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EXTRA HOMEWORK 4A 1. Name the following complex ions. (a) Co(NO2)63- (b) Ni(CO)42+ (c) Ti(en)2Cl22+ (d) UF62- 2. Give the formula for the following complex ions. (a) hexacyanoplumbate(II) (b) tetraamminediaquanickel(II) (c) dibromobis(ethylenediamine)platinum(IV) (d) diaquatetrahydroxoaluminate(III) 3. Name the following coordination compounds. (a) [Co(NH3)6]Cl3 (b) [Co(en)2Cl2]Cl (c) K2[CoCl4] (d) Ir(NH3)3Cl3 4. Identify each ligand as monodentate, bidentate, tridentate, etc. (a) Cl- (b) H2N(CH2CH2)NH(CH2CH2)NH2 (diethylenetriamone) (c) H2O (d) (O2CCH2)2N(CH2CH2)N(CH2CO2)24- (EDTA) 5. Draw and name all the geometrical isomers of square planar complex PtCl2BrI 6. Draw and name all the geometrical isomers of Co(en)2(H2O)23+ 7. Which one of the geometrical isomers in question 6 exhibits optical isomerism? Draw the two optical isomers. EXTRA HOMEWORK 4B 1. Write the complete formation reaction for each of the following complex ions (a) Zn(NH3)42+ (b) V(C2O4)33- 2. The copletel formation constant for Ni(NH3)62+ is 6.0 x 108. Calculate the concentration of Ni2+ ions in a solution that was originally 0.10 M Ni2+ and 3.00 M NH3. 3. (a) Calculate the molar solubility of AgI in pure water if the Ksp for AgI is 1.5 x 10-16. (b) Calculate the molar solubility of AgI in 3.0 M NH3 if the overall formation constant for Ag(NH3)2+ is 1.7 x 107. *4. Calculate the concentration of Pb2+ in each of the following. (a) A saturated solution of Pb(OH)2, Ksp = 1.2 x 10-15. (b) A saturated solution of Pb(OH)2, buffered at pH = 13.00 (c) Solutions of ethylenediamnetetraacetate (EDTA4-) are used treat heavy metal poisoning by removing the heavy metal in the form of a soluble complex ion. The reaction of EDTA4- with Pb2+ is Pb2+ (aq) + EDTA4- (aq) → PbEDTA2- (aq) K = 1.1 x 1018 Consider a solution with 0.010 mol Pb(NO3)2 added to 1.0 L of an aqueous solution buffered at pH = 13.00 and containing 0.050 M Na4EDTA. Does Pb(OH)2 precipitate from the solution? EXTRA HOMEWORK 4C 1. Draw the d-orbital splitting diagrams for the octahedral complex ions of each of the following, identify each as paramagnetic or diamagnetic, and if the ion can be either high-spin or low-spin, predict which would be most stable (a) V2+ (b) Fe2+ (low and high spin) (c) Mn2+ (low and high spin) (d) Cu+ 2. Draw the expected d-orbital splitting for Pd4+ assuming the following geometries, and predict which geometry would be the most stable (a) octahedral (b) tetrahedral (c) square planar (d) linear- 3. Identify each ligand as strong field-ligand or a weak-field ligand (a) F- (b) NO2- 4. Both Co(H2O)63+ and Fe(H2O)62+ have six ligands. The first complex ion is paramagnetic and the second is diamagnetic. Identify the complexes as either high-spin or low-spin. 5. Answer the following concerning the complex ions tris(oxalato)ferrate(II) and tris(ethylenediamine)iron(II) (a) give the formula of each complex ion (b) give the electron configuration of the iron ion in each (c) identify each ligand as strong-field or weak-field (d) draw the d-orbital splitting pattern for each the iron ion in each complex (e) identify the complex ion as paramagnetic or diamagnetic (f) identify the complex ion that produces a red solution, and the complex ion that produces a blue solution 6. The diamminesilver ion aborbs electromagnetic radiation with a wavelength of 2.3 x 10-6 m. Determine the splitting energy of the complex ion. 7. Identify the Lewis acid and Lewis base in each of the following reactions. (a) Ni2+ (aq) + 6CO (g) ⇆ Ni(CO)62+ (aq) (b) Al(OH)3(H2O)3 (aq) + OH- (aq) ⇆ Al(OH)4(H2O)2- (aq) + H2O (l) (c) BH3 (g) + PH3 (aq) ⇆ BH3PH3 (aq) (d) CO2 (g) + H2O (l) ⇆ H2CO3 (aq) EXTRA HOMEWORK 4D 1. Does temperature affect the rate of a chemical reaction? Where does it occur in the rate law? 2. The reaction: 2CO + O2 → 2CO2 is first order in oxygen concentration and first order in carbon monoxide concentration. Write the rate expression for this reaction. 3. For the reaction in question 2, if the initial reaction rate is -0.50 M CO/min, what would be the intial reaction rate in M O2/min and M CO2/min? 4. For the reaction in aqueous solution: S2O82- + 2I- → 2SO42- + I2 the following data were collected at the same temperature Initial [S2O82-] Initial [I-] Initial Rate (M/min) 0.00010 0.00020 0.00020 0.010 0.010 0.005 0.65 x 10-6 1.30 x 10-6 0.65 x 10-6 (a) What is the rate expression for this reaction? (b) What is the overall order of the reaction? (c) Calculate the numerical value of the rate constant, with units. (d) What will be the initial rate if the initial concentration of S2O82- is 0.00015 M and the initial concentration of I- is 0.005 M? 5. For the reaction: 2NO + Br2 → 2NOBr the following data were collected at the same temperature Initial [NO] 0.10 0.10 0.20 Initial [Br2] Initial Rate (M/min) 0.10 0.20 0.20 0.18 0.36 1.44 (a) What is the rate expression for this reaction? (b) What is the order of this reaction? (c) Calculate the numerical value of the rate constant, with units. (d) What will be the initial rate if the initial concentration of NO is 0.15 M and the initial concentration of Br2 is 0.25 M? (continued on next page) *6. For the reaction: NH4+ + NO2- → N2 + H2O the following data were collected at the same temperature [NH4+] [NO2-] 0.50 0.50 1.0 0.50 1.0 2.0 Initial Rate (M/min) 0.015 0.030 0.12 (a) What is the rate expression for this reaction? (b) What is the order of this reaction? (c) Calculate the numerical value of the rate constant, with units. *7. For the gas phase reaction: 2NO + O2 → 2NO2 the following data were collected at the same temperature Initial pNO (atm) 0.20 0.40 0.80 Initial pO2 (atm) Initial Rate (atm/min) 1.8 x 10-4 7.2 x 10-4 57.6 x 10-4 0.30 0.30 0.60 Since the pressure of a gas is directly proportional to the concentration of gas, we can express the rate law for a gaseous reaction in terms of partial pressures. (a) What is the rate expression for this reaction? (b) What is the order of this reaction? (c) Calculate the numerical value of the rate constant, with units. *8. For the catalyzed reaction: 2N2 + O2 → 2N2O the following data were collected at the same temperature [N2] [O2] 0.50 1.0 1.0 0.50 0.50 1.0 Initial Rate (M/min) (a) What is the rate expression for this reaction? (b) What is the order of this reaction? (c) Calculate the numerical value of the rate constant, with units. 0.018 0.072 0.072 EXTRA HOMEWORK 4E 1. For the decomposition of ammonia, the following data were measured. Time (s): Concentration (M): 0.00 0.500 10.0 0.400 20.0 0.320 30.0 0.256 For this first-order reaction, write the rate expression and calculate the rate constant, k. 2. The reaction: CCl2F2 → CF2Cl + Cl is a first order reaction with the rate constant k = 1.9 x 10-3 s-1 at 263 K. What fraction of CCl2F2. is decomposed at 263 K for 60.0 seconds? 3. Given the following data for the reaction: C2H5OH → C2H4 + H2O Time (s): C2H5OH Pressure (torr): 0 250. 200. 171 400. 130. 600. 105 Since the pressure of a gas is directly proportional to the concentration of gas, we can express the rate law for a gaseous reaction in terms of partial pressures. (a) What is the order of the reaction? (b) Calculate the value of the specific rate constant. (c) Predict the pressure of C2H5OH after 900. seconds. 4. Given the following data for the reaction: 2N2O5 → 4NO2 + O2 Time (s): Concentration (M): 0 0.800 10. 0.667 (a) What is the order of the reaction? (b) Predict the concentration of N2O5 after 40. seconds. 20. 0.571 30. 0.500 EXTRA HOMEWORK 4F 1. The reaction CO + NO2 → CO2 + NO occurs via the 2-step mechanism (1) NO2 + NO2 (2) NO3 + CO → NO3 + NO → NO2 + CO2 slow reaction, with rate constant k1 fast reaction, with rate constant k2 Deduce the rate equation that agrees with this mechanism. 2. A potential mechanism for the decomposition of N2O4 is: (1) (2) (3) N2O4 ↔ 2NO2 NO2 → N + O2 N + NO2 → N2 + O2 equilibrium, with equilibrium constant K1 slow reaction, with rate constant k2 fast reaction, with rate constant k3 Deduce the rate equation that agrees with this mechanism. 3. Explain the two components, A and e-Ea/RT, that make up the specific rate constant. 4. How can Ea be calculated from the heat of a reaction, ΔHº? 5. How does a catalyst affect the equilibrium conditions of a reacting system? 6. Calculate the activation energy of a reaction whose rate exactly triples between 20.ºC and 30.ºC. 7. The rate constant for the decomposition of HI at 629 K is 3.02 x 10-5 s-1. Calculate the rate constant at 716 K if the activation energy is 189 kJ. *8. The reaction: H2 + Cl2 → 2HCl occurs explosively in the presence of light. The explosion takes place by a chain reaction, and is initiated by the formation of either hydrogen atoms or chlorine atoms. Using the bond energies found in Table 8.4 of the text book, calculate the wavelength of light needed to initalte the reaction with either the hydrogen atoms or the chlorine atoms. *9. For the decomposition of CH3I at 285 K, the energy of activation is 180 kJ. Assuming that the energy of activation is constant, calculate the percent increase in the fraction of molecules with energy greater than Ea when the temperature is increased to 300. K. EXTRA 4A ANSWERS 1. (a) hexanitritocobaltate(III) (e) dichlorobis(ethylenediamine)titanium(IV) 2. (a) Pb(CN)64- (b) Ni(NH3)4(H2O)22+ (b) tetracarbonylnickel(II) (d) hexafluorouranate(IV) (c) PtBr2(en)22+ (d) Al(H2O)2(OH)4- 3. (a) hexaamminecobalt(III) chloride (b) dichlorobis(ethylenediamine)cobalt(III) chloride (e) potassium tetrachlorocobaltate(II) (f) triamminetrichloroiridium(III) 4. (a) monodentate (b) tridentate (c) monodentate (d) hexadentate 5. trans-bromodichloroiodoplatinum(IV) cis-bromodichloroiodoplatinum(IV) 6. trans-diaquabis(ethylenediamine)cobalt(III) cis-diaquabis(ethylenediamine)cobalt(III) 7. cis-diaquabis(ethylenediamine)cobalt(III) EXTRA 4B ANSWERS 1. (a) Zn2+ (aq) + 4NH3 (aq) → Zn(NH3)42+ (aq) (b) V3+ (aq) + 3C2O42- (aq) → V(C2O4)33- (aq) 2. 8.7 x 10-13 M 3. 1.2 x 10-8 M *4. (a) 6.7 x 10-6 M (b) 1.5 x 10-4 M (b) 1.2 x 10-13 M (c) no EXTRA 4C ANSWERS 1. (a) (b) (c) (d) (continued on next page) 2. (a) octahedral (b) tetrahedral 3. (a) weak-field (b) strong-field 4. (a) high-spin (b) low-spin 5. (a) Fe(C2O4)34- (c) square planar (d) linear Fe(NH2CH2CH2NH2)32+ (g) [Ar]3d6 [Ar]3d6 (h) strong weak (d) (i) diamagnetic paramagnetic (j) red blue 6. 8.6 x 10-20 J 7. (a) acid – Ni2+, base – CO (c) acid – BH3, base – PH3 (b) acid – Al(OH)3(H2O)3, base – OH(d) acid – CO2, base – H2O EXTRA 4D ANSWERS 1. Yes, in the specific rate constant 2. Rate = k[O2][CO] 3. -0.25 M O2/min +0.50 M CO2 M/min 4. (a) Rate = k[S2O82-][I-] (b) 2nd order (c) 0.65 M-1min-1 (d) 5 x 10-7 M/min 5. (a) Rate = k[NO] 2[Br2] (b) 3rd order (c) 180 M-2min-1 (d) 1.0 M/min EXTRA 4E ANSWERS 1. Rate = k[NH3] 0.0223 s-1 2. 0.11 or 11% 3. (a) 2nd order (b) 9.2 x 10-6 (s-1torr-1) (c) 81 torr 4. (a) 2nd order (b) 0.444 M *5. (a) Rate = k[NH4+][NO2-] (b) 2nd order (c) 6.0 x 10-2 min-1M-1 *6. (a) Rate = k[NO]2[O2] (b) 3rd order (c) 1.5 x 10-2 min-1atm-2 *7. (a) Rate = k[N2]2 (b) 2nd order (c) 7.2 x 10-2 min-1M-1 EXTRA 4F ANSWERS 1. Rate = k[NO2]2 2. Rate = k[N2O4]½ 3. Z is the collision frequency, and e-Ea/RT is the fraction of the collisions that are successful in producing a chemical change 4. it can’t 5. A cataslyst does not affect the equilibrium conditions of a reacting system 6. 81 kJ/mol 7. 2.4 x 10-3 s-1 *8. 2.77 x 10-7 m or 5.01 x 10-7 m *9. 4,500%