Covalent Bond Model Basics of Chemical Bond CHM 001 Oluwakemi A. Oloba-Whenu, Ph. D 147A Faculty of Science Covalent Bond • Formed by sharing electrons • More common • A bond where electrons from each atom are shared • • • • Each covalent bond has 2 electrons that are shared. Only the Valence electrons are involved in these covalent bonds. Between nonmetallic elements of similar electronegativity. The atoms involved will share sufficient numbers of electrons in order to achieve a octet or noble gas electron configuration (that is, eight valence electrons). • Examples; O2, CO2, C2H6, H2O, SiC Covalent Bonding • There are several electrostatic interactions in these bonds: – attractions between electrons and nuclei, – repulsions between electrons, and – repulsions between nuclei. • For a bond to form, the attractions must be greater than the repulsions. Covalent Bonding • There are several electrostatic interactions in these bonds: – attractions between electrons and nuclei, – repulsions between electrons, and – repulsions between nuclei. • For a bond to form, the attractions must be greater than the repulsions. Formation • between atoms of the same element N2, O2, diamond,graphite • between atoms of different elements CO2, SO2 on the RHS of the table • when one of the elements is in the middle of the table; CCl4, SiCl4 • with head-of-the-group elements with high ionization energies; BeCl2 Covalent bond and Lewis structure • The shared electrons in H2 spend part of the time in the region around each atom. • In this sense, each atom in H2 has a helium configuration • The formation of a bond between H and Cl to give an HCl molecule can be represented in a similar way. : : : : . + .Cl : : : H H Cl • Thus, hydrogen has two valence electrons about it (as in He) and Cl has eight valence electrons about it (as in Ar) Covalent bonding • Covalently bound species are different from their ionic counterparts • exist as individual, discrete species (vs. 3-D crystal lattice structure for ionic) • tend to exhibit much lower melting and boiling points (vs. ionic) HYDROGEN H H both atoms need one electron to complete their outer shell DOT AND CROSS DIAGRAM H H H H atoms share a pair of electrons to form a single covalent bond H H FLUORINE F F both atoms need one electron to complete their outer shell DOT AND CROSS DIAGRAM F F F F atoms share a pair of electrons to form a single covalent bond F F FLUORINE H F both atoms need one electron to complete their outer shell DOT AND CROSS DIAGRAM H F H F atoms share a pair of electrons to form a single covalent bond H F Covalent bond and Lewis structure • An electron pair that is shared is called a bonding pair or bond pair • An electron pair localized on an atom a lone pair (an electron pair that is not shared). METHANE H H H H C H atom needs four electrons to complete its outer shell DOT AND CROSS DIAGRAM H each atom needs one electron to complete its outer shell C H H Carbon shares all 4 of its electrons to form 4 single covalent bonds H H H C H H C H H H AMMONIA H H H N H atom needs three electrons to complete its outer shell N H H each atom needs one electron to complete its outer shell Nitrogen can only share 3 of its 5 electrons otherwise it will exceed the maximum of 8 A LONE PAIR REMAINS H N H H H N H H WATER H H O H atom needs two electrons to complete its outer shell O H each atom needs one electron to complete its outer shell Oxygen can only share 2 of its 6 electrons otherwise it will exceed the maximum of 8 TWO LONE PAIRS REMAIN H O H H O H Multiple bond • A shared pair is a single bond and is represented by a line • If more than an electron pair is shared then there is more than one bond • Two pair are called double bonds O O O O each atom needs two electrons to complete its outer shell O each oxygen shares 2 of its electrons to form a O DOUBLE COVALENT BOND C H : H C ::: • If more than an electron pair is shared then there is more than one bond • Two pair are called double bonds • Three pairs single bonds H : :C C : Multiple bond H H H or H C C H H or H H C C H Multiple Bonds single bond – 2 electrons (1 pair of electrons) are shared between 2 atoms double bond – 4 electrons (2 pairs of electrons) are shared between 2 atoms triple bond – 6 electrons (3 pairs of electrons) are shared between 2 atoms Multiple bond • The more the number of electron pairs the shorter and stronger the bond • Bond Order Number of electron pairs that are shared between two atoms Exercise • Write Lewis structures for the following covalent molecules • then write their structural formulae using — to represent a shared pair of electrons: • (i) H2 (ii) CH4 • (iii) SiCl4 (iv) OCl2 (vii) PCl3 Polar and non-polar covalent bonds • When the atoms are alike, as in the H-H bond of H2 , the bonding electrons are shared equally (a nonpolar covalent bond). • When the two atoms are of different elements, the bonding electrons need not be shared equally, resulting in a “polar” bond. Polar covalent bond • A polar covalent bond is one in which the bonding electrons spend more time near one of the two atoms involved • It is as a result of unequal sharing of electron pair • Fluorine pulls harder on the shared electrons than hydrogen does. • Therefore, the fluorine end has more electron density than the hydrogen end. • Due to electronegativity difference • The end with the larger electron density gets a partial negative charge and the end that is electron deficient gets a partial positive charge. Polar covalent bond-Electronegativity • Electronegativity is a measure of the ability of an atom in a molecule to draw bonding electrons to itself. • In general, electronegativity increases from the lower-left corner to the upper-right corner of the periodic table. • The current electronegativity scale, developed by Linus Pauling, assigns a value of 4.0 to fluorine and a value of 0.7 to cesium. Polar covalent bond Electronegativity values have no units Arrange the following in order of increasing electronegativity: Na, F, O, K, Al, Si, Mg Polar Covalent Bonds – dipole moment • When two atoms share electrons unequally, a bond dipole results. • Recall that un equal sharing results in partial charges • A bond dipole is a measure of separation of electronic charge between two atoms bonded together. • The size of a dipole is measured by its dipole moment ( 𝜇) • The dipole moment, , produced by two equal but opposite charges separated by a distance, 𝑟, is calculated as 𝜇 = 𝑄𝑟 • It is a quantitative measure of the magnitude of a dipole • It is measured in debyes (D). • It increases as the magnitude of Q increases and as r increases Polar Covalent Bonds-dipole moment • The greater the difference in electronegativity, the more polar is the bond. • The higher the dipole moment Electronegativity and types of bond • The absolute value of the difference in electronegativity of two bonded atoms gives a rough measure of the polarity of the bond. • When this difference is small (less than 0.5), the bond is nonpolar. • When this difference is large (greater than 0.5), the bond is considered polar. • If the difference exceeds approximately 1.8, sharing of electrons is no longer possible and the bond becomes ionic. Rank the following in order of increasing bond polarity: H─F H─Br F─F a)H─F < H─Br < F─F < Na─Cl b)F─F < H─F < H─Br < Na─Cl c)H─Br < H─F < F─F < Na─Cl d)F─F < H─Br < H─F < Na─Cl e)Na─Cl < H─F < H─Br < F─F Na─Cl Exercise • Work out the differences in electronegativities between the elements in the following covalent bonds, rank them in order of increasing polarity, and show the direction of each dipole: • (i) Be—H (ii) O—H • (iii) C—H (iv) C—Cl • (v) C—O. POLAR MOLECULES Occurrence HYDROGEN CHLORIDE NET DIPOLE - POLAR not all molecules containing polar bonds are polar overall if bond dipoles ‘cancel each other’ the molecule isn’t polar if there is a ‘net dipole’ the molecule will be polar TETRACHLOROMETHANE WATER NET DIPOLE - POLAR NON-POLAR Lewis structure for molecules • The Lewis electron-dot formula of a covalent compound is a simple two-dimensional representation of the positions of electrons in a molecule. • Bonding electron pairs are indicated by either two dots or a dash. • In addition, these formulas show the positions of lone pairs of electrons Drawing Lewis Structures 1. 2. 3. 4. 5. Sum the valence electrons from all atoms. Add one electron to the total for each negative charge for an anion and subtract one electron from the total for each positive charge for a cation. Write the symbols for the atoms, show which atoms are attached to which, and connect them with a single bond. (Chemical formulas are often written in the order in which the atoms are connected in the molecule or ion). For example, the formula HCN indicates that the carbon atom is bonded to the H and to the N. In many polyatomic molecules and ions, the central atom is usually written first, as in and SF4. Remember in most cases, that the central atom is generally less electronegative than the atoms surrounding it. Complete the octets around all the atoms bonded to the central atom. Note: a hydrogen atom has only a single pair of electrons around it. Place any leftover electrons on the central atom, even if doing so results in more than an octet of electrons around the atom. If there are not enough electrons to give the central atom an octet, try multiple bonds. Use one or more of the unshared pairs of electrons on the atoms bonded to the central atom to form double or triple bonds. Halogens and hydrogen do not take part in multiple bond Drawing Lewis Structures 1. Consider the structure of PCl3, phosphorus trichloride 2. Total of 5(𝑃) + 3 × 7 𝐶𝑙 = 26 • Write the symbols for the atoms, show which atoms are attached to which, and connect them with a single (Heavier element or The least electronegative atom is often the central element) Drawing Lewis Structures 1. Consider the structure of PCl3, phosphorus trichloride 2. Total of 5(𝑃) + 3 × 7 𝐶𝑙 = 26 3. Write the symbols for the atoms, show which atoms are attached to which, and connect them with a single 4. Complete the octets around all the atoms bonded to the central atom. 5. Place any leftover electrons on the central atom, even if doing so results in more than an octet of electrons around the atom. Writing Lewis Dot Formulas • Consider the covalent compound 𝑆𝐶𝑙2. • Total electrons: 6 𝑆 + 2 × 7 𝐶𝑙 = 20𝑒 − • Sketch structure with single bonds • 4 electrons gone for bonds, 20 − 4 = 16𝑒 − 𝑙𝑒𝑓𝑡 • Complete octet of terminal atoms 12 gone 16 − 12 = 4𝑒 − • Leftovers on central atom Writing Lewis Dot Formulas • Try drawing Lewis dot formulas for the following covalent compound 𝐶𝑂𝐶𝑙2. • Total electrons: 4 C + 6 𝑂 + 2 × 7 𝐶𝑙 = 24𝑒 − • Sketch structure with single bonds • 6 electrons gone for bonds, 24 − 6 = 18𝑒 − 𝑙𝑒𝑓𝑡 • Complete octet of terminal atoms;18 gone;18 − 18 = 0𝑒 − • No Leftovers, central atom octet not complete • One of the oxygen or chlorines must share a lone pair Writing Lewis Dot Formulas • 𝐻𝐶𝑁. • Total electrons: 1 𝐻 + 4 𝐶 + 5 𝑁 = 10𝑒 − • Sketch structure with single bonds • 4 electrons gone for bonds, 10 − 4 = 6𝑒 − 𝑙𝑒𝑓𝑡 • Complete octet of terminal atoms; 6 gone; 6 − 6 = 0𝑒 − (Hydrogen can only take two electrons) • No Leftovers, central atom octet not complete • Nitrogen shares two lone pairs Draw the Lewis structure for the − 𝐵𝑟𝑂3 ion. • Total electrons: 7 𝐵𝑟 + 3 × 6 𝑂 + 1 𝑓𝑟𝑜𝑚 𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑒 𝑐ℎ𝑎𝑟𝑔𝑒 = 26𝑒 − • Sketch (For oxyanions 𝐵𝑟𝑂3− , Cl𝑂3− , 𝑆𝑂42− the oxygen atoms surround the central nonmetal atom) 26 − 6 = 20𝑒 − • Put eight electrons around the outer atoms 20 − 18 = 2𝑒 − • Add excess electrons to central atom • How many valence electrons should appear in the Lewis structure for CH2Cl2? • (b) Draw the Lewis structure • Draw the Lewis structure for (a) NO+ ion, (b) C2H4 (c) ClO2-(d) PO43- Formal Charge and Alternative Lewis Structures • In certain instances, more than one feasible Lewis structure can be illustrated for a molecule. For example, consider the 𝐶𝑂2 molecule • In such cases, to determine the dominant structure formal charge is used • The formal charge of any atom in a molecule is the charge the atom would have if all the atoms in the molecule had the same electronegativity Formal Charge and Lewis Structures • The formal charge of an atom is determined by subtracting the number of electrons in its “domain” from its group number. “domain” electrons 1 e- 4 e- 5 e- H C N: I IV V or 1 e- 4 e- H N C: I V 5 e- group number IV – The number of electrons in an atom’s “domain” is determined by counting one electron for each Copyright © Houghton Mifflin bond and two electrons for each lone pair. Company.All rights reserved. Presentation of Lecture Outlines, 9–42 Formal Charge and Lewis Structures • FC = VE (neutral atom) - LE (atom in molecule) - 1/2BE (atom in molecule) • VE =the number of valence electrons in the neutral atom • LE = the number of lone pair electrons on the atom in the molecule • BE= the number of bonding electrons on the atom in the molecule “domain” electrons 1 e- 4 e- 5 e- H C N: I IV V or 1 e- 4 e- H N C: I V 5 e- group number IV – The number of electrons in an atom’s “domain” is determined by counting one electron for each Copyright © Houghton Mifflin bond and two electrons for each lone pair. Company.All rights reserved. Presentation of Lecture Outlines, 9–43 Formal Charge and Lewis Structures • The most likely structure is the one with the least number of atoms carrying formal charge. If they have the same number of atoms carrying formal charge, choose the structure with the negative formal charge on the more electronegative atom. formal charge H C 0 0 N: 0 or H 0 N C: +1 -1 – In this case, the structure on the left is most likely correct. Copyright © Houghton Mifflin Company.All rights reserved. Presentation of Lecture Outlines, 9–44 Sample Exercise 8.9 Lewis Structures and Formal Charges Three possible Lewis structures for the thiocyanate ion, NCS – , are (a) Determine the formal charges in each structure. (b) Based on the formal charges, which Lewis structure is the dominant one? Solution (a) Neutral N, C, and S atoms have five, four, and six valence electrons, respectively. We can determine the formal charges in the three structures by using the rules we just discussed: As they must, the formal charges in all three structures sum to 1–, the overall charge of the ion. (b) The dominant Lewis structure generally produces formal charges of the smallest magnitude (guideline 1). That rules out the left structure as the dominant one. Further, as discussed, N is more electronegative than C or S. Therefore, we expect any negative formal charge to reside on the N atom (guideline 2). For these two reasons, the middle Lewis structure is the dominant one for NCS–. Formal Charges Formal charge vs oxidation number vs partial charges Resonance Structures • The structure of ozone, O3, can be represented by two different Lewis electron-dot formulas. • Both are identical and have equal weight i.e. they are both equally valid • Experimentally the two bonds have the same length • Both structures are called resonance structures • This is called delocalized bonding, in which a bonding pair of electrons is spread over a number of atoms • According to the resonance description, you describe the electron structure of molecules with delocalized bonding by drawing all of the possible electron-dot formulas. Sample Exercise 8.10 Resonance Structures Which is predicted to have the shorter sulfur–oxygen bonds, SO3or SO32– ? Solution The sulfur atom has six valence electrons, as does oxygen. Thus, SO 3 contains 24 valence electrons. In writing the Lewis structure, we see that three equivalent resonance structures can be drawn: As with NO3– , the actual structure of SO3 is an equal blend of all three. Thus, each S—O bond length should be about one-third of the way between the length of a single bond and the length of a double bond. That is, they should be shorter than single bonds but not as short as double bonds. The SO32– ion has 26 electrons, which leads to a dominant Lewis structure in which all the S—O bonds are single: Our analysis of the Lewis structures leads us to conclude that SO 3 should have the shorter S—O bonds and SO32– the longer ones. This conclusion is correct: The experimentally measured S—O bond lengths are 1.42 Å in SO3 and 1.51 Å in SO32–. Structure of Nitrate ion • NO3- Resonance • The organic compound benzene, C6H6, has two resonance structures. • It is commonly depicted as a hexagon with a circle inside to signify the delocalized electrons in the ring. Exceptions to the octet rule • Although many molecules obey the octet rule, there are exceptions where the central atom has more than eight electrons. • There are three types of ions or molecules that do not follow the octet rule: • ions or molecules with an odd number of electrons, • ions or molecules with less than an octet, • ions or molecules with more than eight valence electrons (an expanded octet • Generally, if a nonmetal is in the third period or greater it can accommodate as many as twelve electrons, if it is the central atom. • These elements have unfilled “d” subshells that can be used for bonding. Odd Number of Electrons Though relatively rare and usually quite unstable and reactive, there are ions and molecules with an odd number of electrons. Fewer Than Eight Electrons • Consider BF3: • Giving boron a filled octet places a negative charge on the boron and a positive charge on fluorine. • This would not be an accurate picture of the distribution of electrons in BF3. Fewer Than Eight Electrons Therefore, structures that put a double bond between boron and fluorine are much less important than the one that leaves boron with only 6 valence electrons. Fewer Than Eight Electrons The lesson is: If filling the octet of the central atom results in a negative charge on the central atom and a positive charge on the more electronegative outer atom, don’t fill the octet of the central atom. More Than Eight Electrons • The only way PCl5 can exist is if phosphorus has 10 electrons around it. • It is allowed to expand the octet of atoms on the third row or below. • Presumably d orbitals in these atoms participate in bonding. Exceptions to the Octet Rule • In xenon tetrafluoride, XeF4, the xenon atom must accommodate two extra lone pairs. F: : : Xe : F: : : Copyright © Houghton Mifflin Company.All rights reserved. : : : :F : : :F Presentation of Lecture Outlines, 9–58 More Than Eight Electrons Even though we can draw a Lewis structure for the phosphate ion that has only 8 electrons around the central phosphorus, the better structure puts a double bond between the phosphorus and one of the oxygens. More Than Eight Electrons • This eliminates the charge on the phosphorus and the charge on one of the oxygens. • The lesson is: When the central atom is on the third row or below and expanding its octet eliminates some formal charges, do so. Covalent Bond Strength H = 242 kJ/mol • The strength of a bond is usually measured by determining how much energy is required to break the bond. • This is the bond enthalpy. • The bond enthalpy for a Cl—Cl bond, D(Cl—Cl), is 242 kJ/mol. Average Bond Enthalpies • Average bond enthalpies are positive, because bond breaking is an endothermic process. NOTE: These are average bond enthalpies, not absolute bond enthalpies; the C—H bonds in methane, CH4, will be a bit different than the C—H bond in chloroform, CHCl3. Enthalpies of Reaction • Yet another way to estimate H for a reaction is to compare the bond enthalpies of bonds broken to the bond enthalpies of the new bonds formed. • In other words, Hrxn = (bond enthalpies of bonds broken) − (bond enthalpies of bonds formed) Enthalpies of Reaction CH4(g) + Cl2(g) CH3Cl(g) + HCl(g) In this example, one C—H bond and one Cl—Cl bond are broken; one C—Cl and one H—Cl bond are formed. CH4(g) + Cl2(g) CH3Cl(g) + HCl(g) Enthalpies of Reaction So, Hrxn = [D(C—H) + D(Cl—Cl) [D(C—Cl) + D(H—Cl) = [(413 kJ) + (242 kJ)] [(328 kJ) + (431 kJ)] = (655 kJ) (759 kJ) = 104 kJ Bond Enthalpy and Bond Length • We can also measure an average bond length for different bond types. • As the number of bonds between two atoms increases, the bond length decreases. Enthalpy problem: • Calculate the enthalpy of reaction for: • CH4 + O2 ---> CO2 + H2O • Calculate the enthalpy of reaction for: • CH4 + 3/2O2 ---> CO2 + 2H2O • 4(C--H) + 3/2(O==O) - 2(C==O) - 4(OH) • 4(413) + 3/2(495) - 2(800) - 4(463) = -563 kJ • HC CH + O2 ------> CO2 + H2O • HC CH + 5/2O2 ------> 2CO2 + H2O • 1(CC) + 2CH + 5/2(O=O) - 4(C==O) - 2(OH) • 1(834) + 2(413) +5/2(495) - 4(800) - 2(463) = -1229 kJ Enthalpy problem: • Calculate the enthalpy of reaction for: • CH4 + 3/2O2 ---> CO2 + 2H2O • 4(C--H) + 3/2(O==O) - 2(C==O) - 4(OH) • 4(413) + 3/2(495) - 2(800) - 4(463) = -563 kJ • HC CH + 5/2O2 ------> 2CO2 + H2O • 1(CC) + 2CH + 5/2(O=O) - 4(C==O) - 2(OH) • 1(834) + 2(413) +5/2(495) - 4(800) - 2(463) = -1229 kJ Sample Exercise 8.12 Using Average Bond Enthalpies Using data from Table 8.4, estimate H for the reaction Solution Analyze We are asked to estimate the enthalpy change for a chemical reaction by using average bond enthalpies for the bonds broken and formed. Plan In the reactants, we must break twelve C—H bonds and two C—C bonds in the two molecules of C2H6 and seven O2 bonds in the seven O2 molecules. In the products, we form eight C==O bonds (two in each CO2) and twelve O—H bonds (two in each H2O). Solve Using Equation 8.12 and data from Table 8.4, we have H = [12D(C—H) + 2D(C—C) + 7D(O2)] – [8D(C==O) + 12D(O—H)] = [12(413 kJ) + 2(348 kJ) + 7(495 kJ)] – [8(799 kJ) + 12(463 kJ)] = 9117 kJ – 11948 k J = –2831 kJ More than one central atom • Many atoms have more than 1 central atom • You just deal with each separately • Example: • Lewis structure for acetate: • CH3CO2- More than 1 central atom • The organic compound benzene, C6H6, has two resonance structures. • It is commonly depicted as a hexagon with a circle inside to signify the delocalized electrons in the ring. Properties of covalent compound Bonding Atoms are joined together within the molecule by covalent bonds. Electrical Don’t conduct electricity as they have no mobile ions or electrons Solubility Tend to be more soluble in organic solvents than in water; some are hydrolysed Boiling point Low - e.g. intermolecular forces (van der Waals’ forces) are weak; they increase as molecules get a larger surface area CH4 -161°C C2H6 - 88°C C3H8 -42°C as the intermolecular forces are weak, little energy is required to to separate molecules from each other so boiling points are low some boiling points are higher than expected for a given mass because you can get additional forces of attraction More Practice • Draw lewis structures for: • SO4-2, CO3-2, CHCl3, CN3H6+ (H’s are attached to the N’s). SO2, PO33-, NO2-1, BrO3-, ClO4-, DATIVE COVALENT (CO-ORDINATE) BONDING A dative covalent bond differs from covalent bond only in its formation Both electrons of the shared pair are provided by one species (donor) and it shares the electrons with the acceptor Donor species will have lone pairs in their outer shells Acceptor species will be short of their “octet” or maximum. Lewis base Lewis acid a lone pair donor a lone pair acceptor Ammonium ion, NH4+ The lone pair on N is used to share with the hydrogen ion which needs two electrons to fill its outer shell. The N now has a +ive charge as - it is now sharing rather than owning two electrons. Boron trifluoride-ammonia NH3BF3 Boron has an incomplete shell in BF3 and can accept a share of a pair of electrons donated by ammonia. The B becomes -ive as it is now shares a pair of electrons (i.e. it is up one electron) it didn’t have before. Ionic versus Covalent IONIC COVALENT Bonded Name Salt Molecule Bonding Type Transfer e- Share e- Types of Elements Metal & Nonmetal Nonmetals Physical State Solid Solid, Liquid, or Gas Melting Point High (above 300ºC) Low (below 300 ºC) Solubility Dissolves in Water Varies Conductivity Good Poor