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Chemical Bonding and Molecular Structure (Chapter 9). Ionic vs. covalent bonding Molecular orbitals and the covalent bond (Ch. 10) Valence electron Lewis dot structures octet vs. non-octet resonance structures formal charges VSEPR - predicting shapes of molecules Bond properties
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Chemical Bonding and Molecular Structure (Chapter 9) • Ionic vs. covalent bonding • Molecular orbitals and the covalent bond (Ch. 10) • Valence electron Lewis dot structures • octet vs. non-octet • resonance structures • formal charges • VSEPR - predicting shapes of molecules • Bond properties • bond order, bond strength • polarity, electronegativity Chemical Equilibrium
Bond Polarity HCl is POLAR because it has a positive end and a negative end (partly ionic). Polarity arises because Cl has a greater share of the bonding electrons than H. Calculated charge by CAChe: H (red) is +ve (+0.20 e-) Cl (yellow) is -ve (-0.20 e-). (See PARTCHRG folder in MODELS.) Chemical Equilibrium
Bond Polarity (2) • Due to the bond polarity, the H—Cl bond energy is GREATER than expected for a “pure” covalent bond. BOND ENERGY “pure” bond 339 kJ/mol calculated real bond 432 kJ/mol measured Difference 92 kJ/mol. This difference is the contribution of IONIC bonding It is proportional to the difference in ELECTRONEGATIVITY, c. Chemical Equilibrium
Electronegativity, c c is a measure of the ability of an atom in a molecule to attract electrons to itself. Concept proposed by Linus Pauling (1901-94) Nobel prizes: Chemistry (54), Peace (63) See p. 425; 008vd3.mov (CD) Chemical Equilibrium
Electronegativity, c Figure 9.7 • F has maximum c. • Atom with lowest c is the center atom in most molecules. • Relative values of c determines BOND POLARITY (and point of attack on a molecule). Chemical Equilibrium
Bond Polarity Which bond is more polar ? (has larger bond DIPOLE) O—H O—F c H 2.1 O F 3.5 4.0 c(A) - c(B)3.5 - 2.1 Dc 1.4 3.5 - 4.0 0.5 (O-H) > (O-F) Therefore OH is more polar than OF Also note that polarity is “reversed.” Chemical Equilibrium
Symmetric molecules Molecular Polarity • Molecules such as HCl and H2O are POLAR • They have a DIPOLE MOMENT. • Polar molecules turn to align their dipole with an electric field. • A molecule will be polar ONLY if a) it contains polar bonds AND b) the molecule is NOT “symmetric” Chemical Equilibrium
Molecular Polarity: H2O Water is polar because: a) O-H bond is polar b) water is non-symmetric The dipole associated with polar H2O is the basis for absorption of microwaves used in cooking with a microwave oven Chemical Equilibrium
HBF2 is polar BF3 is NOT polar Molecular Polarity in NON-symmetric molecules B—F bonds are polar molecule is NOT symmetric Atom Chg. B +ve 2.0 H +ve 2.1 F -ve 4.0 B +ve F -ve B—F bonds are polar molecule is symmetric Chemical Equilibrium
Fluorine-substituted Ethylene: C2H2F2 C—F bonds are MUCH more polar than C—H bonds. (C-F) = 1.5, (C-H) = 0.4 CIS isomer • both C—F bonds on same side molecule is POLAR. TRANS isomer • both C—F bonds on opposite side molecule is NOT POLAR. Chemical Equilibrium
CHEMICAL EQUILIBRIUMChapter 16 • equilibrium vs. completed reactions • equilibrium constant expressions • Reaction quotient • computing positions of equilibria: examples • Le Chatelier’s principle - effect on equilibria of: • addition of reactant or product • pressure • temperature YOU ARE NOT RESPONSIBLE for section 16.7 (relation to kinetics) Chemical Equilibrium
Co(H2O)6Cl2 (aq) Co(H2O)6Cl2 (aq) + 2 H2O Properties of an Equilibrium Equilibrium systems are • DYNAMIC (in constant motion) • REVERSIBLE • can be approached from either direction 16_CoCl2.mov (16z01vd1.mov) Pink to blue Co(H2O)6Cl2 ---> Co(H2O)4Cl2 + 2 H2O Blue to pink Co(H2O)4Cl2 + 2 H2O ---> Co(H2O)6Cl2 Chemical Equilibrium
FeCl3 (aq) NaSCN(aq) Fe3+ + SCN- FeSCN2+ FeSCN (aq) Chemical Equilibrium • After a period of time, the concentrations of reactants and products are constant. • The forward and reverse reactions continue after equilibrium is attained. 16_FeSCN.mov 16m03an1.mov Chemical Equilibrium
Chemical Equilibria CaCO3(s) + H2O(l) + CO2(g) Ca2+(aq) + 2 HCO3-(aq) At a given T and pressure of CO2, [Ca2+] and [HCO3-] can be found from the EQUILIBRIUM CONSTANT. Chemical Equilibrium
a A + b B c C + d D THE EQUILIBRIUM CONSTANT For any type of chemical equilibrium of the type the following is a CONSTANT (at a given T) : If K is known, then we can predict concentrations of products or reactants. Chemical Equilibrium
2 NOCl(g) 2 NO(g) + Cl2(g) Determining K Place 2.00 mol of NOCl is a 1.00 L flask. At equilibrium you find 0.66 mol/L of NO. Calculate K. Solution 1. Set up a table of concentrations: [NOCl] [NO] [Cl2] Before 2.00 0 0 Change -0.66 +0.66 +0.33 Equilibrium 1.34 0.66 0.33 Chemical Equilibrium
2 (0.66) (0.33) = 0.080 K = 2 (1.34) Calculate K from equil. [ ] 2 NOCl(g) 2 NO(g) + Cl2(g) [NOCl] [NO] [Cl2] Before 2.00 0 0 Change -0.66 +0.66 +0.33 Equilibrium 1.34 0.66 0.33 Chemical Equilibrium
S O O S(s) + O2(g) SO2(g) NH3(aq) + H2O(liq) NH4+(aq) + OH-(aq) Writing and ManipulatingEquilibrium Expressions Solids and liquids NEVER appear in equilibrium expressions. Chemical Equilibrium
S(s) + O2(g) SO2(g) [SO3] SO2(g) + 1/2 O2(g) SO3(g) K2 = [SO2][O2]1/2 [SO3] S(s) + 3/2 O2(g) SO3(g) [O2]3/2 Manipulating K: adding reactions K1 = [SO2] / [O2] Adding equations for reactions NET EQUATION Ktot = ADD REACTIONS MULTIPLY K Ktot = K1 x K2 Chemical Equilibrium
S(s) + O2(g) SO2(g) SO2(g) S(s) + O2(g) Manipulating K: Reverse reactions Changing direction Chemical Equilibrium
Chemistry of Sulfur Elemental S : stable form is S8 (s) sources: desulfurizing natural gas roasting metal sulfides Oxides of S : SO2 (g) and SO3 (g) - significant in atmospheric pollution Industrially: Oxides generated as needed; ‘stored’ as the hydrate SO3(g) + H2O (l) H2SO4(aq) Sulfuric acid is HIGHEST VOLUME chemical (fertilizers, refining, manufacturing) Chemical Equilibrium
Manipulating K : Kp for gas rxns Concentration Units We have been writing K in terms of mol/L. These are designated by Kc But with gases, P = (n/V)•RT = conc • RT P is proportional to concentration, so we can write K in terms of PARTIAL PRESSURES. These constants are called Kp. Kc and Kp have DIFFERENT VALUES (unless same number of species on both sides of equation) Chemical Equilibrium
2 H2(g) + O2(g) 2 H2O (g) P(H2O)2 K = p P(H2)2P(O2) The Meaning of K 1. Can tell if a reaction is product-favored or reactant-favored. = 1.5 x 1080 K >> 1 Concentration of products is much greater than that of reactants at equilibrium. The reaction is stronglyproduct-favored. Chemical Equilibrium
AgCl(s) Ag+(aq) + Cl-(aq) Ag+(aq) + Cl-(aq) AgCl(s) Meaning of K: AgCl rxn Kc = [Ag+] [Cl-] = 1.8 x 10-5 K << 1 Conc. of products is much less than that of reactants at equilibrium. This reaction is strongly reactant-favored. What about the reverse reaction ? Krev = Kc-1 = 5.6x104. It is strongly product-favored. Chemical Equilibrium
n-butane iso-butane H H H CH3—C—CH3 CH3 —C —C —CH3 H H CH3 [iso] = 2.5 K = [n] Meaning of K : butane isomerization 2. Can tell if a reaction is at equilibrium. If not, which way it moves to approach equilibrium. If [iso] = 0.35 M and [n] = 0.25 M, is the system at equilibrium? If not, which way does the rxn “shift” to approach equilibrium? Chemical Equilibrium
[iso] 0.35 For n-Butane iso-Butane Q = = = 1.40 [n] 0.25 Q - the reaction quotient Q has the same form as K, . . . but uses existing concentrations All reacting chemical systems can be characterized by their REACTION QUOTIENT, Q. If Q = K, then system is at equilibrium. Q = 1.4 which is LESS THAN K =2.5 Reaction is NOT at equilibrium. To reach EQUILIBRIUM [Iso] must INCREASE and [n] must DECREASE. Chemical Equilibrium
Q/K 1 Q Q = K Typical EQUILIBRIUM Calculations 2 general types: a. Given set of concentrations, is system at equilibrium ? Calculate Q compare to K IF: Q > K or Q/K > 1 REACTANTS Q < K or Q/K < 1 PRODUCTS Q=K at EQUILIBRIUM Chemical Equilibrium
H2(g) + I2(g) 2 HI(g) Examples of equilibrium questions b. From an initial non-equilibrium condition, what are the concentrations at equilibrium? Place 1.00 mol each of H2 and I2 in a 1.00 L flask. Calculate equilibrium concentrations. Chemical Equilibrium
H2(g) + I2(g) 2 HI(g) Kc = 55.3 Step 1. Set up table to define EQUILIBRIUM concentrations in terms of initial concentrations and a change variable Initial 1.00 1.00 0 DEFINE x = [H2] consumed to get to equilibrium. Change -x -x +2x At equilibrium 1.00-x 1.00-x 2x [H2] [I2] [HI] Chemical Equilibrium
H2(g) + I2(g) 2 HI(g) Kc = 55.3 Step 1 Define equilibrium condition in terms of initial condition and a change variable [H2] [I2] [HI] At equilibrium 1.00-x 1.00-x 2x Step 2 Put equilibrium concentrations into Kc expression. Chemical Equilibrium
2x 7.44 = 1.00 - x H2(g) + I2(g) 2 HI(g) Kc = 55.3 Step 3. Solve for x. 55.3 = (2x)2/(1-x)2 In this case, take square root of both sides. Solution gives: x = 0.79 Therefore, at equilibrium [H2] = [I2] = 1.00 - x = 0.21 M [HI] = 2x = 1.58 M Chemical Equilibrium
EQUILIBRIUM AND EXTERNAL EFFECTS • The position of equilibrium is changed when there is a change in: • pressure • changes in concentration • temperature • The outcome is governed by LE CHATELIER’S PRINCIPLE Henri Le Chatelier 1850-1936 - Studied mining engineering - specialized in glass and ceramics. “...if a system at equilibrium is disturbed, the system tends to shift its equilibrium position to counter the effect of the disturbance.” Chemical Equilibrium
Shifts in EQUILIBRIUM : Concentration • If concentration of one species changes, concentrations of other species CHANGES to keep the value of K the same (at constant T) • no change in K - only position of equilibrium changes. ADDING PRODUCTS - equilibrium shifts to REACTANTS ADDING REACTANTS - equilibrium shifts to PRODUCTS - GAS-FORMING; PRECIPITATION REMOVING PRODUCTS - often used to DRIVE REACTION TO COMPLETION Chemical Equilibrium
n-Butane Isobutane [iso] = 2.5 K = [n] Effect of changed [ ] on an equilibrium Solution A. Calculate Q with extra 1.50 M n-butane. INITIALLY: [n] = 0.50 M [iso] = 1.25 M CHANGE: ADD +1.50 M n-butane What happens ? 16_butane.mov (16m13an1.mov) Q = [iso] / [n] = 1.25 / (0.50 + 1.50) = 0.63 Q < K . Therefore, reaction shifts to PRODUCT Chemical Equilibrium
B A Butane/Isobutane B. Solve for NEW EQUILIBRIUM - set up concentration table [n-butane] [isobutane] Initial 0.50 + 1.50 1.25 Change - x + x Equilibrium 2.00 - x 1.25 + x Solution x = 1.07 M. At new equilibrium position, [n-butane] = 0.93 M [isobutane] = 2.32 M. Equilibrium has shifted toward isobutane. Chemical Equilibrium
N2O4(g) 2 NO2(g) Effect of Pressure (gas equilibrium) Increase P in the system by reducing the volume. Increasing P shifts equilibrium to side with fewer molecules (to try to reduce P). Here, reaction shifts LEFT PN2O4 increases 16_NO2.mov (16m14an1.mov) PNO2 decreases See Ass#2 - question #6 Chemical Equilibrium
CO2(g) + H2O(liq) CO2(aq) + heat LOWER T HIGHER T EQUILIBRIUM AND EXTERNAL EFFECTS • Temperature change change in K • Consider the fizz in a soft drink Kc = [CO2(aq)]/[CO2(g)] • Change T: New equilib. position? New value of K? • Increase T • Equilibrium shifts left: [CO2(g)] [CO2 (aq)] • K decreases as T goes up. • Decrease T • [CO2 (aq)] increases and [CO2(g)] decreases. • K increases as T goes down Chemical Equilibrium
N2O4 + heat 2 NO2 (colorless) (brown) Temperature Effects on Chemical Equilibrium Kc = 0.00077 at 273 K Kc = 0.00590 at 298 K Horxn = + 57.2 kJ Increasing T changes K so as to shift equilibrium in ENDOTHERMIC direction 16_NO2RX.mov (16m14an1.mov) Chemical Equilibrium
EQUILIBRIUM AND EXTERNAL EFFECTS Catalytic exhaust system • Add catalyst ---> no change in K • A catalyst only affects the RATE of approach to equilibrium. Chemical Equilibrium
CHEMICAL EQUILIBRIUMChapter 16 • equilibrium vs. completed reactions • equilibrium constant expressions • Reaction quotient • computing positions of equilibria: examples • Le Chatelier’s principle - effect on equilibria of: • addition of reactant or product • pressure • temperature YOU ARE NOT RESPONSIBLE for section 16.7 (relation to kinetics) Chemical Equilibrium