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IONIC AND COVALENT BONDING
I. INTRODUCTION A) Chapters 7 and 8 dealt with isolated atoms and their electronic properties. B) Many chemists are interested in molecules and compounds. C) All the tremendous variety of materials found in our physical world may be interpreted and understood as a combination of about 100 elements.
D) Chemical Abstracts registers compounds and gives each one a number - over 7 million have been registered and there are 17 million names. E) What kind of models do we have for these compounds??? F) What is the glue that holds species together? G) A chemical bond is the glue which holds atoms together to make more than one atom molecules and ionic substances.
H) Two classes of chemical bonds have been mentioned throughout this semester: 1) Ionic bond - formed by the attraction between positive and negative ions - it is electrostatic in nature. 2) Covalent bond - a chemical bond formed by the sharing of a pair of electrons between atoms. I) KEY POINT When atoms interact to form a chemical bond, only their outermost regions are in contact.
For this reason, when we study chemical bonding we are interested in the outermost electrons of an atom primarily; its valence electrons. J) Elements with similar electron configurations (THE SAME NUMBER OF VALENCE ELECTRONS) behave alike chemically, a family, a group, a column.
II. LEWIS (DOT) SYMBOLS FOR THE ELEMENTS A) A Lewis dot structure for an atom consists of the symbol for the element and one dot for each valence electron. It is used for the s and p block elements, the representative elements.
C) Elements in the same column, the A columns or columns 1 and 2 and columns 13 18, have similar dot configurations. (We don't use this symbolism for the transition elements and the inner transition elements the actinides and the lanthanides). We use it only with the representative elements. III. THE IONIC BOND A) Ionic compounds are held together, for the most part, by strong electrostatic forces between oppositely charged species.
B) A simple model, which is not the whole story as with most ideas in this course, is that ions are formed through the transfer of electrons from one atom to another. C) Electrons are given by metal atoms to nonmetal atoms. The metal atom forms a ____________, the nonmetal a________. For the representative metals and nonmetals this involves the formation a species with a noble gas electron configuration. What is that?
D) Na [Ne]3s1 + Cl [Ne] 3s23p5 Na+[Ne] + Cl- [Ar]
E) Cation formation, the formation of a___________, involves the removal of 1 or more electrons from the highest occupied n shell. F) Anion formation, the formation of a __________, involves the addition of _____________________ . G) IONIC RADIUS
1) The radius of a cation (+ ion) is always _____ than the covalent radius of the parent atom. For example: 20Ca [Ar] 4s2 197 pm. It has 20 protons in the nucleus, 18 shielding electrons, and 2 in the outermost shell giving an effective nuclear charge of _______ . For the Ca2+ ion [Ar] or([Ne] 3s23p6) 99 pm is the radius. There are still 20 protons in the nucleus, but now there are only 10 shielding electrons giving an effective nuclear charge of +10.
An increase in the ENC gives a greater attraction on the remaining electrons, making the species ________ . 2) The radius of an anion is always ________ than the covalent radius of the parent atom. For Example: F 1s22s22p5 72 pm, 9 protons 2 electrons shielding and 7 valence electrons. for F- 1s22s22p6 136 pm still 9 protons, and 2 shielding, but now there are 8 electrons in the outermost shell ³seeing´ 7 positive charges in the center.
There is a decrease in the effective nuclear charge "felt" by each outermost electron, 7p/7e vs 7p/8e and a greater repulsive force among the electrons accounts for this increase in size trend. Why greater repulsive force? Arrange the following in order of increasing size: O2- Na+ Mg2+ F- Ne Al3+ N3a) What is special about this series of ions and atom?
They all have the same number of electrons. It is an isoelectronic series. b) We put them in the order of their increasing atomic number, the order as they appear on the periodic chart:
the greater the nuclear charge exerting the attraction on the same number of electrons equals a smaller size:
The order of increasing size would be: _____________________________________ . H) General Statements about ionic compounds: 1) Ionic compounds are electrically neutral the number of positive charges equals the number of negative charges. 2) Ionic compounds have formulas which are empirical formulas. They contain no molecules. 3) The glue which holds the ions together is a strong electrical attraction between ions of opposite charge.
IV. COVALENT BONDS A) Covalent bonds are formed when 2 atoms share 1 or more pairs of electrons achieving the lowest possible energy. B) Atoms which form covalent bonds are very similar in their tendency to gain or lose electron. In general, covalent bonds are formed between nonmetal atoms. C) Lewis structures, which are very elementary models of molecules, work well for lots of molecules especially organic molecules.
D) A Lewis Structure (an electron dot formula) is a representation of covalent bonding using Lewis dot symbols in which shared electron pairs are shown as a pair of dots or a line between two atoms. The lone pairs of electrons are shown as pairs of dots on individual atoms. E) Many molecules obey what is known as the octet rule. That is, when atoms form covalent bonds there is a tendency to share enough electrons so that each atom is surrounded by 8 electrons. (Our magic number)
1) Exceptions - fewer than 8 are required for H, He, Li, Be, and B. H - 2; He - 2; Li is usually ionic where it loses 1 electron, Be when covalent shares 4, and B can sometimes share 6. 2) More than 8 electrons are shared by some atoms especially those atoms beyond the second row which have d orbitals available for bonding. More than 4 positions are available for bonding.
V. LEWIS STRUCTURE BUILDING GAME WITH RULES A) You must determine enough of the structure so that you know which atoms are bonded to which atoms. This comes from your knowledge of what follows or if there are exceptions then I will have to tell you. You will have to make educated guesses based on :
1) H and F can only form ONE bond, therefore they cannot be in the middle of a molecule, they must be on the end of a molecule. H2O must be: not H-H-O BF3 must be:
2) The Central atom of a molecule or polyatomic ion (atoms held together with covalent bonds with extra electrons provided by metal atoms being converted into positive ions) is usually the one that there is only one in the formula.
3) It is very unusual for oxygen atoms to bond together. DON'T DRAW S-O-O-O-O for SO42Do draw:
4) In carbon compounds, the compounds of organic chemistry, the carbon atoms can bond to carbon atoms and each carbon atom generally has 4 bonds altogether.
In organic compounds we find C atoms forming 2 bonds with O atoms, 1 bond with H atoms and atoms of the halogens, 3 bonds with N atoms, 1, 2, or 3 bonds with other C atoms. B) Use the Periodic Table to determine the total number of electrons available for distribution among the atoms in a molecule. 1) Example - CH4 C is in Group 4 = 4 e H is in Group 1 X 4 = 4e. 4e + 4e = 8e
Put 8 dots around the C in the middle and attach an H to the C with each pair of dots. This will give each C 8 electrons to satisfy the octet rule, and each H 2 electrons which will satisfy it. This gives the following structure when the lines are substituted for the dots.
2) for SO42- we obtain the following: S and O are both in group 6 so we multiply 5 atoms times 6e/atom to obtain 30 electrons + 2 for the -2 charge (2 extra electrons) = 32e. We distribute them so that the structure is:
For atoms which require 8e, find the number of electrons shared between atoms by taking 8 times the number of atoms in the molecule requiring 8e and subtract the number available from it to find the number of bonds. CF4 C contributes 4 electrons, the 4 F's each contribute 7, making available 28 + 4 = 32 electrons are available. There are 5 atoms in the molecule which each require 8 electrons to complete their octet which means 40 electrons are required.
Needed minus available = shared 40 - 32 = 8 which are shared, which means 4 bonds are needed since there are 2 electrons per bond. We put C in the middle, allowing each F to bond with it. This uses 8 electrons. There are then 32 - 8 = 24 to place around the 4 F's. This allows 6 e's per F which will complete the octet around each F.
D) For some molecules the above calculation leads to a situation where electrons are in short supply. When this occurs, multiple bonds are required. For example, N2. Each N contributes 5 electrons making a total of 10 available. Each N requires 8 electrons making total of 16 required. 16 - 10 = 6 divided by 2 electrons per bond = 3 bonds required. we must put the three bonds between the two nitrogen atoms as follows:
For SO2, we obtain the following: The S and the O are in the some column of the periodic chart so they each contribute_______. Each S and O require 8 electrons for a total of _____________.
24 electrons needed with 18 available leaving 6 electrons to be shared divided by 2 giving 3 bonds. Where to put them? S must be in the middle so the following is a possibility:
BUT WHAT ABOUT THE FOLLOWING:
This would indicate that one bond would be shorter than the other since double bonds are shorter than the single bonds. The experimental evidence is that both bonds are identical. According to the theory then, one of the bonding pairs in sulfur dioxide is spread over a number of atoms rather than localized between 2 atoms. This is called delocalized bonding and in the Lewis concept both structures must be shown.
A single dot formula cannot properly describe delocalized bonding. Instead a resonance description is used. For the CO32- ion we obtain the following:
We obtain three required resonance structures as follows:
VI. SOME BOND PROPERTIES A) Polarity B) Bond Strength C) Bond Length VII. Bond Polarity A) Bond Polarity is a useful concept for describing entire molecules as well as individual bonds.
B) H2 is the simplest molecule - a nonpolar molecule since the center of positive charge coincides with the center of negative charge. H:H
C) Covalent bonds between two different atoms are generally polar H-F H-Cl
D) Electrons are not shared equally between the bonded atoms. A polar covalent bond is a covalent bond in which the electrons spend more time in the vicinity of one of the atoms than another. E) H-Cl The two bonding electrons spend more time in the vicinity of the Cl atom than the H atom.
The arrow indicates that HCl possesses a dipole moment in the direction of the Cl atom, the partially negatively charged one.
You have a polar molecule when the _____ and ______ charges do not _____________ . F) We need a criterion by which to predict whether a bond is nonpolar covalent, polar covalent, or ionic. G) We have to think of bonding type as a continuum from normal (nonpolar) covalent to polar covalent to ionic.
H) the criterion we will use is the difference in electronegativity. 1) What is electronegativity?
2) It is a measure of how strongly an atom attracts the bonding electrons in a chemical bond. The higher the electronegativity, the stronger an atom's attraction for bonding electrons. 3) We will use the Pauling Scale of Electronegativities - there are other scales known and used.
4) Electronegativity increases______________. We will ignore the noble gases since their compounds are of recent origin. 5) Electronegativity decreases _____________ . 6) Of the commonly occurring elements, this makes _________ the most electronegative and ______________the least.. 7) Atoms of the same electronegativity joined by a covalent bond give an electronegativity difference of zero - i.e. H2 2.1 - 2.1 = 0. This indicates a normal nonpolar covalent bond.
8) Electronegativity differences greater than zero and less than two usually give a polar covalent bond. (Some books use up to a 0.5 difference as still being nonpolar because C-H bonds are generally considered nonpolar.) 9) Electronegativity differences of 2 or greater are associated with ionic bonds. Remember this is an attempt at classification and the real world just doesn't obey these manmade rules, so there will be exceptions. 10) EXAMPLES
VIII. FORMAL CHARGE AND LEWIS FORMULAS
A) The formal charge of an atom in a Lewis formula is the hypothetical charge you obtain by assuming that bonding electrons are equally shared between bonded atoms and that the electrons of each lone pair belong completely to one atom. B) Formal charge = # of electrons in the valence shell minus the number of bonds to the atom minus number of unshared electrons surrounding atom.
C) Two rules that are useful in writing Lewis formulas using the concept of Formal Charge are: 1. When several Lewis Structures can be written for a given compound, the one which contains the smallest formal charges is preferred. 2. When two proposed Lewis formulas for a molecule have the same magnitudes of formal charges, choose the one with the negative formal charge on the more electronegative atom.
3. Example: H2SO4
The formal charge on S is ________. The formal charge on the O's connected to the S and H is ___________. The formal charge on the O's connected to the S only is _____________.
Note that the sum of the formal charges is zero as it should be for a neutral molecule. It should also be noted that a structure for H2SO4 can be written that has zero formal charges. This is accomplished by putting double bonds between the S and O atoms which do not have H's attached to them.
IX. BOND LENGTH A) Bond length is the distance between the nuclei in a bond. These are determined by Xray diffraction. This is always an average distance, because atoms are always vibrating with respect to each other, so there is really no fixed distance between any two nuclei. B) Bond length decreases from single to double to triple bonds. C-C (154 pm) C=C (133 pm) Triple bonded carbon atoms (120 pm).
X. BOND STRENGTH A) Bond energy is the average enthalpy change for the breaking of an A-B bond in a molecule in the gas phase. B) For example: CH4 C(g) + 4 H(g) H = 1662kJ
Because 4 C-H bonds were broken, we obtain an average value of the bond energy for the CH bond as ¼ 1662 kJ = 416 kJ. From other molecules containing C-H bonds we obtain an average value found in the book as 411 kJ
C) Bond energy is a measure of the strength of a bond: the larger the B.E. the stronger the chemical bond. C-C is weaker than C=C, and that in turn is weaker than C triple bond C. D) You can use a table of B.E's. to estimate heats of reaction. The enthalpy of reaction is approximately equal to the sum of the bond energies for bonds broken (always endothermic) minus the sum of the bond energies for the bonds formed (always exothermic - the negative of the B.E.).
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