UNIT 2 CHEMICAL BONDING Introduction: A chemical bond represents a strong force of attraction between two atoms. According to the Lewis's octet rule, atoms of all elements have atendency to acquire an electronic configuration similar to that of inert gases because it represents the most stable electronic configuration. All atoms having an unstable or incomplete outer shell have a propensity to gain or lose electrons s0 as to acquire an electronic configuration of the nearest inert gas in the periodic table. itis this tendency of atoms to complete and hence stabilize their outermost orbit of electrons which is mainly responsible for chemical combination between the atoms. The requirement of electron pairing are mainly accomplished by the following modes: 1. By complete transfer of one or more electrons from one atom to another this results in the formation of ions end hence is called ionic bonding. 2. Bysharingof electrons between the two combining atoms, whi of acovalent bond. 3. A special type of covalent linkage in which both the shered electrons are contributed by one atom only and not ore byeach atom as in the case of proper covalent linkage. results in the formation lonic or electrovalent bond: This type of bond is formed by the transference of electrons from one atom to another. Essentially an atom that losses one or more of itselectron, and aone that can accept them is, required. The metals in group | and group Il in the periodic teble has the greatest tendency to lose electrons and turn into positive ions. The non-metals of group VI and VII the greatest affinity for electrons and readily change into negative ions. The atom which losses electrons acquires positive charge and contracts while the atoms which gains electrons acquires negative charge and increases in size. The cation and anion thus produced are held together by electrostatic lines of force and hence the linkage is called electrovalent bond and the compound so produced is called electrovalent compounds. These are also celled polar ‘compounds since their molecule acquires polarity due to the formation of ions by electron transfer.KCl otaisium (loses transfersan lecvonto Chlorine (ct) (KJICH Peat acres pete cage) ‘tne sau egrtne SeCharacteristics of ionic compounds: 1. They consist of oppositely charged ions held together by electrostatic forces of attraction. 2. They are generally soluble in water and insoluble in organic solvents. 3. Due to the powerful electrostatic force between the ions in the crystals, considerable amount of energy is required to separate the molecules from each other, Hence they have high melting and boiling points. 4. When dissolved in water or in the molten state, they conduct slectricity because then the binding forces in the crystal laitice are weakened. 5. They are crystalline compound. Covalent bond: This type of bond is formed by sharing of one or more electron pairs between the atoms and thus achieve the stability by attaining their octet or duplet in their outermost shell. ‘The electrons for pair formation are contributed equally by the two participating atoms and becometheir common property. The covalent linkage can connect similar atoms when both of them ae short of a few electrons to achieve their nearest inert gas configuration. Since there is no transference of electrons and ionsare not formed, the covalent linkage is also called non-ionised linkage. paired electrons in valence energy level Oe unpaired electrons overlap of electron orbitals and sharing of electron pair Polar and non-polar character: Depending upon whether the electron pairs are shared equally or unequaly between the bonding atoms covalent bond may be non-polar or polar. In homodiatomic moleculeslike Hand Cla, the sharing of electron pair is equal between the two atoms and such a bond is called as a non-polar covelent bond. But in hetero atomic molecules like HF or HCl the sharing of electron pair is unequel because, one of the two atoms is lixely to attract the electrons more strongly than the other. The atom that attracts the electrons more strongly develops some negative charge: and the other atom develops some positivecharge. These fractional charges are designated as 5* and 6 In HCI, Cl atom is more electron attracting then H atom and hence HCI can be depicted as 1 —— C1®. Such covalent bonds are said to be polar and the bond is said to have partial ionic character. Characteristics of covalent compounds: 1. The atoms in a covalent molecule are firmly held together by the shared pair of electrons and hence covalent compounds do nat dissociate or conduct electricity when put in water or melted. 2. Covalent compoundsare generally insoluble in water and soluble in organic solvents. 3. Acovalent molecule isnon polar and hence do nat have external field of force. Dueto this they have low melting and boiling points. 4. Normal covalent compounds are liquids or gases at room temperature. However, covalent compounds with high molecular weights exist as solids. 5. Covalent compoundsin solution react slovily as compared to fonic compounds. Co-ordinate or dative bond This Is @ special type of covalent bond. The atom which donates the electron pair is called asdonor and the other atom which doesnot contribute an electron towards the shared electron pair and also which generally tries to pull the pair towards itself, is called acceptor. The pair of the valency electrons possessed by the donor is called the lone pair. The bord formed as above is called the co-ordinate or co-ordinate covalent or dative bond. Further, since such a bond always renders the molecule polar, itis also called semi polar bond. Compounds contain ing one or more of such co-ordinate bonds in their moleculesare termed co-ordination compounds. A co-ordinate bond is usually represented by an arrow pointing from the donor to the acceptor atom. Example: Characteristics of co-ordinate compounds: 1. The co-ordinate bond is rigid and directional and hence provides opportunity for exhibiting stereoisomerism of molecules. 2. These compounds are generally insoluble in water and soluble in organic solvents. 3. These compounds have reletively higher melting and boiling points than those of ‘covalent compounds and lower than those of electrovelent compounds. 4, The co-ordinate linkage being partly covalent in nature, the atoms are firmly held by electrons and hence these compounds do not dissociate when laced in water or melted. 5. The co-ordinate compounds are stable like covalent compounds. Vander Wealsinteractions: Vander Waals force is a general term used to define attraction of intermolecular forces: between the molecules. These forces are distance dependent between the atoms or molecules. It is important to remember that van der Waals’ forces are forces that existbetween molecules of the same substance. They are quite different from the forces that make up the molecule. Forexample, a water molecule ismade up of hydrogen ‘and oxygen, which are bonded together by covalent bond. The van der Waals’ forces, arethe forces that exist between the millions of separate water molecules, and not between the hydrogen and oxygen atomsin the case of water. There are three types of Vander Waals forces 1. Weak- London dispersion forces 2. Strong: Dipole-dipole forces London dispersion forces: London Dispersion forces are type of van der Waals" forces. They exist between nonpolar molecules. For example, chlorine ges is made up of two chlorine atoms. Inthis bond, the electrons are equally shared and are not dominant on one side of the molecule as is the casein HCl, The atom looks like this Cl - Cl, no overalll charge on either side but, within a bond, electrons are constantly MOVING. They zoom around the atoms really quickly. Asa result, there may be ¢ tiny instant in tine where the electrons happen to be dominant on one side, creatinga situation like, Cl" -Ct However, this temporary charge disapoears as quickly as it appeared because the electrons are moving fast. These temporary dipoles allow the temporarily negative side ofone molecule to attract the temporarily positive side of another molecule, which isthe intermolecular force. Strong: Dipole-dipole forces: Dipole Dipole forces cccur in polar molecules, thatiis, moleculesthat have an unequal sharing of electrons, For example, HCl comprising of Hydrogen and Chlorine is polar molecule. The Chlorine atom hasan extra electron, donated by the hydrogen atom. Because of this, the chlorine part of the molecule is negatively charged, and the hydrogen side of the molecule is positively charged. H* - Cl Hence in an aqueous HC, there are thousands of these moleaules around that are slightly charged on each side, the molecules naturally orient themselves as shown inthe figure Hct He Ht ect The positive part of one molecule will move until it is next to the negative part of a neighbouring molecule. These forces between molecules tend to make them ‘stick together.Hydrogen bonding forces: Ahydrogen bond is dipole dipole interaction that occurs between any molecule with a bond between a hydrogen atom and any of oxygen /fiuorine/nitrogen. So, Hydrogen Fluoride (HF), ‘Water (H20), ammonia (NHs) and any other molecule that has a hydrogen bonded to either anonygen, fluorine or nitrogen atom, exhibits hydrogen bonding. Ae a peers The hydrogen bond is just the dipole dipole force but itis extremely strong compared to either dipole dipole forces like HCl. It is extremely strong because F, N and O are highly electronegative and H is highly electropositive. So basically, the bond is EXTREMELY a one- sided affair, resuting in an extreme dipole situation, thus named, a hydrogen bond. The ‘extremely positive side of the molecule will orient itself with the extremely negative side of another molecule. Types of Hydrogen bonding There are two types of H-bonds, an is classified asthe following: 1. Intermolecular hydrogen bonding ~ This type of bond formation occurs between the different molecules of same or different compounds. For example- p-nitro phenol. 2. Intramolecular hydrogen bonding — This type of bond formation occurs when the hydrogen atom lies in between the two electronegative elementspresent in the same. molecule. For example- o-nitro phenolontvonhenol Hydrogen bonding in o-nitroohenol means that there is less intermolecular hydrogen bonding than in g-nitrophenol, as a consequence, the bolling pointofo-nitrophenol 's less than that of p-nitrophenol. Introduction to co-ordination chemistry A simple ion is single species and exist as a free ion. If an ion is composed of two or more species, the resultant ion is called complexion and thecorrespondingcompound is called complex compound. A complex isa species comprising of several parts, each of which has an independent existence in solution. It usually consists of a positive metal ion and a number of electron rich ligands which can be anions or neutral molecules, for example Ke [Fe(CN)s] where, K is central metal cation, [Fe(CN):]* is anionic complex ion denoted by square bracket and K: [Fe(CN)«] is a complex compound. Number of ligands attached to the central metal Icn Is called as co- ordination number. The species that binds directly to the central metal ion is called a co-ordinating group or ligand. The central metal cation Is a lewis acid and the ligand Isa lewis base. They may be bound at only one position to the central ion or they may be linked at two, three, or even upto six positions. Ligandsthat can bind at more than one position ie. polydentate are also called as chelates. The ligands may be anions such as, F, Ct, CN" , OH, I’ and neutral molecules with lone pair of electrons such as, H20:, :NHs. Some typical examples of complex compositions are given below: Lewis acids Lewis bases Complexes co + 6NHs = ————® _Co[NHs).** neutral ligand Fe > GCN ee Fe CH et ‘anionicligand Pet + 2NHs+4Ct ————p Pt(NHs)2l? ied ligand: The complex may have a positive, negative or zero charge. The charge is always the sum of the charges on the individual components. The structures of some of the complexes are shown below:a / " A Ho * Joe a aati tae \ Uy “UAT oe! be a Wi Fereyanigelon Seaton To explain the complex ion Alfred Werner introduced the concept of secondary valency. Transition d-block elements form ionic or covalent bonds to fulfil their octet, thisis primary valency of metals. In addition to that d-block elements have incomolete inner d-orbital. Both these factors are responsible to attract surrounding anions or neutral molecules having lone pair of electrons to form co-ordinate bonds, this is secondary valency. The important postulates of Werner's theory are: 1. The central metal or the metal atoms in coordination compounds show two types of valency. They are the primary and the secondary valency. 2. The primary valencyrelatesto the oxidation state and the secondary valencyrelates to the coordinate number. 3. The number of secondary valences is fixed for every metal atom. Itmeans that the coordination number isfixed. 4. The metal atom works towards satisfying both its primary and secondary valencies. A negative ion satisfies the primary valency. On the other hand, a negative ion or neutral molecules atisly secondary valencies. 5. The secondary valencies point towards a fixed position in space. This is the reason behind the definite geometry of the coordinate compound.itations of Werner's Theory: 1. it could not explain the inability of all elements to form coordinaticn compounds. 2. The Wemer’s theory could not explain the directional properties of bondsin various coordination compounds. 3. It doesnot explain the colour, the magnetic and optical properties shown by coordination compounds. Sidgwick proposed the following postulates to explain the limitation of Werner’s theory: 1. Co-ordinating groups also called as ligands, donate their pair of elecironsto central metal cation to form inner co-ordination sphere. So each and every ligand must have atleast one pair of electron. 2. Co-ordination number will be such that central metal cation achieves the electronic configuration of next inert gas. In a complex ion total number of electrons possessed by central metal cation is called effective atomic number (EAN) of that metal. This is known as EAN rule of Sidgwi Complex “Aionic | Oxidation | Toul No. | No. of donated | EAN valve No. sate of | of electrons | electrons to | metal in the ‘metal | possessed by | meral carton | complex metal cation (Co(NH)" a 8 a 6x2=12 | 244 12=36 teeny % 2 24 6x2=12 | 244 12-36 NiCO), 2 ° 2B 4x2=8 B+8=%6 INF AY 2 22 26 6x2=12 | 26+ 12-38Classification of Ligands: On the basis of co-ordinate bonds ligands can be divided in to different categories: 1. Monodentate ligands: Any ligand donating one ps ligands, examples, :NHs, Hz:0:, C:N" 2. Bidentate ligands Any ligand donzting two pairs of electron iscalledbidentateligands, examples, of electron is called monodentate Ethylened Oxalate ion 3. Tridentate ligands: Any ligand donating three pairs of electron is called tridentate ligands, examples Ethylene diamine H HaNg a “INH 4. Polydentate ligands: Any ligand donating more than three pairs of electron is called bidentate ligands, examples Ethylene diamine tetra acetic acid (EDTA) ation of EDTAhad water analysis: Hardness of wat isthat characteristic which prevents the lathering of soap. The hardnessis imparted due to the presence of certain salts of multivalent cations like Ca”, Mg**, Fe", Mn?" and Al? (heavy metals) dissolved in water especially bivalent cations like Ca, Mg2* present ‘abundantly in nature. Temporary hardness (Carbonate/Alkaline Hardnes:) is caused by the ‘soluble bicarbonates of Ca and Mg. Temporary hardness is removed by mere boiling and filtering off the precipitates formed. Permanent hardness (Non-carbonate/Nor-alkaline Hardness) is due to the more soluble chlorides, sulfates, nitrates of Ca, Mg, Fe, and other heavy metals.of EDTA) metho Disodium salt of EDTA forms a soluble (1:1) complex with the hardness causing metal ions. EDTA is used as titrant and the hard water is titrated against the EDTA using an indicator dye (Eriochrome Black-T) to mark the endpoint of titration, ie. the complete complex formation between metal ions and EDTA. An initial unstable complex between the Ca® & Mg ions and EBT indicator gives a wine red coloration, but at the end point of the titration, a more stable [ca-EDTAJ/ [Mg-EDTA] complexes are formed which release the free EBT and the color changes from wine red (or purple) to 3 persistant blue or bluish green color of free i REACTIONS: EBT + Mg’/Ca”*(aqc) ——__—y»-_ [Ca-EBT] / [Mg-EBT] (wine red ot purple -complexed Indicator) [Ca-EBT] /[Mg-EBT] + EDTA ————f—[Ca-EDTA]/[Mg-EDTA] + EBT (blue or bluishgreen free indicator) Since hardness of water is expressed in terms of calcium carbonate equivalent, after performing titration hardness is calculated by below mentioned relation end its un! per million (ppm): 1000 mL 1N EDTA = 1 equivalent of CaCOs| 250mL of sample hard water consumed 40mL of 0.01 M EDTA, what is the CaCOs equivalent hardness of the sample water? (ans: 160 ppm 13200 ml sample water consumed 50 ml of 0.02 N EDTA. What is the hardness of the water sample? (Ans: 250 ppm] 14.100 mLof standard hard water (1.4 g CaCOy/L) requires 40 mL of EDTA solution. 120 mL. of water sample consumes 20 mL EDTA. 209 mL of boiled and ‘filtered water sample consumes 15 mL of EDTA. Calculate the hardness of sample. (Ans: Total hardness = 583.33 ppm, Temoorary = 26250ppm, Permanent hardness = 320.83 ppm] 15Calculate the hardness of a water sample. whose 100 ml required 25 mL EDTA. 20 ml of CaClz whose strengthis equivalent to 1.02 g of CaCOs per litre, required 32 mLof EDTA solution. (Ans: 159.38 ppm 16.100 ml sample hard water required 12 ml of N/10 (0.1 N) disodium EDTA for titration. After boiling ard filtration, 200 mLof the same sample required 63 mL of 0.1 EDTA. Calculate the temporaryhardness. [Ans: Total hardness = 600 pom, Permanent hardness = 220 ppm, Temporary hardness = 380 ppm] 1740 mL of sample water consumed 12 mL 0.03 M EDTA before boilingand 10 mLofsame EDTAafter boiling, Calculate the total, perrranent and temporary hardiess. [Ans: Total hardness = 900 ppm, Permanent hardness = 750 ppm. ‘Temporary hardness = 150 ppm]