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Chemistry The Central Science 12th edition Theodore Brown, Eugene LeMay, Bruce Bursten, Catherine Murphy, Patrick Woodward - Solutions

As shown in Figure 23.26, the d-d transition of [Ti(H2O)6]3+ produces an absorption maximum at a wavelength of about 500 nm. (a) What is the magnitude of Δ for [Ti(H2O)6]3+ in kJ/mol? (b) What is the spctrochemical series? How would the magnitude of Δ change if the H2O ligands in [Ti (H2O)6]3+
Explain why many cyano complexes of divalent transitionmetal ions are yellow, whereas many aqua complexes of these ions are blue or green.
The [Ni (H2O)6]2+ ion has an absorption maximum at about 725 nm, whereas the [Ni (H2O)6]2+ ion absorbs at about 570nm. Predict the color of a solution of each ion. (b) The [Ni(en)3]2+ ion occurs at about 520 nm. From these data, indicate the relative strengths of the ligand fields created by the
Give the number of (valence) d electrons associated with the central metal ion in each of the following complexes: (a) K3 [TiCI6], (b) Na3 [Co(NO2)6], (c) [Ru (en)3]Br3, (d) [Mo(EDATA)]CIO4, (e) K3 [ReCI6].
Give the number of (valence) d electrons associated with the central metal ion in each of the following complexes (a) K3[Fe(CN)6], (b) [Mn(H2O)6](NO3)2, (c) Na[Ag(CN)2], (d) [Cr(NH3)4Br2]ClO4, (e) [Sr (EDATA)2-.
A classmate says, "A weak-field ligand usually means the complex is high spin." Is your classmate correct? Explain.
A classmate says, "A strong-field ligand means that the ligand binds strongly to the metal ion." Is your classmate correct? Explain.
For each of the following metals, write the electronic configuration of the atom and its 2 + ion: (a) Mn, (b) Ru, (c) Rh. Draw the crystal-field energy-level diagram for the d orbitals of an octahedral complex, and show the placement of the delectrons for each 2+ ion, assuming a strong-field
Which of the complexes shown here are chiral? Explain. [Section 23.4]
For each of the following metals, write the electronic configuration of the atom and its ion: (a) Ru, (b) Mo, (c) Co.Draw the crystal-field energy-level diagram for the d orbitals of an octahedral complex, and show the placement of the d electrons for each ion, assuming a weak-field complex. How
Draw the crystal-field energy-level diagrams and show the placementof d electrons for each of the following:(a) [Cr(H2O)6]2 + (four unpaired electrons), (b) [Mn (H2O)6]2+ (high spin),(c) [Ru (NH3) 5H2O]2+ (low spin), (d) [IrCI6]2- (low spin),(e) [Cr (en)3]3+ , (f) [Nif6]4-.
Draw the crystal-field energy-level diagrams and show the placement of electrons for the following complexes:(a) [VCI6]3-,(b) [FeF6]3- ( a high-spin complex), (c) [Ru (bipy)3]3+ ( a low spin complex), (d) [NiCI4]2- (tetrahedral),(e) [PtBr6]2-(f) Ti(en)3]2+
The complex [Mn (NH3)6]2+ contains five unpaired electrons. Sketch the energy-level diagram for the d orbitals, and indicate the placement of electrons for this complex ion. Is the ion a high-spin or a low-spin complex?
The ion [Fe(CN)6]3- has one unpaired electron, whereas [Fe(NCS)6]3- has five unpaired electrons. From these results, what can you conclude about whether each complex is high spin or low spin? What can you say about the placement of NCS- in the spectrochemical series?
The Curie temperature is the temperature at which a ferromagnetic solid switches from ferromagnetic to paramagnetic, and for nickel, the Curie temperature is 354°C. Knowing this, you tie a string to two paper clips made of nickel and hold the paper clips near a permanent magnet. The magnet
Explain why the transition metals in periods 5 and 6 have nearly identical radii in each group.
(a) A compound with formula RuCl3.5H2O is dissolved in water, forming a solution that is approximately the same color as the solid. Immediately after forming the solution, the addition of excess AgNO3(aq) forms 2 mol of solid AgCl per mole of complex. Write the formula for the compound, showing
The solutions shown here each have an absorption spectrum with a single absorption peak like that shown in Figure 23.26. What color does each solution absorb most strongly? [Section 23.5]
(a) Which complex ions in Exercise 23.69 have a mirror plane? (b) Will any of the complexes be optically active? Explain.
The molecule dimethylphosphinoethane [(CH3)2PCH2- CH2P(CH3)2, which is abbreviated dmpe] is used as a ligand for some complexes that serve as catalysts. A dmpe, and compare it with ethylenediammine as a coordinating ligand. (b) What is the oxidation state of Mo in Na2[Mo(CN)2(CO)2(dmpe)]? (c)
Although the cis configuration is known for [Pt(en)Cl2], no trans form is known. (a) Explain why the trans compound is not possible. (b) Would NH2CH2CH2CH2CH2NH2 be more likely than en (NH2CH2CH2NH2) to form the trans compound? Explain.
The acetylacetone ion forms very stable complexes with many metallic ions. It acts as a bidentate ligand, coordinating to the metal at two adjacent positions. Suppose that one of the CH3 groups of the ligand is replaced by a CF3 group, as shown here,
Give brief statements about the relevance of the following complexes in living systems: (a) Hemoglobin, (b) Chlorophylls, (c) Siderophores.
Write balanced chemical equations to represent the following observations. (In some instances the complex involved has been discussed previously in the text.) (a) Solid silver chloride dissolves in an excess of aqueous ammonia.
Some metal complexes have a coordination number of 5. One such complex is Fe(CO)5, which adopts a trigonal bipyramidal geometry (see Figure 9.8). (a) Write the name for Fe(CO)5, using the nomenclature rules for coordination compounds. (b) What is the oxidation state of Fe in this compound? (c)
The complexes ﴾V(H2O5)3 and 6VFare both known. Draw the d-orbital energy-level diagram for V(III) octahedral complexes What gives rise to the colors of these complexes? Which of the two complexes would you expect to absorb light of higher energy? Explain.
One of the more famous species in coordination chemistry is the Creutz-Taube complex,It is named for the two scientists who discovered it and initially studied its properties. The central ligand is pyrazine, a planar six-membered ring with nitrogens at opposite sides. (a) How can you account for
Which of these crystal-field splitting diagrams represents:(a) A weak-field octahedral complex of Fe3+,(b) A strong-field octahedral complex of Fe3+,(c) A tetrahedral complex of Fe3+,(d) A tetrahedral complex of Fe3+? (The diagrams do not indicate the relative magnitudes of Î”.) [Section
Solutions of [Co(NH3)6]2+,[Co(H2O)6]2+ (both octahedral), and (tetrahedral) are colored. One is pink, one is blue, and [CoCI4]2- one is yellow. Based on the spectrochemical series and remembering that the energy splitting in tetrahedral complexes is normally much less than that in octahedral ones,
Consider the tetrahedral anions VO43- (orthovanadate ion), GrO42- (chromate ion), and MnO4 (permanganate ion). (a) These anions are isoelectronic. What does this statement mean? (b)Would you expect these anions to exhibit d-d transitions? Explain. (c) As mentioned in "A Closer Look" on
Given the colors observed for VO43-(orthovanadate ion), (chromate ion), and MnO4-(permanganate ion) (see Exercise 23.82), what can you say about how the energy separation between the ligand orbitals and the empty d orbitals changes as a function of the oxidation state of the transition metal at the
The red color of ruby is due to the presence of Cr(III) ions at octahedral sites in the close-packed oxide lattice of Al 2O3. Draw the crystal-field splitting diagram for Cr(III) in this environment. Suppose that the ruby crystal is subjected to high pressure. What do you predict for the variation
In 2001, chemists at SUNY-Stony Brook succeeded in synthesizing the complex trans-[Fe(CN)4(CO)2]2- , which could be a model of complexes that may have played a role in the origin of life. (a) Sketch the structure of the complex. (b) The complex is isolated as a sodium salt. Write the complete
When Alfred Werner was developing the field of coordination chemistry, it was argued by some that the optical activity he observed in the chiral complexes he had prepared was because of the presence of carbon atoms in the molecule. To disprove this argument,Werner synthesized a chiral complex of
Generally speaking, for a given metal and ligand, the stability of a coordination compound is greater for the metal in the +3 rather than in the +2 oxidation state (for metals that form stable +3 ions in the first place). Suggest an explanation, keeping in mind the Lewis acid-base nature of the
Many trace metal ions exist in the blood complexed with amino acids or small peptides. The anion of the amino acid glycine (gly),
Suppose that a transition-metal ion was in a lattice in which it was in contact with just two nearby anions, located on opposite sides of the metal. Diagram the splitting of the metal dorbitals that would result from such a crystal field. Assuming a strong field, how many unpaired electrons would
In the linear crystal field shown here, the negative charges are on the z-axis. Using Figure 23.28 as a guide, predict which d orbital has lobes closest to the charges. Which two have lobes farthest from the charges? Predict the crystal-field splitting of the d orbitals in linear complexes.
Metallic elements are essential components of many important enzymes operating within our bodies. Carbonic anhydrase, which contains Zn2+ in its active site, is responsible for rapidly interconverting dissolved CO2 and bicarbonate ion, HCO3. The zinc in carbonic anhydrase is tetrahedrally
Two different compounds have the formulation CoBr(SO4) ∙5NH3. Compound A is dark violet, and compound B is red-violet. When compound A is treated with AgNO3 (aq), no reaction occurs, whereas compound B reacts with AgNO3(aq) to form a white precipitate.When compound A is treated with BaCl2(aq), a
A manganese complex formed from a solution containing potassium bromide and oxalate ion is purified and analyzed. It contains10.0% Mn, 28.6% potassium, 8.8 carbon, and 29.2% bromine by mass. The remainder of the compound is oxygen. An aqueous solution of the complex has about the same electrical
The Eo values for two low-spin iron complexes in acidic solution are as follows: (a) Is it thermodynamically favorable to reduce both Fe(III) complexes to their Fe(II) analogs? Explain. (b) Which complex, [Fe(o-phen)3]3+ or [Fe(CN)6]3- , is more difficult to reduce? (c) Suggest an explanation for
A palladium complex formed from a solution containing bromide ion and pyridine, C5H5N (a good electron-pair donor), is found on elemental analysis to contain 37.6% bromine, 28.3% carbon,6.60% nitrogen, 2.37% and hydrogen by mass. The compound is slightly soluble in several organic solvents; its
(a) In early studies it was observed that when the complex [Co(NH3)4Br2]Br was placed in water, the electrical conductivity of a 0.05 M solution changed from an initial value of 191 ohm -1 to a final value of374 ohm -1 over a period of an hour or so. Suggest an explanation for the observed
The total concentration of Ca2 + and Mg2+ in a sample of hard water was determined by titrating a 0.100-L sample of the water with a solution of EDTA4-.The EDTA4- chelates the two cations: It requires 31.5 mL of 0.0104 M [EDTA]4- solution to reach the end point in the titration. A second 0.100-L
Carbon monoxide is toxic because it binds more strongly to the iron in hemoglobin (Hb) than does O2, as indicated by these approximate standard free-energy changes in blood:Using these data, estimate the equilibrium constant at 298 K for the equilibrium
The molecule methylamine (CH3NH2) can act as a monodentate ligand. The following are equilibrium reactions and the thermochemical data at 298 K for reactions of methylamine and en with Cd2+ (aq);(a) Calculate Î”Go and the equilibrium constant K for the following ligand exchange
The value of ∆ for the (CrF6)3- complex is 182kj/mol . Calculate the expected wavelength of the absorption corresponding to promotion of an electron from the lower energy to the higher-energy d-orbital set in this complex. Should the complex absorb in the visible range?
All the structures shown here have the molecular formula C8H18. Which structures are the same molecule? (Hint: One way to answer this question is to determine the chemical name for each structure.) [Section 24.2]
Identify the carbon atom(s) in the structure shown that has (have) each of the following hybridizations: (a) sp3, (b) sp, (c) sp2.
A typical amino acid with one amino group and one carboxylic acid group, such as serine (Figure 24.18), can exist in water in several ionic forms. (a) Suggest the forms of theamino acid at low pH and at high pH. (b) Amino acids generally have two pKa values, one in the range of 2 to 3 and the other
The protein ribonuclease A in its native, or most stable, form is folded into a compact globular shape: Native ribonuclease A (a) Does the native form have a lower or higher free energy than the denatured form, in which the protein is an extended chain? (b) What is the sign of the entropy
The monoanion of adenosine monophosphate (AMP) is an intermediate in phosphate metabolism:where A = adenosine. If the PKa for this anion is 7.21, what is the ration of [AMP - OH-] to [AMP - O2] inblood at pH 7.4
Are carbon monoxide or ammonia considered organic molecules? Why or why not?
Organic compounds containing C-O and C-1 bonds are more reactive than simple alkane hydrocarbons. Considering the comparative values of C - H, C - C, C--O and C -- 1 bond enthalpies (Table 8.4), why is this so?
(a) What is the difference between a straight-chain and branched-chain alkane? (b) What is the difference between an alkane and an alkyl group?
What structural features help us identify a compound as (a) an alkane, (b) a cycloalkane, (c) an alkene, (d) an alkyne, (e) a saturated hydrocarbon, (f) an aromatic hydrocarbon?
Give the the name or condensed structural formula, as appropriate:(c) 2-methylheptane (d) 4-ethyl-2,3-dimethyloctane (e) 1,2-dimethylcyclohexane
Give the name or condensed structural formula, as appropriate:(c) 2,5,6-trimethylnonane (d) 3-propyl-4,5-methyldecane
Give the name or condensed structural formula, as appropriate:(b) 2,2-dimethylpentane (c) 4-ethyl-1,1-dimethylcyclohexane (d) (CH3)2CHCH2CH2C(CH3)3 (e) CH3CH2CH(C2H5)CH2CH2CH2CH3
Give the name or condensed structural formula, as appropriate:(a) 3-phenylpentane(b) 2,3-dimethylhexane(c) 2-ethyl-2-methylhepane(d) CH3CH2CH(CH3)CH2CH(CH3)2
What is the octane number of a mixture that is 35% heptanes and 65% is ooctane?
Which of these molecules is unsaturated? [Section 24.3]
Describe two ways in which the octane number of a gasolineconsisting of alkanes can be increased.
(a) Why are alkanes said to be saturated? (b) Is C4H6 a saturatedhydrocarbon? Why or why not?
(a) Is the compound CH3CH"CH2 saturated or unsaturated? Explain. (b) What is wrong with the formula CH3 CH2CH"CH3?
Give the molecular formula of a hydrocarbon containing five carbon atoms that is (a) an alkane, (b) a cycloalkane, (c) an alkene, (d) an alkyne.Which are saturated and which are unsaturated hydrocarbons?
Give the molecular formula of a cyclic alkane, a cyclic alkene, alinear alkyne, and an aromatic hydrocarbon that in each case contains six carbon atoms.Which are saturated and which are unsaturated hydrocarbons?
Enediynes are a class of compounds that include some antibiotic drugs. Draw the structure of an "enediyne" fragment that contains six carbons in a row. (Hint: di means "two.")
Annlyze/Plan. Follow the logic in Sample Exercise 24.3. Solve.
Draw all the possible noncyclic structural isomers of C5H10. Name each compound.
Name or write the condensed structural formula for the following compounds:(a) Trans -2-pentene(b) 2,5-dimethyl-4-octene
Which of these molecules most readily undergoes an addition reaction? [Section 24.3]
Name or write the condensed structural formula for the following compounds: (a) 4-methyl-2-pentene (b) cis-2,5-dimethyl-3-hexene (c) ortho-dimethylbenzene (d) HC'CCH2CH3 (e) trans-CH3CH"CHCH2CH2CH2CH3
Why is geometric isomerism possible for alkenes but not for alkanes and alkynes?
Draw all structural and geometric isomers of butene and name them.
Indicate whether each of the following molecules is capable of geometrical (cis-trans) isomerism. For those that are, draw the structures: (a) 1,1-dichloro-1-butene, (b) 2,4-dichloro-2- butene, (c) 1,4-dichlorobenzene, (d) 4,5-dimethyl-2-pentyne.
Draw the three distinct geometric isomers of 2,4-hexadiene.
(a) What is the difference between a substitution reaction and an addition reaction? Which one is commonly observed with alkenes and which one with aromatic hydrocarbons? (b) Using condensed structural formulas, write the balanced equation for the addition reaction of 2-pentene with Br2 and name
Using condensed structural formulas, write a balanced chemical equation for each of the following reactions: (a) hydrogenation of cyclohexene; (b) addition of H2O to trans-2- pentene using H2SO4 as a catalyst (two products); (c) reaction of 2-chloropropane with benzene in the presence of AlCl3.
(a) When cyclopropane is treated with HI, 1-iodopropane is formed. A similar type of reaction does not occur with cyclopentane or cyclohexane. How do you account for the reactivity of cyclopropane? (b) Suggest a method of preparing ethylbenzene, starting with benzene and ethylene as the only
(a) One test for the presence of an alkene is to add a small amount of bromine, a red-brown liquid, and look for the disappearance of the red-brown color. This test does not work for detecting the presence of an aromatic hydrocarbon. Explain. (b) Write a series of reactions leading to
The rate law for addition of Br2 to an alkene is first order in Br2 and first order in the alkene. Does this fact prove that the mechanism of addition of Br2 to an alkene proceeds in the same manner as for addition of HBr? Explain.
Which of these compounds would you expect to have the highest boiling point? Explain. [Section 24.4]
Describe the intermediate that is thought to form in the addition of a hydrogen halide to an alkene, using cyclohexene as the alkene in your description.
The molar heat of combustion of gaseous cyclopropane is -2089 kJ / mol; that for gaseous cyclopentane is -3317 kJ/mol Calculate the heat of combustion per CH2 group in the two cases, and account for the difference.
The heat of combustion of decahydronaphthalene (C10H18) is -6286 kJ / mol The heat of combustion of naphthalene (C10H8) is-5157 kJ / mol. [In both cases CO2(g) and H2O(l) are the products.] Using these data and data in Appendix C, calculate the heat of hydrogenation of naphthalene. Does this value
Identify the functional groups in each of the following compounds:(a) H3 C--- CH2--- OH(b)(c) (d) (e) CH3CH2CH2CH2CHO
Identify the functional groups in each of the following compounds:
Give the structural formula for (a) an aldehyde that is an isomer of acetone, (b) an ether that is an isomer of 1-propanol.
(a) Give the empirical formula and structural formula for a cyclic ether containing four carbon atoms in the ring. (b) Write the structural formula for a straight-chain compound that is a structural isomer of your answer to part (a).
The IUPAC name for a carboxylic acid is based on the name of the hydrocarbon with the same number of carbon atoms. The ending -oic is appended, as in ethanoic acid, which is the IUPAC name for acetic acid. Draw the structure of the following acids: (a) methanoic acid, (b) pentanoic acid, (c)
Aldehydes and ketones can be named in a systematic way by counting the number of carbon atoms (including the carbonyl carbon) that they contain. The name of the aldehyde or ketone is based on the hydrocarbon with the same number of carbon atoms. The ending -al for aldehyde or -one for ketone is
Draw the condensed structure of the compounds formed by condensation reactions between (a) benzoic acid and ethanol, (b) ethanoic acid and methylamine, (c) acetic acid and phenol. Name the compound in each case.
Which of these compounds can be a member of an isomer pair? In each case where isomerism is possible, identify the type or types of isomerism. [Sections 24.2, 24.4]
Write a balanced chemical equation using condensed structural formulas for the saponification (base hydrolysis) of (a) methyl propionate, (b) phenyl acetate.
Write a balanced chemical equation using condensed structural formulas for the saponification (base hydrolysis) of (a) methyl propionate, (b) phenyl acetate. Discuss.
Write a balanced chemical equation using condensed structural formulas for (a) the formation of butyl propionate from the appropriate acid and alcohol, (b) the saponification (base hydrolysis) of methyl benzoate.
Would you expect pure acetic acid to be a strongly hydrogenbonded substance? How do the melting and boiling points of the substance (16.7°C and 118°C) support your answer?
Acetic anhydride is formed from acetic acid in a condensation reaction that involves the removal of a molecule of water from between two acetic acid molecules. Write the chemical equation for this process, and show the structure of acetic anhydride.

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