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chemistry a molecular approach

Chemistry A Molecular Approach 5th Edition Nivaldo Tro - Solutions

Identify the central metal atom in each complex.a. Hemoglobinb. Carbonic anhydrasec. Chlorophylld. Iron blue
Hemoglobin exists in two predominant forms in our bodies.One form, known as oxyhemoglobin, has O2 bound to the iron and the other, known as deoxyhemoglobin, has a water molecule bound instead. Oxyhemoglobin is a low-spin complex that gives arterial blood its red color, and deoxyhemoglobin is a
What structural feature do hemoglobin, cytochrome c, and chlorophyll have in common?
Carbon monoxide and the cyanide ion are both toxic because they bind more strongly than oxygen to the iron in hemoglobin (Hb).Calculate the equilibrium constant value for this reaction:Does the equilibrium favor reactants or products? Hb + O₂ Hb+ CO: HbO₂ HbCO K = 2 x 10¹2 K = 1 X 10¹4
Recall that Cr and Cu are exceptions to the normal orbital filling, resulting in a [Ar] 4s13dx configuration.Write the ground state electron configuration for each species. Cr, Cr, Cr2+, Cr³+ a. b. Cu, Cut, Cu²+
Most of the second row transition metals do not follow the normal orbital filling pattern. Five of them—Nb, Mo, Ru, Rh, and Ag—have a [Kr] 5s14dx configuration and Pd has a [Kr] 4d10 configuration.Write the ground state electron configuration for each species. a. Mo, Mot, Ag, Ag+ 3+ b. Ru,
Draw the Lewis diagrams for each ligand. Indicate the lone pair(s) that may be donated to the metal. Indicate any you expect to be bidentate or polydentate.a. CN¯b. Bipyridine (bipy), which has the following structure:c. NO2¯ FN N
Draw the Lewis diagrams for each ligand. Indicate the lone pair(s) that may be donated to the metal. Indicate any you expect to be bidentate or polydentate.a. NH3 b. SCN¯ c. H2O
Amino acids, such as glycine (gly), form complexes with the trace metal ions found in the bloodstream. Glycine, whose structure is shown here, acts as a bidentate ligand coordinating with the nitrogen atom and one of the oxygen atoms.Draw all the possible isomers of:a. Square planar [Ni(gly)2]b.
List all the different formulas for an octahedral complex made from a metal (M) and three different ligands (A, B, and C).Describe any isomers for each complex.
Oxalic acid solutions remove rust stains. Draw a complex ion that is likely responsible for this effect. Does it have any isomers?
W, X, Y, and Z are different monodentate ligands.a. Is the square planar [NiWXYZ]2+ optically active?b. Is the tetrahedral [ZnWXYZ]2+ optically active?
Hexacyanomanganate(III) ion is a low-spin complex. Draw the crystal field splitting diagram with electrons filled in appropriately.Is this complex paramagnetic or diamagnetic?
Draw the structures of all the geometric isomers of [Ru(H2O)2(NH3)2Cl2]+ . Draw the mirror images of any that are chiral.
A 0.32 mol amount of NH3 is dissolved in 0.47 L of a 0.38 M silver nitrate solution. Calculate the equilibrium concentrations of all species in the solution.
When a solution of PtCl2 reacts with the ligand trimethylphosphine, P(CH3)3, two compounds are produced. The compounds share the same elemental analysis: 46.7% Pt; 17.0% Cl; 14.8% P; 17.2% C; 4.34% H. Determine the formula, draw the structure, and give the systematic name for each compound.
Draw a crystal field splitting diagram for a trigonal planar complex ion. Assume the plane of the molecule is perpendicular to the z-axis.
Draw a crystal field splitting diagram for a trigonal bipyramidal complex ion. Assume the axial positions are on the z-axis.
Sulfide (S2-) salts are notoriously insoluble in aqueous solution. a. Calculate the molar solubility of nickel(II) sulfide in water. Ksp(NiS) = 3 x 10-16 b. Nickel(II) ions form a complex ion in the presence of ammonia with a formation constant (K) of 2.0 x 108: Ni²+ + 6 NH3 [Ni(NH3)6]²+.
Calculate the solubility of Zn(OH)2(s) in 2.0 M NaOH solution. You must take into account the formation of Zn(OH)4², 2 x 10¹5. which has a Kf =
Explain why [Ni(NH3)4]2+ is paramagnetic, while [Ni(CN)4]2- is diamagnetic.
Halide complexes of metal M of the form [MX6]3- are found to be stable in aqueous solution. But it is possible that they undergo rapid ligand exchange with water (or other ligands) that is not detectable because the complexes are less stable. This property is referred to as their lability. Suggest
The Kf for [Cu(en)2]2+ is much larger than the one for [Cu(NH3)4]2+.This difference is primarily an entropy effect. Explain why and calculate the difference between the ΔS° values at 298 K for the complete dissociation of the two complex ions.
When solid Cd(OH)2 is added to a solution of 0.10 M NaI, some of it dissolves. Calculate the pH of the solution at equilibrium
Two ligands, A and B, both form complexes with a particular metal ion. When the metal ion complexes with ligand A, the solution is green. When the metal ion complexes with ligand B, the solution is violet. Which of the two ligands results in the larger Δ ?
Which element has the higher ionization energy, Cu or Au?
The complexes of Fe3+ have magnetic properties that depend on whether the ligands are strong or weak field. Explain why this observation supports the idea that electrons are lost from the 4s orbital before the 3d orbitals in the transition metals.
Choose a row of the transition metals in the periodic table. Have each group member look up and graph (where appropriate) a separate trend for the elements in that row, choosing from electron configuration, atomic size, ionization energy, and electronegativity.Each member should present a graph to
Have each group member write down the names and formulas for two coordination compounds. Taking turns, show each formula to the group and have the rest of the group name the compound, with each member contributing one step in the process.Once all group members have had their formulas named, repeat
Working individually, draw a pair of coordination compounds that are isomers. Take turns showing your drawings to the group and have them identify the type of isomerism and the reasons your drawing demonstrates that type of isomerism. If your group misidentifies your type of isomerism, rather than
Divide the electron configurations d1 through d10 among the group members so that every configuration is assigned to at least two group members. Working individually, draw the orbital diagram for the configurations assigned to you, including both high-spin and low-spin diagrams where possible.
Working individually, review one of the applications of coordination complexes. Without referring to the text or mentioning the key words in the heading of the subsection, describe the application you reviewed. As group members each describe the application they reviewed, take turns attempting to
Many aqueous solutions of complex ions display brilliant colors that depend on the identities of the metal ion and ligand(s). Some ligands bind selectively to certain metal ions, producing complex ions with characteristic colors. These distinctive complex ions serve as qualitative indicators for
Solve an equilibrium problem (using an ICE table) to calculate the pH of each solution.a. 0.18 M CH3NH2b. 0.18 M CH3NH3Clc. A mixture that is 0.18 M in CH3NH2 and 0.18 M in CH3NH3C
The fluids within cells are buffered by H2PO4– and HPO42–.a. Calculate the ratio of HPO42– to H2PO4– required to maintain a pH of 7.1 within a cell.b. Could a buffer system employing H3PO4 as the weak acid and H2PO4– as the weak base be used as a buffer system within cells? Explain.
Write balanced equations and expressions for Ksp for the dissolution of each ionic compound. a. BaSO4b. PbBr2c. Ag2CrO4
Sketch the titration curve from Problem 123 by calculating the pH at the beginning of the titration, at one-half of the equivalence point, at the equivalence point, and at 5.0 mL beyond the equivalence point. Pick a suitable indicator for this titration from Table 18.1.Problem 123A 0.552-g sample
A 0.552-g sample of ascorbic acid (vitamin C) was dissolved in water to a total volume of 20.0 mL and titrated with 0.1103 M KOH. The equivalence point occurred at 28.42 mL. The pH of the solution at 10.0 mL of added base was 3.72. From this data, determine the molar mass and Ka for vitamin C.
One of the main components of hard water is CaCO3. When hard water evaporates, some of the CaCO3 is left behind as a white mineral deposit. If a hard water solution is saturated with calcium carbonate, what volume of the solution has to evaporate to deposit 1.00 * 102 mg of CaCO3?
Gout—a condition that results in joint swelling and pain—is caused by the formation of sodium urate (NaC5H3N4O3) crystals within tendons, cartilage, and ligaments. Sodium urate precipitates out of blood plasma when uric acid levels become abnormally high. This sometimes happens as a result of
Pseudogout, a condition with symptoms similar to those of gout (see Problem 126), is caused by the formation of calcium diphosphate (Ca2P2O7) crystals within tendons, cartilage, and ligaments. Calcium diphosphate will precipitate out of blood plasma when diphosphate levels become abnormally high.
Calculate the solubility of silver chloride in a solution that is 0.100 M in NH3.
Calculate the solubility of CuX in a solution that is 0.150 M in NaCN. Ksp for CuX is 1.27 * 10-36.
Aniline, abbreviated ϕNH2, where ϕ is C6H5, is an important organic base used in the manufacture of dyes. It has Kb = 4.3 * 10-10. In a certain manufacturing process, it is necessary to keep the concentration of ϕNH3+ (aniline’s conjugate acid, the anilinium ion) below 1.0 * 10-9 M in a
The Kb of hydroxylamine, NH2OH, is 1.10 * 10-8. A buffer solution is prepared by mixing 100.0 mL of a 0.36 M hydroxylamine solution with 50.0 mL of a 0.26 M HCl solution. Determine the pH of the resulting solution.
A 0.867-g sample of an unknown acid requires 32.2 mL of a 0.182 M barium hydroxide solution for neutralization. Assuming the acid is diprotic, calculate the molar mass of the acid.
A 25.0-mL volume of a sodium hydroxide solution requires 19.6 mL of a 0.189 M hydrochloric acid for neutralization.A 10.0- mL volume of a phosphoric acid solution requires 34.9 mL of the sodium hydroxide solution for complete neutralization.Calculate the concentration of the phosphoric acid
You are asked to prepare 2.0 L of a HCN/NaCN buffer that has a pH of 9.8 and an osmotic pressure of 1.35 atm at 298 K. What masses of HCN and NaCN should you use to prepare the buffer?
Derive an equation similar to the Henderson–Hasselbalch equation for a buffer composed of a weak base and its conjugate acid. Instead of relating pH to pKa and the relative concentrations of an acid and its conjugate base (as the Henderson–Hasselbalch equation does), the equation should relate
Since soap and detergent action is hindered by hard water, laundry formulations usually include water softeners—called builders—designed to remove hard water ions (especially Ca2+ and Mg2+) from the water. A common builder used in North America is sodium carbonate. Suppose that the hard water
A 0.558-g sample of a diprotic acid with a molar mass of 255.8 g/mol is dissolved in water to a total volume of 25.0 mL. The solution is then titrated with a saturated calcium hydroxide solution.a. Assuming that the pKa values for each ionization step are sufficiently different to see two
When excess solid Mg(OH)2 is shaken with 1.00 L of 1.0 M NH4Cl solution, the resulting saturated solution has pH = 9.00. Calculate the Ksp of Mg(OH)2.
What amount of solid NaOH must be added to 1.0 L of a 0.10 M H2CO3 solution to produce a solution with [H+] = 3.2 * 10-11 M ?There is no significant volume change as the result of the addition of the solid.
Calculate the solubility of Au(OH)3 in (a) Water and (b) 1.0 M nitric acid solution (Ksp = 5.5 * 10 - 46).
Calculate the concentration of I– in a solution obtained by shaking 0.10 M KI with an excess of AgCl(s).
What volume of 0.100 M sodium carbonate solution is required to precipitate 99% of the Mg from 1.00 L of 0.100 M magnesium nitrate solution?
Find the solubility of CuI in 0.40 M HCN solution. The Ksp of CuI is 1.1 * 10-12 and the Kf for the Cu(CN)2 - complex ion is 1 * 1024.
Find the pH of a solution prepared from 1.0 L of a 0.10 M solution of Ba(OH)2 and excess Zn(OH)2(s). The Ksp of Zn(OH)2 is 3 * 10-15 and the Kf of Zn(OH)4 2 - is 2 * 1015.
What amount of HCl gas must be added to 1.00 L of a buffer solution that contains [acetic acid] = 2.0 M and [acetate] = 1.0 M in order to produce a solution with pH = 4.00 ?
Without doing any calculations, determine if pH = pKa, pH > pKa, or pH < pKa. Assume that HA is a weak monoprotic acid.a. 0.10 mol HA and 0.050 mol of A– in 1.0 L of solutionb. 0.10 mol HA and 0.150 mol of A– in 1.0 L of solutionc. 0.10 mol HA and 0.050 mol of OH– in 1.0 L of solutiond. 0.10
A buffer contains 0.10 mol of a weak acid and 0.20 mol of its conjugate base in 1.0 L of solution. Determine whether or not each addition exceeds the capacity of the buffer.a. Adding 0.020 mol of NaOHb. Adding 0.020 mol of HClc. Adding 0.10 mol of NaOHd. Adding 0.010 mol of HCl
Consider three solutions:i. 0.10 M solution of a weak monoprotic acidii. 0.10 M solution of strong monoprotic acidiii. 0.10 M solution of a weak diprotic acidEach solution is titrated with 0.15 M NaOH. Which quantity is the same for all three solutions?a. The volume required to reach the final
Two monoprotic acid solutions (A and B) are titrated with identical NaOH solutions. The volume to reach the equivalence point for solution A is twice the volume required to reach the equivalence point for solution B, and the pH at the equivalence point of solution A is higher than the pH at the
Why does the titration of a weak acid with a strong base always have a basic equivalence point?
Name a compound that you could add to a solution of each of the compounds to make a buffer. Explain your reasoning in complete sentences.a. Acetic acidb. Sodium nitritec. Ammoniad. Potassium formatee. Na2HPO4
Derive the Henderson–Hasselbalch equation as a group. Take turns having each group member write and explain the next step in the derivation.
With group members acting as atoms or ions, act out the reaction that occurs when HCl is added to a buffer solution composed of HC2H3O2 and NaC2H3O2. Write out a script for a narrator that describes the processes that occur, including how the buffer keeps the pH approximately the same even though a
Have each group member look up the Ksp for a different compound.Calculate the molar solubility. Do the numerical values suggest that the compound is soluble or insoluble?Compare answers with the solubility rules from Chapter 5, and have each group member present his or her findings to the group.
A base is known to be one of the three listed in the table. You are given a sample of the base and asked to identify it. To do so, you dissolve 0.30 g of the base in enough water to make 25.0 mL of the basic solution. You then titrate the solution with 0.100 M HCl and record the pH as a function of
A certain town gets its water from an underground aquifer that contains water in equilibrium with calcium carbonate limestone.a. What is the symbol for the equilibrium constant that describes calcium carbonate dissolving in water? What is the numerical value?b. Calculate the molar solubility of
Predict the sign of ΔS for each process.(a) H2O(g) → H2O(l )(b) Solid carbon dioxide sublimes.(c) 2 N2O(g) → 2 N2(g) + O2(g)
Which reaction is most likely to have a positive ΔSsys? a) SiO₂ (s) + 3 C(s) SiC(s) + 2 CO(g) b) 6 CO₂(g) + 6H₂O(g) → C6H12O6(s) + 6 O₂(g) c) CO(g) + Cl₂(8) COCl2(g) d) 3 NO₂(g) + H₂O(1) → 2 HNO3(1) + NO(g)
Which process is inconsistent with the the second law of thermodynamics?(a) The spontaneous creation of energy from nothing.(b) The spontaneous creation of matter from nothing.(c) The spontaneous concentration of energy from dispersed energy.
What is the first law of thermodynamics, and how does it relate to energy use?
Consider these three changes in the possible distributions of six gaseous particles within three interconnected boxes. Which change has a positive ΔS? |00 00 ■■ 8 00 ■■ 00 (a) ロロ ■■ ■ロロロ ■■ .. (b) 00 ロロ .. □ ロロ 0. ロ @
Calculate the change in entropy that occurs in the system when 25.0 g of water condenses from a gas to a liquid at the normal boiling point of water (100.00 °C).
Consider the combustion of propane gas:(a) Calculate the entropy change in the surroundings when this reaction occurs at 25 °C.(b) Determine the sign of the entropy change for the system.(c) Determine the sign of the entropy change for the universe. Is the reaction spontaneous? C3H8(g) + 5O₂(g)
What is nature’s heat tax, and how does it relate to energy use?
Arrange the gases—F2, Ar, and CH3F—in order of increasing standard molar entropy (S°) at 298 K. a) F₂
Which process undergoes a decrease in entropy for water?(a) The melting of ice in a glass(b) The boiling of water in a saucepan(c) The condensation of water on the sides of a cold glass
Consider the reaction for the decomposition of carbon tetrachloride gas:(a) Calculate ΔG at 25 °C and determine whether the reaction is spontaneous.(b) If the reaction is not spontaneous at 25 °C, determine at what temperature (if any) the reaction becomes spontaneous. CC14(8) C(s, graphite) + 2
What is a perpetual motion machine? Can such a machine exist given the laws of thermodynamics?
By absorbing energy from their surroundings and synthesizing large, complex biological molecules, plants and animals tend to concentrate energy, not disperse it. How can this happen?(a) Biological systems only appear to concentrate energy. In reality, large, complex biological molecules have more
Calculate the change in entropy that occurs in the system when 1.00 mol of methanol (CH3OH) vaporizes from a liquid to a gas at its boiling point (64.6 °C). For methanol, ΔHvap = 35.21 kJ/mol.a) 104 J/K b) -104 J/K c) 545 J/K d) -545 J/K
Calculate ΔS°rxn for the balanced chemical equation: 4 NH3(g) + 5 O2(g) 4 NO(g) + 6 H₂O(g)
Is it more efficient to heat your home with a natural gas furnace or an electric furnace? Explain.
A reaction has a ΔHrxn = 54.2 kJ. Calculate the change in entropy for the surroundings (ΔSsurr) for the reaction at 25.0 °C. (Assume constant pressure and temperature.) a) 2.17 x 10³ J/K c) -182 J/K b) -2.17 x 10³ J/K d) 182J/K
Which statement is true regarding the sublimation of dry ice (solid CO2)?(a) ΔH is positive, ΔS is positive, and ΔG is positive at low temperatures and negative at high temperatures.(b) ΔH is negative, ΔS is negative, and ΔG is negative at low temperatures and positive at high
One of the possible initial steps in the formation of acid rain is the oxidation of the pollutant SO2 to SO3 by the reaction:Calculate ΔG°rxn at 25 °C and determine whether the reaction is spontaneous. SO2(g) + O2(g) SO3(g)
What is a spontaneous process? Provide an example.
A reaction has ΔH°rxn = -255 kJ and ΔS°rxn = 211 J/K. Calculate ΔG°rxn at 55 °C. a) 11.9 × 10³ kJ c) -267 kJ b) 69.5 x 10³ kJ d) -324 kJ
Explain the difference between the spontaneity of a reaction (which depends on thermodynamics) and the speed at which the reaction occurs (which depends on kinetics). Can a catalyst make a nonspontaneous reaction spontaneous?
For the reaction in Example 19.6, estimate the value of ΔG°rxn at 125 °C. Is the reaction more or less spontaneous at this elevated temperature? That is, is the value of ΔG°rxn more negative (more spontaneous) or more positive (less spontaneous)?Example 19.6One of the possible initial steps in
According to Le Châtelier’s principle and the dependence of free energy on reactant and product concentrations, which statement is true? (Assume that both reactants and products are gaseous.)(a) A high concentration of reactants relative to products results in a more spontaneous reaction than
Use standard entropies to calculate ΔS°rxn for the balanced chemical equation: 2 PC13 (1) + O₂(g) Substance POCI3(1) POCI3(g) PC13(1) PC13(g) O₂(g) a) -194.4 J/K c) 10.8 J/K 2 POCIĄ(1) S° (J/mol.K) 222.5 325.5 217.1 311.8 205.2 b) -199.8 J/K d) 1084.4 J/K
Ozone in the lower atmosphere is a pollutant that can form by the following reaction involving the oxidation of unburned hydrocarbons:Use the standard free energies of formation to determine ΔG°rxn for this reaction at 25 °C. CH4(8) + 8 0₂ (8) CO₂(g) + 2 H₂O(g) + 403(g)
What is the precise definition of entropy? What is the significance of entropy being a state function?
The reaction A(g) ⇌ B(g) has an equilibrium constant that is less than one. What can you conclude about ΔG°rxn for the reaction? (a) ΔGxn = 0 (b) ΔGxn < 0 (c) ΔGxn > 0
Use standard free energies of formation to calculate ΔG°rxn for the balanced chemical equation: Mg(s) + N₂O(g) Substance N₂O(g) MgO(s) a) 673.0 kJ b) -673.0 kJ c) -465.6 kJ d) 465.6 kJ MgO(s) + N₂(g) AGxn (kJ/mol) 103.7 -569.3
Why does the entropy of a gas increase when it expands into a vacuum?

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