4 TOPIC 3 MOLECULAR SHAPE AND BONDING
Transcription
4 TOPIC 3 MOLECULAR SHAPE AND BONDING
Topic 3 Molecular Shape and Chemical Bonding Content 3.1. COVALENT BONDING......................................................................................... 51 3.1.1. The octet rule .......................................................................................... 52 3.1.2. Valency ................................................................................................... 52 3.1.3. Co-ordinate covalent bonds .................................................................... 53 3.1.4. Multiple bonds ......................................................................................... 53 3.1.5. Bond polarity ........................................................................................... 54 3.2. LEWIS STRUCTURE OF MOLECULES ................................................................... 55 3.2.1. Charged and delocalized species ........................................................... 55 3.2.2. Exceptions to octet rule ........................................................................... 57 3.2.3. Bridging atoms ........................................................................................ 59 3.2.4. Bond order, bond length and bond energy .............................................. 60 3.3. MOLECULAR SHAPE .......................................................................................... 63 3.3.1. Geometry and shape ............................................................................... 63 3.3.2. VSEPR .................................................................................................... 64 3.3.3. Further examples of Lewis structure / VSEPR ........................................ 70 3.3.4. Inert pair effects ...................................................................................... 72 3.3.5. Shape and Molecular Dipoles ................................................................. 74 3.4. VALENCE BOND (VB) THEORY........................................................................... 76 3.4.1. Basis ....................................................................................................... 76 3.4.2. Hybrid Orbitals ........................................................................................ 77 3.4.3. VB construction ....................................................................................... 79 3.5. MOLECULAR ORBITAL (MO) THEORY- A BRIEF INTRODUCTION .............................. 81 Learning objectives Basic Concepts of Chemical Bonding – chemical formulae ; ionic bonding ; covalent bonding – octet rule, valency, bond polarity, Lewis structures, resonance, hypervalency, bond order, length and dissociation energy ; molecular geometry – VSEPR Theory ; dipole moments ; valence bond theory – hybrid orbitals ; molecular orbital theory. TOPIC 3. Molecular Shape and Chemical Bonding 51 3.1. Covalent Bonding A covalent bond is a chemical bond that involves the sharing of an electron pair between neighbouring atoms. Covalent bonding is energetically favoured. The bond energy is defined as the energy that must be supplied to separate the bonded atoms to infinity. The bond length is the distance between the two nuclei; it is the internuclear distance for which the bond energy is minimal. Covalent bonds are affected by the electronegativity of the connected atoms. For two atoms with equal electronegativity, the covalent bond is non-polar. E.g.: The hydrogen molecule: H-H; bond energy = 435 KJ mol-1; bond distance = 74 pm 1 e- 2 e- H H H H H Figure. Non-polar covalent bonding formed by the interaction of two shared bonding electrons. In a heteroatomic bond, the more electronegative atom tends to attract the electron pair of the bond. The covalent bond is polar with a negative partial charge over the more electronegative atom and a positive partial charge over the less electronegative. Example: The hydrochloride molecule: H-Cl unpaired electron lone pair 1 e- bonding pair + - 1+ + - H Cl H Cl + H Cl - Figure. Polar covalent bonding formed by the interaction of two shared bonding electrons. The bonding pair is not shared equally but is more attracted by the more electronegative atom (here Cl) which polarises the bond. ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 52 3.1.1. The octet rule The octet rule states that atoms tend to be more stable when their electronic configuration is similar to that of a noble gas. As a result, atoms tend to gain, lose or share electrons so that their outer shell is populated by 8 electrons. (8 = octet). This rule applies to the main group elements of low atomic number (<20), including carbon, nitrogen, oxygen, halogens, sodium, potassium, magnesium. The number 8 correspond to a full n-shell: 2 electrons in ns-orbital plus 6 electrons in np-orbitals. On ammonia (NH3) the nitrogen (which has 5 valence electrons) is bond to three hydrogen atoms: each hydrogen brings one electron to the molecule - so the total number of electron in the nitrogen's outer shell is 8 (5(N) + 3(H)). On water molecule, the oxygen (6 valence electrons) is bond to two hydrogens. Each hydrogen brings one electron to the oxygen's outershell, which is then populated by 8 electrons. (6(O) + 2(H)) 3.1.2. Valency The valency or valence number of an atom is the number of chemical bonds that an atom may form to satisfy the octet rule. It is equal to the number of unpaired electron (upe). The lone pair electrons are not counted as bonding, therefore the valency is the number of valence electrons, less the lone pair electrons (lp). The valency of an atom in a molecule is equal to the number of bond to the atom (single bond count as one bond, double bond two and triple bond three). Example: Nitrogen, has 5 valence electrons. Two of them are organised in one lone pair and three are available for bonding: the valency is 3. lp upe N upe upe Nitrogen has one lone pair (lp) and three unpaired electrons (upe) Chlorine, has 7 valence electrons. Six electrons are organised in three lone pairs and one electron is available for bonding: the valency is 1. lp lp Cl upe lp Chlorine has three lone pairs (lp) and one unpaired electron (upe) ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 53 3.1.3. Co-ordinate covalent bonds This is also known as a dipolar bond; a dative covalent bond or a co-ordinate bond and is a covalent bond in which the two electrons of the bond are provided by the same atom. Example: Adduct of ammonia and boron trifluoride. The two electrons of the B-N bond are provided by the nitrogen: as a result a positive charge appears on the nitrogen and a negative charge on the boron. Ground state Boron: [He] 2s22p1 lp eo empty orbital (eo) upe B F B upe upe empty orbital Excited state Boron: [He] 2s12p2 F H N H F H Boron trifluoride ammonia F H F B N F H H F H F B N F H H Adduct of ammonia and boron trifluoride 3.1.4. Multiple bonds A double bond is a chemical bond involving four bonding electrons shared between two atoms. Example: Ethylene C2H4. Each carbon is surrounded by 8 valence electrons. The bonding between the two carbons involves four valence electrons making a double bond. H H C H H H C C C H H H Figure. Double bond of ethylene. A triple bond involves six bonding electrons shared by two atoms. Example: Acetylene C2H2. Each carbon is surrounded by 8 valence electrons. The bonding between the two carbons involves six valence electrons: a triple bond. H C C H H C C H Figure. Triple bond of acetylene. ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 54 The valency of carbon is 4 in ethylene and acetylene: In ethylene, each carbon has four bonds: two single bonds with hydrogen plus one double bond with carbon. In acetylene, each carbon has four bonds: one single bond with hydrogen plus one triple bond with carbon. 3.1.5. Bond polarity When one of the two atoms involved in a covalent bond attracts the bonding electron pair more than the other atom, partial charges appear and the bond is polar. A negative partial charge ( -) appears over the atom attracting the electronic density and a positive partial charge ( +) appears over the other one. The ability to attract the electronic density is evaluated using the empirical value of electronegativity . The higher the value the greater the pull on electrons and the higher the difference in electronegativity between the two atoms bonded the higher the polarity. The polarity scale spreads continuously from non polar (the two atoms share the electron density equally -have equal ) to ionic (one atom takes the totality of the electron density leaving nothing to the other atom - the difference in between the two atoms is well over 0.5). Between these two extremes the covalent bond is essentially non polar (difference less than 0.5) or polar (difference over 0.5). The polarity of a bond is measured by the values of the partial charge ( + and -) created. = q x e x r (C m) is the dipole moment measured in Debye (D) -30 ( 1D = 3.336 x 10 Cm) q is the partial charge on the atoms e is the charge of an electron in C (coulomb) r is the bond length in m (metre Example. HF has a dipole moment of 1.83 D and a bond length of 92 pm (92x10 -12m) Calculate the value of q q = / (e x r) = 0.41 ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 55 3.2. Lewis Structure of Molecules Lewis electron dot diagrams show the valence electrons arround the atoms of a molecule and identify their nature as lone pair (lp), bonding pair (bp) or unpaired electrons (upe). The molecular shape is dictated by the position of the electrons around the central atoms. Building the Lewis structure of molecules in 5 steps: Methanol, CH 3OH 1. Start from the molecular formula. Determine for each atom the total number of valence electrons. When dealing with an anion, add one electron per charge. For a cation, remove one electron per charge. 2. Place the element of lowest valence around the element of highest valence. Then assign the bonds (single double or triple) to satisfy the valency of the atoms of lowest valency. 3. Calculate the number of valence electrons around the central atom, adding the shared electrons from the peripheral atoms. 4. Assign the shared electrons to bond pairs (bp). 5. Assign the residual valence electrons to lone pairs (lp). 3.2.1. Charged and delocalized species To draw the Lewis structure of negatively charged species, the general method of construction is followed, adding one extra valence electron per negative charge. Example. Tetrahydroborate ion: BH4-. eo B Boron Electron H H H H H H B H H H B H Four hydrogens H H Tetrahydroborate Note: Boron is surrounded by 8 electrons. The octet rule is satisfied. The Lewis structure of positively charged species is constructed following the general method, removing one valence electron per positive charge. ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 56 Example. Ammonium ion: NH4+. H H H H N H H N H N H H H H Nitrogen H Four hydrogens, of which one had its electron removed (proton with positive charge) Ammonium ion Note: Nitrogen is surrounded by 8 electrons. The octet rule is satisfied. When dealing with delocalised bonding: more than one Lewis structure can be drawn. This happen when a bond pair does not have a definite position between two atoms only but over three or more atoms. Each possible Lewis structure is called a resonance structure; the molecular skeleton does not change but the arrangements of the electrons change. Example. Nitrate: [NO3]-. Three equivalent Lewis structures (resonance structures) are possible, because one bond pair is delocalized over four atoms. The nitrogen is positively charged and two negative charges are delocalized between the three oxygens. Each oxygen has a charge of -2/3. N Three oxygens Nitrogen O O N O O O N -2/3 O N O O O O O O N One electron N O O O O O O O N O O O or N O O -2/3 Nitrate ion: three equivalent Lewis structure are possible Note. The phenomenon of resonance is symbolized by double arrow between the resonance structures. ©HERIOT-W ATT UNIVERSITY -2/3 TOPIC 3. Molecular Shape and Chemical Bonding 57 3.2.2. Exceptions to octet rule Hypervalence. (more than 8 valence electrons) A hypervalent molecule contains one or more main group elements formally bearing more than eight electrons in their valence shells. It can happen when: o The central atom is a main group element with a valence shell n ≥ 3. * o Central atom must use more than 4 valence orbitals, o Peripheral atoms have large (O, F, Cl, …) Example of hypervalent molecules: Phosphorus pentafluoride (PF 5), sulfur hexafluoride (SF6), SF4,Chlorine trifluoride (CIF3), Triiodite (I3-), SOCl2, XeOF4, … ClF5, XeF6 (*) Note. The central atom must use more than 4 valence orbitals, so hypervalence is naturally limited to valence shell, n ≥ 3. upe F [He] 2s2 2p5 [Ne] 3s2 3p3 3d0 P in PF5 F P F p d s p d [Ne] 3s2 3p3 3d0 Ground state P F s F F ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 58 Figure. Hypervalent phosphorus pentafluoride (PF5). The phosphorus undergoes excitation to promote one electron from 3s orbital to one empty 3d orbital, providing five unpaired electrons and allowing the formation of PF 5 molecule. I 5s 5p 5s 5p 5s 5p 5d [Kr] 4d105s2 5p5 10 2 5d 6 ground state of I -[Kr] 4d 5s 5p I- in I3- 5d [Kr] 4d105s2 5p5 5d1 Lewis structure of triiodide I I I Figure. Hypervalent triiodide (I3-). The central atom is ion iodide; its extra electron is promoted to the empty 5d orbital – allowing the formation of two single bounds. The central atom has therefore three lone pairs. Less than 8 valence electrons. The case of boron trifluoride. Looking at the atomic orbitals, the central atom of boron trifluoride has only 6 valence electrons, hence does not follow the octet rule. 2s B [He] 2s2 2p1 F 2s B in BF3 2p 1 2 B 2p F F [He] 2s 2p Lewis structure of BF3 ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 59 However, three resonance structures can be drawn in which one fluoride, already bonded to the boron by a single bond, provides co-ordinate pi-bond to the central atom’s empty porbital. In these three resonance structures, the octet rule is respected (but fluorine has to bear a positive charge). F F F F B B B F F F F F Resonance structures of BF3 Which Lewis structure best describe BF3? If several Lewis structure are possible; choose the one with the lowest charges The zwitterion description shows a positive charge on fluorine (not best). 3.2.3. Bridging atoms Bridging chloride. If boron is stable with 6 valence electrons as in BF3, aluminium although in the same group is not so stable in AlCl3. Al [Ne] 3s2 3p1 Cl high temperature, gas phase Al Cl Cl lower temperature, gas phase and liquid phase Cl Cl Cl Cl Al Al Cl Cl Cl Cl Cl Al Al Cl Cl Cl At lower temperatures dimers form via Cl bridging using Cl lone pairs and the Al empty porbital, forming a co-ordinate covalent bond (2 centers and 2 electrons). Note. In the solid phase, the structure is polymeric ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 60 Bridging hydrogen. Borane, BH3 dimerises to form diborane B 2H6. Here the bridge uses bond pair: the electron pair from BH bond is shared to make a second BH bond: 3 center 2 electrons bond. 2 1 B [He] 2s 2p H H H B 2 H B H H H H B H B H H H H H H B H H B H H 3.2.4. Bond order, bond length and bond energy Bond order (bo) is the number of chemical bonds between two atoms. Example: The bond order in diatomic nitrogen (N≡N) is 3 The bond order in hydrogen chloride (H-Cl) is 1. Covalent radius is half the internuclear distance (the bond length) in homonuclear bond and is bond order specific. Example: Molecules Bond length Covalent radius H3C CH3 154 pm 77 pm H2C CH2 134 pm 67 pm HC CH 120 pm 60 pm Bond length (bl) between two atoms is the addition of their covalent radii. Example: Molecules Cl Bond length Covalent radius Cl 198 pm Clcr = 99 pm H3C CH3 154 pm Ccr = 77 pm H3C Cl 178 pm Clcr + Ccr = 176 pm ©HERIOT-W ATT UNIVERSITY B H H TOPIC 3. Molecular Shape and Chemical Bonding 61 Bond energy (be) is directly correlated with bond order (bo) and inversely correlated with bond length (bl). Example: Molecules Bond order Bond length Bond energy (kJ.mol-1) H3C CH3 1 154 pm 346 H2C CH2 2 134 pm 598 HC CH 3 120 pm 813 Bond energy is always positive: it is the energy required to break up the bond. When a bond is made, energy is released (exothermic). C H C N O S F Cl Br I H 435 416 391 464 366 570 432 366 298 C=C C≡C N=N N≡N P≡P 598 813 400 945 490 C=N C≡N N=O O=O S=S 346 285 359 272 485 327 285 213 N Single Bonds O S 159 201 146 272 193 615 866 607 498 425 266 326 255 217 190 218 201 201 Multiple Bonds C=O C≡O S=O (in SO2) S=O (in SO3) Si=O F Cl Br I 159 247 249 278 242 216 208 193 175 151 806 1072 532 469 642 Table of single and double bonds energy (in kJ .mol-1). ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 62 Exercise 1: Calculate the heat of reaction H (ie enthalpie change) for the reaction: C2H6 C2H2 + 2H2 H H C C H H H H H Bond broken H be total H C C H H H bond made energy released total 1 C C 813 813 1 C C -346 -346 2 H H 2 X 435 870 4 C H 4 X -416 -1664 1683 kJ - 2010 kJ H = 1683 -2010 = -327 kJ Exercise 2: Calculate the heat of reaction ( H) for the formation of sulfur bromide (S 2Br2) from the elements in their standard states and comment on its sign. 4 S2Br2 S8 + 4 Br2 S S S S S S S Br 4 Br S 4 Br Br S Bond broken S be total bond made 8 x Br 4x S S 4 x 266 1064 4 x Br Br 4 x 193 772 1836 kJ H = 1836 -1736 = + 100 kJ ©HERIOT-W ATT UNIVERSITY S energy released 8 x - 217 total - 1736 - 1736 kJ (ie reaction is endothermic) TOPIC 3. Molecular Shape and Chemical Bonding 63 3.3. Molecular Shape The molecular shape is determined experimentally: By electron diffraction in gas phase By X-ray diffraction in crystalline phase The molecular shape can be predicted from the Lewis structure of the molecule, using the VSEPR theory (Valence Shell Electron Pair Repulsion). Valence electron pairs form groups and are arranged around the central atom and repel each other. Therefore the shape of the molecule depends primarily on the number of groups. Example: the molecular shapes of boron trichloride and nitrogen trichloride . lp Cl Cl N N B B Cl Cl Cl BCl3: planar shape Cl Cl Cl Cl Cl Cl Cl NCl3: non-planar shape The shape of a molecule is determined by the three-dimensional arrangement of the valence electrons; whether in bonding pairs, in lone pairs or unpaired. 3.3.1. Geometry and shape The shape of a molecule is the disposition of all the molecule’s atoms. It is determined by the arrangement of the bond pairs (bp) around central atoms. The geometry of a molecule is the three-dimensional arrangement of the molecule’s valence electrons (bond pairs, lone pairs and unpaired electrons). The molecular geometry determines many of the substance’s properties such as chemical reactivity, polarity, colour or magnetism. ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 64 Examples: sulfur hexafluoride (SF6), chlorine pentafluoride (ClF5), xenon tetrafluoride (XeF4). ClF 5 SF6 XeF4 F F F F F F F Cl S F F F F Xe F F F Shape F square pyramidal octahedral square planar F F F F F F F F Xe Cl S F F F F F F F Geometry octahedral octahedral octahedral 3.3.2. VSEPR The Valence Shell Electron Pair Repulsion (VSEPR) theory is used to predict the shape of molecules and is based on electron-pair electrostatic repulsion. The model is based on a central atom A and a number of valence electron group (electron-pairs) which can be bonding (X) to a substituent or non-bonding (lone pair) (E). All valence electrons groups repel each other and dictate the shape of the molecule. The basic geometry. For simple molecules, made of a central atom A and where all electron-pairs X are bonding to substituent(s) we describe five basic geometries depending on the number of valence electron group X (from 2 to 6X). Example: 2X 3X X X o A 108 4X A X X X linear X o 120 trigonal planar ©HERIOT-W ATT UNIVERSITY o 109 A X 6X 5X X X tetrahedral X X A X o X 90 X X 120o X X trigonal bipyramidal A X 90o X X octahedral TOPIC 3. Molecular Shape and Chemical Bonding 65 Predicting molecular shape with VSEPR theory. Determine the basic geometry from the Lewis structure. Lone pairs have greater electrostatic repulsion than bonding pairs, therefore they require more space than bonding pairs. When they are present; refine the geometry and determine the molecular shape. Examples: with one lone pair AXnE. 1 lp 1 lp 1 lp AX2E AX3E AX4E X <120o A A X X X X o <109 1 lp AX5E <90o X X <120o A X X bent or angular trigonal pyramid X X A X X X <90o see-saw square pyramidal Example: with two lone pairs AXnE2. 2 lp 2 lp AX2E2 AX3E2 X A <<109o X bent or angular ©HERIOT-W ATT UNIVERSITY o <90 X X A 2 lp AX4E2 X A X X o 90 X X T-shape square planar TOPIC 3. Molecular Shape and Chemical Bonding 66 Example: with three lone pairs AXnE3. 3 lp 3 lp AX2E3 AX3E3 X 180o X A A X o <90 X X linear T-shape The VSEPR theory in four simple rules: rule 1. The distances between valence electron groups X are maximized rule 2. Lone pairs (lp) require more space than bonding pairs (bp). rule 3. Multiple bonds require more space than single bonds rule 4. The space required by bp decreases with increasing of peripheral atom. The rules 1 and 2 give the basic shape of the molecule and rules 3 and 4 refine the shape. Rule 1: The distances between valence electron groups X are maximized - Two groups (AX2): linear geometry. Note: a multiple bond counts as one group. o 180 F Be F 2 bp, 2 single bonds AX 2 F Be F Linear shape o 180 O C O 4 bp, 2 double bonds AX2 O C O Linear shape o 180 H C N 4 bp, 1 triple bond and 1 single bond ©HERIOT-W ATT UNIVERSITY AX2 H C N Linear shape TOPIC 3. Molecular Shape and Chemical Bonding 67 - Three groups (AX3): trigonal geometry. Note: a lone pair E counts as one group. F F F o 120 F B 3 bp, 3 single bonds B AX3 trigonal planar geometry (trigonal planar shape) F F O O S 5 bp, 2 double bonds and 1 lone pair AX 2E S trigonal planar geometry (angular shape) O O - Four groups (AX4): tetrahedral geometry. H H H H C 4 bp, 4 single bonds H C H H H H N 4 bp, 3 single bonds o 109.5 AX 4 AX 3E H H tetrahedral geometry N H H tetrahedral H (trigonal pyramidal shape) H O 4 bp, 2 single bonds AX 2E2 H tetrahedral geometry O H H (bent or angular shape) -Five groups (AX5): trigonal bipyramidal (tbp) geometry. F F F F P 5 bp, 5 single bonds AX 5 o 90 P F trigonal bipyramidal F F F F F F F F S F 5 bp, 4 single bonds and 1 lone pair F AX 4E F S F F (see-saw shape) ©HERIOT-W ATT UNIVERSITY trigonal bipyramidal TOPIC 3. Molecular Shape and Chemical Bonding 68 -Six groups (AX6): octahedral geometry. F F F F F F F F F F F P F octahedral geometry F F F I F AX 6 6 bp, 6 single bonds P F AX 5E 6 bp, 5 single bonds and 1 lone pair F F I F octahedral geometry F F (square pyramidal shape) O F Xe F F F AX 5E 7 bp, 4 single bonds, 1 double bond, and 1 lone pair F F Xe F octahedral geometry F O (square pyramidal shape) Rule 2: Lone pairs (E) require more space than bonding pairs (X). The electrostatic repulsion caused by lone pairs is greater than the repulsion caused by bonding pairs. This has an effect on the molecule’s angles (the lone pair(s) push the bonding pairs away). H H C H H H o 109.5 O N H H H H o o 105 107 And has an effect on molecular shape (lone pairs have more space in equatorial position than in axial): F F F S S F F F F (see-saw shape) prefered isomer: lp equatorial ©HERIOT-W ATT UNIVERSITY X F (trigonal pyramidal shape) lp axial is not favourable TOPIC 3. Molecular Shape and Chemical Bonding F equatorial to equatorial angle F o 102 F S 69 F F Cl Xe F F F F o 173 axial to axial angle lone pairs in equatorial position Rule 3: Multiple bonds require more space than single bonds. A double bond is made of four valence electrons, a triple bond of six; they have a greater electrostatic repulsion than a bond pair. H H F O C B C C F F H o 120 H H o H o 116 117 Rule 4: The space required by bp decreases with increasing of peripheral atom. The bonding pairs are attracted by the more electronegative atom. The more electronegative the peripheral atom the greater the attraction toward the periphery and less space is required by the bonding pair around the central atom. O O + H H electronic density is between C and H - F F - electronic density attracted by F more space available around the central atom O O H H o 116 F F 108 o The rules 1 and 2 give the basic shape of the molecule and rules 3 and 4 refine the shape. ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 70 When the peripheral atoms are different the refined shapes is inevitably a distorted basic shapes. Example of sulfur hexafluoride (SF6) and sulfur monochloride pentafluoride (SClF 5). Chloride is less electronegative than fluoride, therefore requires more space . o 90 F F o F 90 S F F Cl >90o F F S F each angle is 90o F F F Cl is less than F Cl requires more space than F no distorsion o each angle is 90 octahedral distorsion octahedral distorted octahedral 3.3.3. Further examples of Lewis structure / VSEPR Chlorine dioxide (ClO2+) First; write the Lewis structure. 6 e per O plus 7 e on Cl O each O needs 8 valence electrons remove one electron to make positive charge Lewis structure O Cl Cl O O Cl O O Then apply the VSEPR rules; count the number of groups and apply rules 1 to 4 to determine and refine the molecular shape. 3 groups of valence electron-pairs gives a basic trigonal planar geometry. 2 groups are double bond Cl=O and 1 is a lone pair. AX2E Cl O O bent shape trigonal planar geometry The molecule has a bent or angular shape and a trigonal planar geometry. ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 71 Azide ion (N3-) First; write the Lewis structure. one lone pair from central N is used to make a co-ordinate covalent bond lp 5 e per N N N N each N needs 8 valence electrons N N N add one electron to make negative charge Lewis structure N N N Then apply the VSEPR rules; count the number of groups and apply rules 1 to 4 to determine and refine the molecular shape. 2 groups of valence electron-pairs, Linear geometry. AX2. N N N The molecule has a linear shape and a linear geometry. Note: the charges on the nitrogens; the central atom forms a co-ordinate covalent bond with one peripheral nitrogen atom and therefore gets a positive charge (for the same reason the peripheral nitrogen gets a negative charge). The electron is added to the second peripheral nitrogen which comes with a negative charge . ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 72 Nitric acid (HNO3) First; write the Lewis structure. H 5 valence electrons on N, 1 on H and 6 per O lone pair of N forms a co-ordinate bond with one O H H Lewis structures: O O N O O N O O N O O O Then apply the VSEPR rules; count the number of groups and apply rules 1 to 4 to determine and refine the molecular shape. 3 groups of valence electron-pairs, Trigonal planar geometry. AX3. 1 group is a single bonding pair (N-O) and 2 groups are partial double bond (the structure is delocalized). These two groups require more space than the first one: therefore the molecule has a distorted trigonal planar shape. O HO -1/2 N O -1/2 3.3.4. Inert pair effects The inert pair effect is a tendency of the s valence electrons to remain as a lone pair in compounds of post-transition metals. Selenium hexachloride (SeCl6 2-) s p d s p d s p d Se [Ar] 4s2 4p4 Ground state Se2- [Ar] 4s2 4p6 2- 2 3 3 Excited state Se [Ar] 4s 4p 4d ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 73 We expect the 8 valence electrons to form seven valence electron groups: six bonding pairs with Cl and one lone pair; a AX6E geometry (pentagonal bipyramidal geometry). pentagonal bipyramidal We do not obverse a AX6E geometry but a AX6 octahedral geometry. 2 Cl Cl Cl Se Cl Cl Cl octahedral geometry The valence electrons of the 4s-orbital are inert, they do not affect the shape of the molecule: they are stereochemically inactive. For post-transition elements, such as Se, the valence s-electrons are relatively deeply buried and are not really valence. So if s-electrons are not part of the valence, only 12 valence electrons are involved in forming six groups and we observe a AX6 octahedral geometry. Note. This is related to the tendency of post-transition elements to form two oxidation states: a normal oxidation state (using all valence s- and p-electrons and a lower oxidation state (leaving the s-electrons). This phenomenon is known as the thermodynamic inert pair effect. ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 74 Example: Sn (IV) Tin Sn 10 [Kr] 4d 2 [Kr] 4d10 2 5s 5p Lead Pb [Xe] 4f 14 10 5d 10 2 2 6s 6p 14 2 10 14 10 5d [Xe] 4f 2 [Kr] 4d Tl (III) 1 [Xe] 4f 14 14 10 5d 10 [Kr] 4d 6s 6p 2 6s 2 In (I) 10 1 5s 5p 5d [Xe] 4f 5s Pb (II) In (III) Thallium Tl [Xe] 4f 10 [Kr] 4d Pb (IV) Indium In [Kr] 4d Sn (II) 5s 2 Tl (I) 10 [Xe] 4f14 5d10 6s2 5d 3.3.5. Shape and Molecular Dipoles The shape of molecule has an effect on the molecular magnetism. When two bonded atoms have different electronegativity the bond is polarized. In molecules where there is more than one polarized bond; the dipoles resulting from polar bonds can either cancel each other (and the molecule is not polar) or contribute to create a molecular dipole and the molecule is polar, depending on the shape of the molecule. Bond dipole moment (expressed in Debye) is used to measure the polarity of a chemical bond, where d is the bond length and the value of the partial charge . = d It is a vector, parallel to the bond axis. It is pointing from negative to positive charge. In polyatomic molecules the total molecular dipole moment is the vector sum of individual bond dipole moment and is depending on the molecular shape. The measure of the molecular dipole gives information on molecular shape. ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 75 Example: The molecular dipole moment of water H2O is 1.85 Debye, of carbon dioxide is 0 Debye. O H + net dipole = 1.85 D + C - O molecule is bent H + O - net dipole = 0 D molecule is linear Example 2 : Two isomers of 1,2-Dichloroethylene are isolated, one (a) is polar with a molecular dipole moment of 1.90 D and the second (b) is non-polar with a molecular dipole moment of 0 D. Determine which is the cis and trans-isomers from the value of the molecular dipole moment. Cl Cl + C + C H (a) is cis-isomer net dipole = 0 D (b) is trans-isomer H Cl H + C H net dipole = 1.90 D + C Cl - ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 76 3.4. Valence Bond (VB) Theory The valence bond (VB) theory is a complement to the molecular orbital (MO) theory and was developed to explain chemical bonding. It focuses on localized bonding (when MO theory describes orbitals covering the whole molecule). Is not suited to describing delocalization. Is a good qualitative model 3.4.1. Basis According to the theory, a covalent bond is formed between two atoms by the overlap of two atomic orbitals of the same phase. Each atomic orbital containing one unpaired electron. Example. Two s-orbitals of the same phase form the single bond in H 2. AO AO H (1s) H (1s) orbital overlap H2 (Sigma s) Example. One s-orbital from H and one p-orbital from Cl form HCl single bond. AO AO orbital overlap H (1s) Cl (3p) HCl (Sigma sp) Note. The electrons have opposite spin in the overlapped orbital. ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 77 3.4.2. Hybrid Orbitals Atomic hybrid orbitals are the result of mixing atomic orbitals (s, p, d, etc) from the same atom and have their own shape and energy. Hybrid orbitals are very useful in explaining molecular geometry and bonding properties. Example. Methane CH4 is a tetrahedral molecule in which each bond is similar and identical in energy. Looking at the atomic orbital of carbon: Ground state of C [He] 2s 2 2 2p Energy 2p 2p 2s 2s In order to create four bonding pairs, one electron from the 2s-orbital is promoted to an empty 2p orbital. The result is an excited state where all four valence electrons (upe) from C are available for bonding with the upe of the four hydrogen atom . 1 3 Energy Excited state of C [He] 2s 2p 2p 2p 2s 2s In the excited state, four upe are available for bonding, but are from two different energy levels. To reflect the fact that all bonds formed are of identical energy one s-orbital is mixed with all three p-orbitals resulting in four hybrid sp 3 orbitals (of identical energy level). sp3 hybridisation Energy 3 sp sp3 ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 78 The shape of the hybrid sp3 atomic orbitals One s-AO is mixed with three p-AO Each of the four hybrid sp 3 orbitals retains 25% of the s-AO character and 75 % of the p-AO. The energy level of the new hybrid orbitals is intermediate, between the s and p AO’s energy levels. 25% 75% s p sp3 Bonding hybrid orbital: Four covalent bonds are formed between the four sp 3 hybrid orbitals of carbon and by the overlap of four s-atomic orbitals of the four hydrogen atoms making four sigma ( ) bonds. CH4 C+4H 3 The hybridization reflects the geometry; sp hybridisation of the central carbon is consistent with the observed tetrahedral geometry on CH 4. For other geometries, other hybridisation schemes are used . Example: H sp H C C C H H H H trigonal 3 dsp P F F trigonal bipyramidal sp H F F F d2sp3 S F F C tetrahedral F F 3 2 C sp H linear H H F F octahedral Valence bond theory allows a simple view of chemical bonding once the geometry is known. ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 79 3.4.3. VB construction To construct the valence bonds, first the Lewis structure and then the geometry (using VSEPR) must be determined. Example. BF3 2 1 sp2 hybridised B B [He] 2s 2p F 2p F 2p F 2 sp 2s two p-orbitals are mixed with s-orbitals, making three sp2 hybrids one p-orbital is not hybridised and is perpendicular to the molecular plane Example. H2O AO O [He] 2s2 2p4 sp3 hybridised O lp 2p 3 sp lp H H 2s three p-orbitals are mixed with s-orbital, making four sp3 hybrids. two sp3 orbitals overlap a H (1s) orbital and two are lone pairs. ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 80 Example. SF6 F AO 2 4 2 S [Ne] 3s 3p 3 F F F F d sp hybridised S 3d F 3d 3p d2sp3 3s six d2sp3 orbitals result from mixing two d threep and one s AO. Example : C2H4. Representation of multiple-bonds with VB theory Three sp2 orbitals result from mixing one s and two p-orbitals. These three new orbitals overlap with two hydrogen (1s) orbital and one (sp 2) orbital from the second carbon; forming three single bonds (sigma bonds). 2 2 2 ground state of C [He] 2s 2p hybridisation sp p p C C Energy H H p 2p H H 2 sp 2s The sp2 hybridisation leaves one p-orbital unchanged on each carbon. Each p-orbitals are perpendicular to the molecular plan and parallels to each other: they overlap and form a bond. 2 hybridisation sp + p bond H C C H H H p sp2 A double bond is made of one sigma ( ) bond and one pi ( Note. The bond. bond has two opposite phases, one above and one bellow the molecular plan. ©HERIOT-W ATT UNIVERSITY TOPIC 3. Molecular Shape and Chemical Bonding 81 3.5. Molecular Orbital (MO) Theory- a brief introduction The molecular orbital theory is a method for determining molecular structures in which electrons are not assigned to individual bonds between atoms, but are delocalised on the whole molecule. Atomic orbitals have phase (+ or -). Bonding molecular orbitals (BMO) are formed when two AO of the same phase combine, they are more stable than the two AO. Antibonding molecular orbitals (ABMO) are formed when two AO of opposite phase combine, they are less stable than the two AO. In AMO, the electronic density between the two atoms is zero. Molecule of H 2, constructed from two H, called H A and HB Energy ABMO A - B B A BMO A + B The bond order of a pi orbital is: Bo = (number of electron pairs in BMO) – (number of ep in ABMO) = 1 ©HERIOT-W ATT UNIVERSITY