals in presence of magnetic field. s, p, d, f orbitals contains suborbitals 1, 3, 5, 7. The relation between m and / is, m = 2/ + 1 including zero. For e.g. if / = 2, m = 2/ + 1 i.e., 5, then the m values are 2, 1, 0, -1, -2 = 5

(iv)   Spin Quantum Number, s: It

These four numbers describes the position of electron in an atom.

Quantum Numbers Associated with Vector Atom Model

The Quantum Numbers are:

(i)   Principal quantum number, n

(ii)   Orbital angular momentum quantum number, l

(iii)   Spin angular momentum quantum number, s

(iv)   Total angular momentum quantum number, j - vectorial sum of orbital angular momentum and spin angular momentum.

(v)   Orbital magnetic momentum quantum number, ml.

(vi)   Spin magnetic momentum quantum number, ms.

(vii)   Total magnetic momentum quantum number mj - vectorial sum of ml and ms.

Quantum Numbers Associated with Quantum Mechanical Model

(i)   Principal Quantum Number: It is represented by n. It can have any integral value except zero. This arises from the solution for the radial part of wave function y and to the first approximation determines the energy of the orbital. It is quantitatively related to the distance from the nucleus to the most probable position of finding the electron. It describes the size of the orbital. This quantum number corresponds to K, L, M etc shells in the Bohr Model. n = 1, 2, 3, ……

(ii)   Orbital Quantum Number: Represented by l, all possible l values corresponding to n are given by

l = n –1, …. 0

Where ….. line = all integers necessary to complete the series

This quantum number arises from the solution of angular part y and refer, respectively to the magnitude and orientation of the angular momentum of an electron in a particular orbital.

The quantum numbers l describes the shape of the orbital

s for l = 0

p for l = 1

d for l = 2

f for l = 3

(iii)    Magnetic Quantum Number: Represented by ml for orbital. The possible ml values corresponding to a given l are

The angular momentum is a vector quantity. When an external magnetic field is applied to system, the quantum number ml can be employed to indicate the direction and magnitude for the component of projection of angular momentum vector relative to applied field. This quantum number also arises from the solution of the angular part of y. The principal component of this vector can only occupy certain quantized positions relative to the field.

For e.g., l = 2, the possible ml values are equal to 2l + 1(2 × 2+1) = 5 and the values are +2, +1, 0, -1, -2.

Where +2 has lowest energy

The orientation of angular momentum vector for five d orbitals relative to the external field H, are shown in Fig. 2.5.

Where +2 has lowest energy

Fig. 2.5 Orientation of d Orbitals.

These three quantum numbers are solutions o 2 Schrodinger equation.

(iv)   Spin Quantum Number: Spin magnetic moment quantum number is represented by ms. Each orbital can accommodate two electrons and these are distinguished by ms of either + 1/2 or -1/2. This quantum number is required to label uniquely all the electrons in an atom. This quantum number is associated with electron spin angular momentum. The spin angular momentum vector can be aligned parallel or anti parallel to the external field of direction and the corresponding values of the spin are

The quantum numbers and the orbitals are given in Table 2.1.

Table 2.1 The Quantum numbers and orbitals.