RGANIC CH on KALYAN! INO! IEMISTRY (Sey g s almost like a naked proton. There The hydrogen atom has such a large positive charge that iti: being inner level electrons, it will be strongly attracted to the negative end of an adjacent ee ule, Electrostatic force of attraction between H* of one molecule ae C ei ; Present within y, same molecule or another molecule of the same or different substances is known as Hydrogen bond, This bond is represented by a dotted line while covalent bond is shown by a thick line bet, two atoms as shown below. » . ie aa Ho oF’ ...,.H- Fo ....H WF Covalentbond Hydrogen bond Causes and conditions for the formation of H-bond £ atom bonded to H-atom. Whenever a H-atom is bonded to a small sized highly electronegative atom, N, O ot F, the latter atom withdraws maximum electron density of H-atom towards itself. As a result, the H-nucleus becomes almost bare (naked). It attains partial positive charge, H?*. N, O or F atoms become electron rich and attain partial negative charge, N*, O~ or F*. The positively charged H® and negatively charged N~, O~ or F* are held together by electrostatic force of attraction called hydrogen bond. (ii) Small size of the atom bonded to H-atom. Atoms bigger in size than, N, O or F are unable to form H-bond. The reason is as follows. ‘Atoms bigger in size than N, O or F are unable to attract covalent electrons effectively. Itis due to the screening effect of electrons between valence electrons and nucleus. Thus, the covalent bond between hydrogen and other atom is less polar. The electrostatic force of attraction becomes very weak in them. Hence, H-bond is not formed, e.g., H-bonding in HCI or HBr is not possible due to big size of Cl and Br-atoms. Thus, the factors favouring the H-bond are : (i) High electronegativity, and (ii) Small size of atom bonded to H-atom Co en RAS Fav only nit “oxygen and fluorine for ger they have! . Only nitrogen, oxygen and fluorine form strong hydrogen bonds because they have |.” high value of electronegativity and small atomic sve, 2 se |2. ©, N and F atoms involved in hydrogen bonding possess at least one lone pair of | L__Slectrons that can interact with the hydrogen atom in hydrogen bonding. e (i) High electronegativity o Theories of hydrogen bond Hydrogen atom (,H) has only one electron in its v. 1), So, i a alence shell (1s), So, it can form gee covalent bond. Hydrogen atom cannot be bivalent in Saat ike ‘A -H..B (where and B are N, O or F) because its 2s and 2p orbitals being of much high energies, can not take Pa" in bonding. So, it " ‘i 5 a ee pose to explain bonding in compounds like A — H...B, following theo" 1. Electrostatic approach. i ing, can be understood with the help of one of electrostatic theory of hydrogen bondi electronegative atom than H-atom. The sh: bond shifts more to-wards X-atom artial and i i ‘ gets same amount of patal positive aoa Fey ae OP} A oa en two or more HX molecules cor : ce mi vo OF m me close to-gether, H®* speci HX mol attracted by X* specie of another HX molecule and forges eee called hydroe™ bond or hydrogen bridge... H*— Xt | Hoe ya be becHEMICAL BONDING-II Facts is support of electrostatic approach are given below. () This bond is formed between H- (N, O or F) only. (ii) The bonded atoms tend to become linear because of the Weaknesses of the electrostatic approach are given below : ( This theory does not explain the shortening of bond distance X* ... H°* HY — X® ... H bond. . _ on (i) This theory does not explain the symmetry of O% ~ H°* ... O% bond in f-oxalic acid and that of F* ~ H®* ... F> bonds in HE3. (ii) This theory does not explain the repulsion between H and X at short distances as found in hydrogen bonded compounds. For example, the bond distance (H - F) in HF; has been found to be only 20 pm (= 0.20A) more than that found in H - F molecule. 2, Valence bond theory (Resonance Theory). According to this theory, hydrogen bonding in HX molecules involves the following resonance structures and is not electrostatic. ‘atom and most electronegative and small sized atoms electrostatic repulsion. * . XO-H...Y¥) XY X-H+ Structure III does not make much contribution to the overall energy of the hydrogen bond because it indicates hydrogen as bivalent and a lengthy H < Y bond. Structure I arises due to dipole interactions while structure II arises due to induced dipole interactions. Structures I and I make major contributions to the overall energy. So, hydrogen bond may be considered as electrostatic in nature. There are a few cases (e.g. HF5) in which structure I, It and III may have equal contributions to the overall energy. F*:H-F+—>F-H:F -—>F-:H":F i) a (ay Resonance theory explains all the weaknesses (i) to (iii) of electrostatic approach. It, however, does not give the correct value of resonance energy. For example, the experimental value of bond energy of hydrogen bond in H - F molecule is 6.0 kcal mol” while calculated one is 7.85 kcal mol-. Also the stability of hydrogen bonding obtained is far off the mark (33 kJ mol”) for ice vs its observed value of 25 kJ mol”. 3. Molecular orbital treatment. Hydrogen bonding in HF3 has been explained (by Pimentel) using molecular orbital theory. He took linear combination of 1s-atomic orbital of H-atom and two 2p, atomic orbitals of two fluorine atoms directed along the bond to form = Py and Py represent 2p, atomic orbitals of two F-atoms (A and B, say), then the symmetrical ~H.F bond is described by Se 1 (bonding) = PatPgt ays ; 2 MOLECULAR ORBITAL (3) (ton-bonding) = P., + Py; 3 (anti bonding) = P,+ Py — ays _ Where a, and a, are mixing co- sificients, The two electrons are Ffssent in bonding molecular orbital W). These electrons spread out BONDING MOLECULAR aay On either sides of the hydrogen SABA tetas re nega = a result, two equivalent Fig. 5.51. The molecular orbital diagram Boe onds Skctrons are pacts ane ee non-bonding molecular orbital (Fig. 5.51). cay, Calculation of hydrogen bond energy. The hydrogen bond energy (E) in A~ H..B can be - ae with the help of Allen equation E = kiya Vr . te = distance H...B ; I= Ionisation energy of donor atom B ; QD swo252 ops tom |----> [Q@_ tor atom ENERGY STABILITY14-4 = dipole moment of Strength of H-bonding. It is chemical bond. Its strength depends * walently bonded. Since electronegativity oF 7 5 TP. F (20 keals/mole) > 07 ~ H™ -~ ! keal per mole). H-bonds are comparatively weaker 0-100 keals/mole). i ee ‘Types of H-bond. Hydrogen bond is of two "YP'S * i (i) Intermolecular H-bonding or Association, (ii) Intra-molecular H-bonding. i i ing is formed between H-atom of o, Inter-molecular H-bonding. This type of bonding 1s r a easy He), and N, OorF nef another molecule of the same (HF) or different substance say H,0), e.8., - and k= 244 x 08 C- e a ae because it is merely an electrostatic force and no sends upon the electronegativity of atom to which H-atom i, tof F > O> N, the strength of H-bond is in the orde, _O7* (7 kcal per mole) > N?- HS NG (2-10 keals/mole) than covalent bond, H-O. H=O8 H-0.. 1 ()H-F.WH-F.H-F~ i" H H H fi (i) ..H-N-H. 9-H...NOH.. (@) H-O... CO H-0.., hi H H R R R (ii) Intra-molecular H-bonding. This type of bonding is formed between H-atom and N, O or F-atom of the same substance. The most important examples of this type are shown in Fig. 5.52 Effect of inter and Intra-molecular H-bonding, The individual molecules involved in inter and intra molecular H-bonding do not lose their identity. The reason is that H-bond is very ‘weak and gets easily ruptured. However, these types of bonding affect the physical properties of substances as shown below: 1. Higher melting and boiling points of hydrides of N, O and F atoms of second period elements. Boiling point of H,O > HF > NH. Water has a higher boiling point than HE, even though HF is more polar than HO. This is because in HF, each molecule can be hydrogen bonded to two others whereas in water, each molecule can be hydrogen bonded to four others. Therefore, even though HF forms somewhat stronger hydrogen bonds than water, the total strength of four hydrogen bonds in a water molecule exceeds the total strength of two hydrogen bonds in an HF molecule. The hydrogen bonding in NH; is much weaker than in H,O or HF because of the considerably lower electronegativity of nitrogen. ——> BOILING POINT (°0) MOLECULAR WEIGHT. — n Fig. 5.52. Abnormal boiling points of Hr In addition, the nitrogen in NH has only one HO end NHS.ciEMICAL BONDING-I pair to which a hydrogen bond can be formed. So each molecule, on the =i; hydrogen bonds. The total strength of th THe by me 1e hydrogen bonding is so small that 2B ehas a lower boiling point than either HF or HO) (fe 5 a ee pene mint at HO is liquid and H,S i PLO. (fig. 552) > (a) H,0 is li ,S is a gas. Also NH, is a liquid but phosphine (PH,) is a gas, These explained with the help of table 5.4 a mh iad but phoepltine (PH) ie gos. Th From the table it is clear that the electronegativity difference between H and O in H,O (1.4 y a 0 (1.4) s geater than that between H and § in H,S (0.4), Thus inter molecular H-bonding is stronger in 1,0 but negligible in H,S. Strong H-bonding in H,O brings H,0 molecules close enough to liquid. It is not possible in HS due to large size and low electronegativity of sulphur atom and hence absence of H-bonding in it. Hence H,O is a liquid and H,$ is a gas. Similarly, we can Slain that NH is a liquid but PH, is a gas, ‘ (@ Although electronegativity difference of H and Cl in HCI is same (0.9) as of N and H in NH, yet liquid but HCL is a gas (Table 5.4). Reason. It is explained on the basis that due to large size and low electronegativity of Clatom, Clatom is unable to form H-bonding in HCl. So HCl behaves as a discrete molecule. NH Table 5.4. Molecule > HS PH. Hel Electronegativity > S=25 P=21 | a=30 H=21 H-21 | H=21 Difference of electro- 04 Zero 09 negativity > 3. Solubility of alcohol in water. The solubility of alcohol (ROH) in water is due to inter- molecular H-bonding between H-atom of H,O and O-atom of alcohol and vice-versa. R-0...H-0...H-O... R H R 4. Wet glass vessels in the laboratory are dried by using acetone (CH;COCH,), ethyl alcohol, etc. The H-atom of H,O sticking to the sides of the glass apparatus forms inter molecular H-bonding with oxygen atom of ethyl alcohol or acetone. When alcohol or acetone is thrown out after washing the apparatus, water also gets removed with them. The vessel thus becomes dry. i HC C= 0 -H-O CH Acetone Water 5. Alcohol is better drying agent than acetone. Each alcohol molecule contains one oxygen and one H atom. Thus, one alcohol molecule forms three inter molecular H-bonding with one Water molecule. On the other hand, each acetone molecule contains only one oxygen atom available for H-bonding and forms two inter-molecular H-bonding with water. Hence, alcohol is a better drying agent than acetone. 6. Cotton clothes dry later than synthetic clothes (e.g, polyester). It is due to the strong eonding between OH-groups of cotton (cellulose) and ‘H and O atoms’ of water. “bonding is negligible in synthetic clothes. “i 58 7. Ice floats on water. We know that Density = Yojume| 300] KALYANI INORGANIC CHEMISTRY (SEMI & 4) Density of ice is less than water. It is possible only if the volume occupied by ice (say 1 gm) is more than that of water (1 gm). It can be explained on the basis of structure of ice. Structure of Ice. Ice has tetrahedral structure (fig. 5.53a). In Ice, one H,O molecule is present jn the centre of tetrahedron. Other four water molecules are bonded to it through inter molecular H-bonding and are directed towards its four corners. Due to this arrangement, ice attains cage like structure with many empty spaces in it. These empty spaces increase the volume of ice (fig 5.53b), When ice is heated, the inter molecular H-bonds break and the cage like structure collapses. Liquid water is thus formed which occupies less volume and hence higher density than ice. Thus, ice floats on water. 8. Water has maximum density yi and minimum volume at 4°C. In ice, 49 each water molecule is tetrahedrally surrounded by water molecules 4 through inter molecular H-bonding. | 178em fos Ice has a cage like structure withempty |, YS -5>4, space in it. Thus, it occupies large | ~ Yo} > volume and hence less density. As ice i J: is heated, the weak H-bonds break and H Dae water molecules come close. They ia acquire less volume and more density. Hh is This process goes on upto 4°C. Beyond 4°C, the kinetic energy of water | Fig. 5.53. strona et uctureLoICeNG) Jevansiel molecules increases and they move |ffangement of water zu apart. This increase in volume is more lle) au =estaleeu(a) Vai: -aseceulililiges a) than decrease in volume due to breaking of H-bonds. Thus, density decreases. (Fig. 5.53(b)). 9. Glycerine and glycol are more viscous than ethyl alcohol. Glycerine (CH,OH.CHOH. CH,OH) and glycol (CH;OH.CH;OH) can form more number of hydrogen bonds as compared to ethyl alcohol (CH,CH,OH). This is because of the presence of three and two -OH groups in glycerine and glycol respectively as compared to one OH group in ethyl alcohol. Thus the intermolecular hydrogen bonding in glycerine and gylcol are stronger than that in alcohol. Hence these are more viscous than ethyl alcohol. Due to the same reason, honey having many -OH groups is more viscous than ethyl alcohol, 10. Glycerol and glycol (CH,OH.CH,OH) have higher boiling points than ethyl alcohol. Glycerol and glycol have three and two -OH groups respectively. Thus, there are greater intermolecular attractive forces due to H-bonds in them as compared to ethyl alcohol (having one = OH group). Hence, higher energy is needed to break H~bonds in glycerol and glycol than in alcohol. Thus glycerol and glycol have higher boiling points than ethyl alcohol. 11. Ortho-nitrophenol is more volatile than para-nitrophenol. In the para form, nitto (- NO.) and phenolic (~ OH) groups are at maximum distance, apart. These molecules show intermolecular H-bonding, Thus, association of molecules takes place, Their molecular weight increases and hence boiling point increases. In ortho-form, nitro and phenolic groups are ver) near to each other. They show intra moelcular H-bonding. Association does not take place: Their molecular weight remains same and hence boiling points do not increase too much. Thus ortho form has lower boiling point and hence more volatile than para form, , 12, Ortho-nitrophenol is less soluble in water than para nitrophenol. In para form, nitro and phenolic groups are at maximum distance apart. When this compound is put in water, a? inter molecular H-bonding takes place between H-atom of H,O and oxygen atom of para form a -_|cHEMICAL BONDING-It om and vice-versa. Thus, para form comes in contact ajith many water molecules and hence more oto 17° vpjuble. In ortho-form, oxygen atom of nitro group 4 GR No snd H-atom of phenolic group form intra- \ molecular H-bonding. When this compound is 2 put in water, the H-atom of water feels difficulty eo 6 fo form H bonding with the oxygen atom of ortho | 2.0R ORTHO. Nomen form. Thus, it is less soluble in water (Fig. 5.54). | NITROPHENOL. 4-OR PARA-NITROPHENOL| 13. Comparison among structures of NH,E, Fig. 5.54. NH,CI, NH,Br and NH4I. The radius ratio value of NHJF (- 0.92) suggests that it should have CsCl structure, but its crystals have wurtzite structure (zinc blende structure). In this structure, each NHj ion is tetrahedrally surrounded by F-ions and hydrogen bonds are formed between F ions and H-atom of NH,F. Hydrogen bonds are only formed in NH,F (F being more electronegative and small size) and not in other halides (HCI, HBr and Hi) because of their large size and low electronegativity. On the other hand, NH,CI, NH,Br and NH,I have CsCl structure below 457.3 K, 410.8 K and 255.4 K respectively. ‘Above these temperatures, these have NaCl structure. 14, Structure of molecular crystals. Consider a-oxalic acid, H3C,0,. Its sheet structure is shown in fig. 5.55. The formation of sheet structure (a-oxalic acid), or three dimensional net work (e.g, KH.PO,), linear chain (HCN), zig-zag chain in HF, HCOOH (formic acid), CH,OH etc,, is due to small size Fig. 5.55. and high electronegativity of O-atom in oxalic acid etc. and F- atoms, N-atoms in other examples given. 15. Formation of hydrogen fluoride ion, HF}. This ion is formed as, F- + HF —> HF, because due to small size and high electronegativity of F, a H-bond is formed between H and F-atoms as (:F:.... H-: FI or HF. 16, 1-Hydrogen bonding, Recently, it has been proved that hydrogen bonding inter- actions also take place between.-electrons of aromatic or olefinic systems and H-atom of the same or different molecule. These x-electrons act as a ee aoe ar Proton acceptor or a base. These interactions rete ae are of two types. (i) Intermolecular a-hydrogen | <7 ms bonding. Such type of bonding takes place between H-atom of one molecule and 1-bond of another molecule of same or different substance (Fig. 5.56). ( Intramolecular x-hydrogen bonding. Such type of bonding takes place between H-atom and z-bond within the same molecule (Fig. 5.57). c 17. Monomeric or polymeric nature of molecules. ‘nsider HE, HCl, HBr and HI molecules. Due to small8 & KALYAN! INORGANIC CHEMISTRY (SEI 4 yp size and high electronegativity of F-atom, HF molecules behave as follows under ditferery conditions. (i) Above 353 K and 1 atmospheric pressure, HF vapour is monomer. (ii) At low temperature and high pressure, it exists as liquid as well as gas (due to inter-molecular hydrogen bonds) which are polymeric associated molecules, (HF),, (1 = 2 to 6) (Fig. 5.58). Solid HF possesses a zig-zag chain structure with H ... F (1.55A), H - F (1A), HFH angle 140°. Anhydrous acid probably exists as a mixture of HF, H3Fy HF, and HsFs.HCl, HBr and HI exist as monomeric molecules because hydrogen bonding is not possible in these molecules due to their large size and low electronegativity. Importance of H-bonding (i) Life would have been impossible without liquid water which is the result of inter molecular H-bonding in it. (ii) Hydrogen bonding increases the rigidity and strength of wood fibres and thus makes it an article of great utility to meet requirements of housing, furniture etc. (iii) The cotton, silk or synthetic fibres also owe their rigidity and tensile strength to hydrogen bonding, (io) Most of our food materials such as carbohydrates and proteins also consist of hydrogen bonded molecules. (0) Hydrogen bonding also exists in various tissues, organs, skin, blood and bones. Application of hydrogen bonding to biological macro-molecules Experiments reveal that hydrogen bond plays a significant role in biology. A few of these are given (i) It helps the antibodies to bind to their antigens. (@ It helps transcription factors to bind to DNA. (i It holds the two strands of DNA double helix together. (ie) It helps enzymes (biocatalyst) to bind to their substrate. aan aie PsPtides (rings of aminoacids) to form secondary structures (eg. betasheet 5.17 METALLIC BOND — About 80% of the known elements are metals, These c elasticity and bright lustre. These properties cannot be explained in terms of ionic and | ( Evidence against the presence of ionic bond. the anor oe Ionic bonds are. formed by