Among the isomeric alkanes of molecular formula C5H12, identify the one that on photochemical chlorination yields (a) A single monochloride (c) Four isomeric monochlorides (b) Three isomeric...

Arrange the following alkenes in order of decreasing stability: 1-pentene; (E)-2-pentene; (Z)-2-pentene; 2-methyl-2-butene.

Give the IUPAC names for each of the following compounds: (a) (CH3CH2)2C = CHCH3 (b) (CH3CH2)2C = C (CH2CH3)2 (c) (CH3)3CCH = CCl2

(a) Suggest an explanation for the fact that 1-methylcyclopropene is some 42 kJ/mol (10 kcal/mol) less stable than methylenecyclopropane

(a) The sex attractant of the Mediterranean fruit fly is (E)-6-nonen-1-ol. Write a structural formula or build a molecular model for this compound, showing the stereochemistry of the double bond. (b)...

(a) Write the structures or build molecular models of all the isomeric alcohols having the molecular formula C5H12O. (b) Which one will undergo acid-catalyzed dehydration most readily? (c) Write the...

As a method for the preparation of alkenes, a weakness in the acid-catalyzed dehydration of alcohols is that the initially formed alkene (or mixture of alkenes) sometimes isomerizes under the...

Alcohol A (C10H18O) is converted to a mixture of alkenes B and C on being heated with potassium hydrogen sulfate (KHSO4). Catalytic hydrogenation of B and C yields the same product. Assuming that...

Assign absolute configurations as R or S to each of the following compounds:

Use curved arrows to show how calcium carbide reacts with water to give acetylene.

All the compounds in Problem 9.19 are isomers except one. Which one?

All the following reactions have been described in the chemical literature and proceed in good yield. In some cases the reactants are more complicated than those we have so far encountered....

Sodium nitrite (NaNO2) reacted with 2-iodooctane to give a mixture of two constitutionally isomeric compounds of molecular formula C8H17NO2 in a combined yield of 88%. Suggest reasonable structures...

All the reactions of 1-bromopropane in the preceding problem give the product of nucleophilic substitution in high yield. High yields of substitution products are also obtained in all but one of the...

Alkynes of the type RCPCH may be prepared by nucleophilic substitution reactions in which one of the starting materials is sodium acetylide (a) Devise a method for the preparation of CH3CH2C CH from...

(a) Suggest a reasonable series of synthetic transformations for converting trans-2-methylcyclopentanol to cis-2-methylcyclopentyl acetate.

Write structural formulas and give the IUPAC names for all the isomers of C6H5C4H9 that contain a monosubstituted benzene ring.

Acridine is a heterocyclic aromatic compound obtained from coal tar that is used in the synthesis of dyes. The molecular formula of Acridine is C13H9N, and its ring system is analogous to that of...

Each of the following reactions has been carried out under conditions such that disubstitution or trisubstitution occurred. Identify the principal organic product in each case. (a) Nitration of...

Treatment of the alcohol whose structure is shown here with sulfuric acid gave as the major organic product a tricycles hydrocarbon of molecular formula C16H16. Suggest a reasonable structure for...

max for the * transition in ethylene is 170 nm. Is the HOMOLUMO energy difference in ethylene greater than or less than that of cis, trans-1,3-cyclooctadiene?

Analyze the following structures so as to determine all the practical combinations of Grignard reagent and carbonyl compound that will give rise to each:

(a) Unlike other esters, which react with Grignard reagents to give tertiary alcohols, ethyl formate (HCOCH2CH3) yields a different class of alcohols on treatment with Grignard reagents. What kind of...

Adapt the mechanism shown in Figure 16.4 to the reaction:

Many ethers, including diethyl ether, are effective as general anesthetics. Because simple ethers are quite flammable, their place in medical practice has been taken by highly halogenated...

Although epoxides are always considered to have their oxygen atom as part of a threemembered ring, the prefix epoxy in the IUPAC system of nomenclature can be used to denote a cyclic ether of various...

The last step in the synthesis of divinyl ether (used as an anesthetic under the name Vinethene) involves heating ClCH2CH2OCH2CH2Cl with potassium hydroxide. Show how you could prepare the necessary...

All the following questions pertain to 1H NMR spectra of isomeric ethers having the molecular formula C5H12O. (a) Which one has only singlets in its 1H NMR spectrum? (b) Along with other signals,...

Alfred Nobels fortune was based on his 1866 discovery that nitroglycerin, which is far too shock-sensitive to be transported or used safely, can be stabilized by adsorption onto a substance called...

(a) The cis isomer of 3-hexen-1-ol (CH3CH2CHCHCH2CH2OH) has the characteristic odor of green leaves and grass. Suggest a synthesis for this compound from acetylene and any necessary organic or...

Arachidonic acid is the biosynthetic precursor to PGE2. The structures of PGE1 (see Figure 26.5) and PGE2 are identical except that PGE2 has one more double bond than PGE1. Suggest a reasonable...

An article in the October 1998 issue of the Journal of Chemical Education (p. 1266) describes the following reaction.

As an allergen for testing purposes, synthetic 3-pentadecylcatechol is more useful than natural poison ivy extracts (of which it is one component). A stable crystalline solid, it is efficiently...

Compound A undergoes hydrolysis of its acetal function in dilute sulfuric acid to yield 1, 2- ethanediol and compound B (C6H6O2), mp 54C. Compound B exhibits a carbonyl stretching band in the...

Aryl halides react too slowly to undergo substitution by the SN2 mechanism with the sodium salt of diethyl malonate, and so the phenyl substituent of phenobarbital cannot be introduced in the way...

All the following questions concern ethyl (2-oxocyclohexane) carboxylate

(a) Only a small amount (less than 0.01%) of the enol form of diethyl malonate is present at equilibrium. Write a structural formula for this enol. (b) Enol forms are present to the extent of about...

(a) On addition of one equivalent of methylmagnesium iodide to ethyl acetoacetate, the Grignard reagent is consumed, but the only organic product obtained after working up the reaction mixture is...

After the compound shown was heated in D2O containing K2CO3 at 70C the only signals that could be found in its 1H NMR spectrum were at 3.9 ppm (6H) and 6.76.9 ppm (3H). What happened?

Acrolein (CH2CHCHO) reacts with sodium azide (NaN3) in aqueous acetic acid to form a compound, C3H5N3O in 71% yield. Propanal (CH3CH2CHoeO), when subjected to the same reaction conditions, is...

(a) Write structural formulas or build molecular models for all the noncyclic aldehydes and ketones of molecular formula C4H6O. (b) Are any of these compounds stereoisomeric? (c) Are any of these...

(a) A synthesis that begins with 3,3-dimethyl-2-butanone gives the epoxide shown. Suggest reagents appropriate for each step in the synthesis.

Outline reasonable mechanisms for each of the following reactions:

Amino acid analysis of a certain tetrapeptide gave alanine, glycine, phenylalanine, and valine in equimolar amounts. What amino acid sequences are possible for this tetrapeptide?

Acrylonitrile (CH2=CHCPN) readily undergoes conjugate addition when treated with nucleophilic reagents. Describe a synthesis of 0-alanine (H3NCH2CH2CO2) that takes advantage of this fact.

(a) The 5`-nucleotide of inosine, inosinic acid (C10H13N4O8P), is added to foods as a flavor enhancer. What is the structure of inosinic acid? (The structure of inosine is given in Problem 27.38.)...

Another hexose gives the same aldaric acid on oxidation as does D-glucose. Which one?

a) Which stereoisomer of 4-hydroxycyclohexanecarboxylic acid (cis or trans) can form a lactone? Make a molecular model of this lactone. What is the conformation of the cyclohexane ring in the...

Apply the knowledge gained by studying Table 20.3 to help you predict the major organic product of each of the following reactions:

Ambrettolide is obtained from hibiscus and has a musk-like odor. Its preparation from a compound A is outlined in the table that follows. Write structural formulas, ignoring stereochemistry, for...

Asked you to write a mechanism describing formation of benzaldehyde diethyl acetal from benzaldehyde and ethanol, write a stepwise mechanism for the acid hydrolysis of this acetal.

Acetal formation is a characteristic reaction of aldehydes and ketones, but not of carboxylic acids. Show how you could advantageously use a cyclic acetal protecting group in the following synthesis:

(a) Showed the preparation of 3-methyl-3-heptene by a Wittig reaction involving the ylide shown. Write equations showing the formation of this ylide beginning with 2-bromobutane

(a) Write structural formulas and provide IUPAC names for all the isomeric aldehydes nd Ketones that have the molecular formula C5H10O, Include stereoisomers. (b) Which of the isomers in part (a)...

Amygdalin, a substance present in peach, plum, and almond pits, is a derivative of the R enantiomer of benzaldehyde cyanohydrin. Give the structure of (R)-benzaldehyde cyanohydrin.

Assign alkanamine names to N-methylethylamine and to N, Ndimethylcycloheptylamine.

As the extent of electron delocalization into the ring increases, the geometry at nitrogen flattens. P-Nitroaniline, for example, is planar. Write a resonance form for p-nitroaniline that shows how...

Apply the HendersonHasselbalch equation (see Quantitative Relationships Involving Carboxylic Acids, the box accompanying Section 19.4) to calculate the CH3NH3 +/CH3NH2 ratio in water buffered at pH 7.

Alkylation of ammonia is sometimes employed in industrial processes; the resulting mixture of amines is separated by distillation. The ultimate starting materials for the industrial preparation of...

Arrange the members of each group in order of decreasing basicity: (a) Ammonia, aniline, methylamine (b) Acetanilide, aniline, N-methylaniline (c) 2, 4-Dichloroaniline, 2, 4-dimethylaniline, 2,...

Ammonia and amines undergo conjugate addition to a, -unsaturated carbonyl compounds (Section 18.12). On the basis of this information, predict the principal organic product of each of the following...

A sample of2.00 mol CH30H (g) is condensed isothermally and reversibly to liquid at 64oC. The standard enthalpy of vaporization of methanol at 64C is 35.3 kJ mol-1. Find w, q, U, and H for this...

Calculate the standard enthalpy of solution of AgBr(s) in water from the enthalpies of formation of the solid and the aqueous ions.

A sample consisting of2.0 mol CO2 occupies a fixed volume of 15.0 dm3 at 300 K. When it is supplied with 2.35 kJ of energy as heat its temperature increases to 341 K. Assume that CO2, is described by...

Calculate the molar entropy of a constant-volume sample of argon at 250 K given that it is 154.84 J K-I mol-1 at 298 K.

Calculate LVI and i1S'OIwhen two iron blocks, each of mass 1.00 kg, one at 200C and the other at 25C, are placed in contact in an isolated container. The specific heat capacity of iron is 0.449 J K-I...

In a study of the properties of an aqueous solution of Th(N03)4 (by A. Apelblat, D. Azoulay, and A. Sahar,]. Chem. Sac. Faraday Trans., I, 1618, (1973, a freezing point depression of 0.0703 K was...

The excess Gibbs energy of solutions of methylcyclohexane (MCH) and tetrahydrofuran (THF) at 303.15 K was found to fit the expression GE=RTx (1- x) {0.4857 - 0.1077(2x -1) + 0.0191(2x- 1)2} where x...

Explain how the compression factor varies with pressure and temperature and describe how it reveals information about intermolecular interactions in real gases.

The standard molar entropy of NHJ (g) is 192.45 T K-I mol-1 at 298 K, and its heat capacity is given by eqn 2.25 with the coefficients given in Table 2.2. Calculate the standard molar entropy at (a)...

Draw phase diagrams for the following types of systems. Label the regions and intersections of the diagrams, stating what materials (possibly compounds or azeotropes) are present and whether they are...

Sketch the phase diagram of the system NH3/NzH. given that the two substances do not form a compound with each other, that NH3 freezes at -78C and N2H. freezes at +2C, and that a eutectic is formed...

Figure 6.40 is the phase diagram for silver and tin. Label the regions, and describe what will be observed when liquids of compositions a and bare cooled to 200 K.

Indicate on the phase diagram in Fig. 6.42 the feature that denotes incongruent melting. What is the composition of the eutectic mixture and at what temperature does it melt?

Sketch the cooling curves for the isopleths a and b in Fig. 6.42

Use the phase diagram in Fig. 6.41 to state (a) The solubility of B in A at 500C and (b) The solubility of AB2 in A at 390C, (c) The solubility of ABz in Bat 300e.

Carbon dioxide at high pressure is used to separate various compounds in citrus oil. The mole fraction of CO, in the liquid (x) and vapour (y) at 323.2 K is given below for a variety of pressures (Y....

The emf of the cell Pt | H2 (g, p) | HCI (aq, b) | Hg2Cl2 (s) | Hg (l) has been measured with high precision (G.]. Hills and D].G. Ives, J. Chem. Soc., 311 (1951)) with the following results at 25C:...

Account for the uncertainty relation between position and linear momentum in terms of the shape of the wave function.

Calculate the size of the quantum involved in the excitation of (a) An electronic oscillation of period 2.50 fs, (b) A molecular vibration of period 2.21 fs, (c) A balance wheel of period 1.0 ms....

The Planck distribution gives the energy in the wavelength range dA at the wavelength A. Calculate the energy density in the range 650 nm to 655 nm inside a cavity of volume 100 em3 when its...

Identify which of the following functions are eigen functions of the operator d/dx: (a) D2/dx2, (b) Cos kx, (c) K, (d) Kx, (e) e-ax2. Give the corresponding eigen value where appropriate.

Discuss the physical origin of quantization energy for a particle confined to moving inside a one-dimensional box or on a ring.

Assuming that the vibrations of a 14N2molecule are equivalent to those of a harmonic oscillator with a force constant k = 2293.8 N m3, what is the zero-point energy of vibration of this molecule? The...

(a) Write the electronic configuration of the V2+ ion. (b) What are the possible values of the total spin quantum numbers 5 and Ms for this ion?

The Bohr model of the atom is specified in Problem 10.18. What features of it are untenable according to quantum mechanics? How does the Bohr ground state differ from the actual ground state? Is...

Arrange the species 0+2, 02, 0-2, O2-2 in order of increasing bond length.

Predict the electronic configurations of (a) The benzene anion, (b) The benzene cation. Estimate the -electron binding energy in each case.

Molecular orbital calculations may be used to predict trends in the standard potentials of conjugated molecules, such as the quinones and flavins that are involved in biological electron transfer...

The CCl4 molecule belongs to the point group Td. List the symmetry elements of the group and locate them in the molecule.

Assign the following molecules to point groups: (a) HF, (b) IF7 (pentagonal bipyramid), (c) XeO2F2, (see-saw), (d) Fe,(CO)9 (22), (e) Cubane, C8H8, (f) Tetrafluorocubane, C8H4F4 (23) cO Fe co 23

Which of the following molecules may show a pure rotational microwave absorption spectrum? (a) H20, (b) H202, (c) NH4 (d) N20?

Calculate, by explicit summation, the vibrational partition function and the vibrational contribution to the molar internal energy of is molecules at (a) 100 K, (b) 298 K given that its vibrational...

Assume that the electronic states of the re electrons of a conjugated molecule can be approximated by the wave functions of a particle in a one-dimensional box, and that the dipole moment can be...

From the results of Exercise 17.5b, calculate the rotational contribution to the molar entropy of sulfur dioxide at 25e.

The NOF molecule is an asymmetric rotor with rotational constants 3.1752 cm-1, 0.3951 cm-1, and 0.3505 cm-1. Calculate the rotational partition function of the molecule at (a) 25C, (b) 100e

Calculate the resultant of two dipole moments of magnitude 1.5 D and 0.80 D that make an angle of 109.5 to each other.

Self-assembled monolayers (SAMs) are receiving more attention than Longmuir-Blodgett (LB) films as starting points for nanofabrication. How do SAMs differ from LB films and why are SAMs more useful...

What is the relative rate of sedimentation for two spherical particles with densities 1.10 g cm and 1.18 g cm and which differ in radius by a factor of8.4, the former being the larger? Use p = 0.794...

A synthetic polymer has a specific volume of 8.01 x 10-4 m kg-1, a sedimentation constant of7.46 Sv, and a diffusion coefficient of 7.72 x 10-11 m2 S-1 Determine its molar mass from this information.