Draw a plausible mechanism for the following transformation: , [H2SO4]
Propose a plausible mechanism for the reaction below: [H2SO4] N- - . -N.
Predict the products obtained when 1-pentyne reacts with each of the following reagents: (a) H 2 SO 4 , H 2 O, HgSO 4 (b) 9-BBN followed by H 2 O 2 , NaOH (c) Two equivalents of HBr (d) One...
Lindane (hexachlorocyclohexane) is an agricultural insecticide that can also be used in the treatment of head lice. Draw both chair conformations of lindane. CI CI 'CI CI I Lindane
Which of the following compounds has the larger dipole moment? Explain your choice: CHCl 3 or CBrCl 3
Draw curved arrows for each step of the following mechanism: . . -CH;So --S0 NO2
Draw curved arrows for each step of the following mechanism: : : : 0: . : : -O: : - : : : : H20 -
What reagents would you use to prepare each of the following thiols: a. b. c. SH SH
There are four isomers with molecular formula C 4 H 9 Cl. Only one of these isomers (compound A) has a chirality center. When compound A is treated with sodium ethoxide, three products are formed:...
Propose an efficient synthesis for each of the following transformations: (a) (b) (c) OH
Draw a plausible mechanism for the following transformation: -NH2 [H,SO] NH2 [-H,0]
Predict the product(s) for each reaction below: (a) (b) (c) (d) * OMe * OMe
Predict the major product for each of the following intramolecular reactions: (a) (b) [H*] -2 NH2 [H] NH2 -H20
Identify the reactants that you would use to make each of the following imines: (a) (b) (c) N.
Benzene was treated with isopropyl chloride in the presence of aluminum trichloride under conditions that favor dialkylation. Draw the major product expected from this reaction.
Identify the reactants that you would use to make each of the following enamines: (a) (b) (c) -N
Predict the major product for each of the following reactions: (a) (b) (c) (d) 1) LAH 2) H20 H NABH4,
Predict the major product of each reaction below: (a) (b) (c) 1) EtMgBr 2) H20 :? H. 1) PhMgBr 2) H20
Propose an efficient synthesis for each of the following transformations: (a) (b) (c) (d) (e) (f) (g) -OH
Starting with benzene and using any other necessary reagents of your choice, design a synthesis for the following compound. -NH2 -
For each of the following compounds determine which (if any) lone pairs are participating in aromaticity. a. b. c. d. e. f. g. h. :N-H
When para-bromotoluene is treated with sodium amide, two products are obtained. Draw both products, and propose a plausible mechanism for their formation.
Draw a mechanism for the acid-catalyzed conversion of cyclohexanone into its tautomeric enol.
Identify whether each transformation below involves an increase, a decrease, or no change in the number of hydrogen atoms: a. b.
The vapor pressure of methanol(l) is 16.94 10 3 Pa at 298.15 K. Use this value to calculate G o f (CH 3 OH, g) G o f (CH 3 OH, l). Compare your result with those in Table 4.1.
The normal melting point of H 2 O is 273.15 K, and H fusion = 6010 J mol -1 . Calculate the change in the normal freezing point at 100. and 500. bar compared to that at 1 bar assuming that the...
Draw all lone pairs on each of the oxygen atoms in the compounds below. Before doing this, review in the following table, and then come back to these problems. Try to identify all lone pairs without...
At 298.15 K, G f (HCOOH, g) = -351.0 kJ mol -1 and G f (HCOOH, l) 361.4 kJ mol -1 . Calculate the vapor pressure of water at this temperature.
For each of the problems below, determine whether each curved arrow violates either of the two rules, and describe the violation, if any. (Dont forget to count all hydrogen atoms and all lone pairs.)...
In the double-slit experiment, researchers found that an equal number of electrons passes through each slit. Does this result allow you to distinguish between particle-like and wave-like behavior?
Why is a diffraction pattern generated by an electron gun formed by electrons interfering with themselves rather than with one another?
Arrange the following compounds in order of increasing boiling point: -, - -, -0
For each pair of compounds, identify whether they are constitutional isomers or two representations of the same compound: (a) (b) (c) (d)
Calculate the highest possible energy of a photon that can be observed in the emission spectrum of H.
In each case below, identify the highest and lowest energy conformations. In cases where two or three conformations are degenerate, draw only one as your answer. (a) (b) (c) (d)
For each of the following processes predict the sign of ÎS for the reaction. In other words, will ÎS sys be positive (an increase in entropy) or negative (a decrease in entropy)? a. b. c....
Which of the following functions are eigenfunctions of the operator B if B f (x) = d 2 f (x) / dx 2 : x 2 , cos x, e 3ix ? State the eigenvalue if applicable.
Find the result of operating with d 2 /dx 2 2x 2 on the function 2 e ax2 . What must the value of a be to make this function an eigenfunction of the operator? What is the eigenvalue?
Consider the following reaction: (a) Use Table 6.1 to estimate ÎH for this reaction. (b) ÎS of this reaction is positive. Explain. (c) Determine the sign of ÎG. (d) Is the sign of...
For each of the following reactions identify the arrow-pushing pattern that is being utilized: a. b. c. d. H,
Find the result of operating with d 2 /dx 2 + d 2 /dy 2 + d 2 /dz 2 on the function x 2 + y 2 + z 2 . Is this function an eigenfunction of the operator?
Find the result of operating with (1/r 2 ) (d /dr) (r 2 d /dr) + 2/r on the function Ae br . What must the values of A and b be to make this function an eigenfunction of the operator?
Draw a complete mechanism for the following transformation. NaOH, heat
Draw curved arrows for each step of the following mechanism: : : H-OSO3H H I IN- N- NH2 OsoH : :SO3H NH2 `NH2 NH2 H-OSO3H le CsoH N- --0 N, "9 NH2 NH2 H-OSO3H CsoH HEos: .. - - NH2 H-OSO3H...
In Problem 7.4, we saw that an intramolecular substitution reaction can occur when the nucleophilic center and electrophilic center are present in the same compound. Draw the transition state of the...
Propose an efficient synthesis for the following transformation. Take special notice of the fact that the starting material has a six-membered ring while the product has a fivemembered ring.
Draw a reasonable mechanism for the following transformation. NaOH, H,0 Heat
Draw the product of the Robinson annulation reaction that occurs when the following compounds are treated with aqueous sodium hydroxide.
Draw a plausible mechanism for the following transformation. NO2 NO2 NaOH, H,0 eat
The following two drawings are resonance structures of one compound: But the following two drawings are not resonance structures: They are, in fact, two different compounds. Explain. Not resonance...
Predict the major product of the following reactions. a. b. c. d. NBS Heat or light Na,Cr,0, H,SO,, H20
One variation of the Gabriel synthesis employs hydrazine to free the amine in the final step of the synthesis. Draw the by-product obtained in this process. ? RNH, + N-R H,N-NH2
What is the relationship between the zero point energy for a H atom and a H 2 molecule in a one-dimensional box?
Why must the amplitudes of the first derivatives of the energy eigenfunctions in the finite depth box and in the adjoining barrier regions have the same value at the boundary?
Predict the expected product(s) when benzene is treated with each of the following alkyl halides in the presence of AlCl 3 . In each case, assume conditions have been controlled to favor...
A compound with molecular formula C 8 H 8 O produces an IR spectrum with signals at 3063, 1686, and 1646 cm -1 . The 1 H NMR spectrum of this compound exhibits a singlet at 2.6 ppm (I = 3H) and a...
Consider the equilibrium NO 2 (g) NO(g) + 1/2O 2 (g). One mole of NO 2 (g) is placed in a vessel and allowed to come to equilibrium at a total pressure of 1 bar. An analysis of the contents of the...
The vibrational frequency for D 2 expressed in wave numbers is 3115 cm 1 . What is the force constant associated with the DD bond? How much would a classical spring with this force constant be...
The infrared spectrum of 7 Li 19 F has an intense line at 910.57 cm 1 . Calculate the force constant and period of vibration of this molecule.
Predict the product(s) obtained when each of the following compounds is treated with a mixture of nitric acid and sulfuric acid: (a) (b) (c) (d) (e) Br
Calculate the expectation value of the radius r at which you would find the electron if the H atom wave function is 100 (r).
Ions with a single electron such as He + , Li 2+ , and Be 3+ are described by the H atom wave functions with Z/a 0 substituted for 1/a 0 , where Z is the nuclear charge. The 1s wave function becomes ...
At 47C, the vapor pressure of ethyl bromide is 10.0 Torr and that of ethyl chloride is 40.0 Torr. Assume that the solution is ideal. Assume there is only a trace of liquid present and the mole...
The observed lines in the emission spectrum of atomic hydrogen are given by In the notation favored by spectroscopists, = 1/ = E/hc and R H =109,677 cm 1 . The Lyman, Balmer, and Paschen series...
Determine in each of the following cases if the function in the first column is an eigenfunction of the operator in the second column. If so, what is the eigenvalue? a. b. c. sine cos 3x (1/x) d/dx
Determine in each of the following cases if the function in the first column is an eigenfunction of the operator in the second column. If so, what is the eigenvalue? a. b. c. 1 cose sin e- sin e de...
Identify the base you would use for each of the following transformations. (a) (b) 1) ? 2) , OEt OEt 1) ? 2) H,o*
Identify the major product formed when each of the following compounds is treated with Et2CuLi followed by mild acid. (a) (b) (c) CN
Using a Stork enamine synthesis, show how you might accomplish each of the following transformations. (a) (b) (c) H
Propose an efficient synthesis for each of the following transformations: (a) (b) (c) (d) (e) (f) TH.
Draw the product obtained when each of the following compounds is heated in the presence of a base to give an aldol condensation. (a) (b) (c) H.
Identify the reagents you would use to convert cyclohexanone into each of the following compounds. (a) (b) (c) (d) (e) (f) (g)
Show two different ways of preparing each of the following compounds via a reductive amination: (a) (b) (c) (d) (e) Z
How would you use IR spectroscopy to distinguish between the following pairs of compounds? (a) (b) N.
Atomic chlorine has two naturally occurring isotopes, 35 Cl and 37 Cl. If the molar abundance of these isotopes is 75.4% and 24.6%, respectively, what fraction of a mole of molecular chlorine (Cl 2 )...
Determine the number of permutations of size 3 that can be made from the set {1, 2, 3, 4, 5, 6}. Write down all of the permutations.
For a particle in a two-dimensional box, the total energy eigenfunctions are a. Obtain an expression for E nx , n y in terms of n x , n y , a, and b by substituting this wave function into the two...
Does the average length of a quantum harmonic oscillator depend on its energy? Answer this question by referring to the harmonic potential function shown in Figure 18.7. The average length is the...
The 13 C nucleus is a spin 1/2 particle as is a proton. However, the energy splitting for a given field strength is roughly 1/4 of that for a proton. Using a 1.45-T magnet as in Example Problem 30.6,...
Although the vibrational degrees of freedom are generally not in the high-T limit, is the vibrational partition function evaluated by discrete summation?
In this problem, you will calculate the transmission probability through the barrier illustrated in Figure 16.10. We first go through the mathematics leading to the solution. You will then carry out...
In this problem, you will solve for the total energy eigenfunctions and eigenvalues for an electron in a finite depth box. We first go through the calculation for the box parameters used in Figure...
Purification of water for drinking using UV light is a viable way to provide potable water in many areas of the world. Experimentally, the decrease in UV light of wavelength 250 nm follows the...
Arrange v mp , v ave , and v rms in order from largest to smallest speed.
For N 2 at 298 K, what fraction of molecules has a speed between 200. and 300.m s 1 ? What is this fraction if the gas temperature is 500. K?
Using Table 22.3, which lists the possible terms that arise from a given configuration, and Hunds rules, write the term symbols for the ground state of the atoms H through F in the form (2s+1) L J ....
You are performing an experiment using 3 H (half-life = 4.50 10 3 days) labeled phenylalanine in which the five aromatic hydrogens are labeled. To perform the experiment, the initial activity cannot...
Determine the expression for fractional coverage as a function of pressure for the dissociative adsorption mechanism described in the text in which adsorption is accompanied by dissociation: R,(g) +...
Calculate the bond order in each of the following species. Predict which of the two species in the following pairs has the higher vibrational frequency: a. Li 2 or Li + 2 b. C 2 or C + 2 c. O 2 or O...
The angular functions, Π(θ)Φ(), for the one-electron HartreeFock orbitals are the same as for the hydrogen atom, and the radial functions and radial probability...
There are only two stereoisomeric ketotetroses. (a) Draw both of them. (b) Identify their stereoisomeric relationship. (c) Identify which is a d sugar and which is an l sugar.
Which of the following terms best describes the relationship between d-fructose and d-glucose? Explain your choice. (a) Enantiomers (b) Diastereomers (c) Constitutional isomers
Provide a complete name for the following compound: CH-
Draw the open-chain form of the following cyclic monosaccharide: CH,OH -
VSEPR (valence state electron pair repulsion) theory was formulated to anticipate the local geometry about an atom in a molecule (see discussion in Section 25.1). All that is required is the number...
When vibrational transitions are observed in an electronic absorption spectrum, these transitions can be used to determine dissociation energies. Specifically, a BirgeSponer plot is constructed where...
Chemists recognize that the cyclohexyl radical is likely to be more stable than the cyclopentylmethyl radical, because they know that six-membered rings are more stable than five-membered rings and,...
Identify the reagents necessary to make each of the following amino acids via the amidomalonate synthesis. (a) Isoleucine (b) Alanine (c) Valine
Identify the reagents necessary to make each of the following amino acids using a HellVolhardZelinski reaction. (a) Leucine (b) Alanine (c) Valine