The best laboratory vacuum pump can generate a vacuum of about 1 n Torr. At 25C and assuming that air consists of N, molecules with a collision diameter of395 pm, calculate (a) The mean speed of the...
Plot the molar entropy of a collection of harmonic oscillators as a function of T/ by and predict the standard molar entropy of ethyne at (a) 298 K, (b) 500 K. For data, see the preceding exercise.
Set up and solve the Huckel secular equations for the n electrons of NO-3. Express the energies in terms of the Coulomb integrals ao and aN and the resonance integral 13. Determine the delocalization...
Write down the expression for the radial distribution function of a 3p electron in a hydrogenic atom and determine the radius at which the electron is most likely to be found.
The second-order rate constant for the reaction A + 2 B --7 C + D is 0.21 dm 3 mol-J S-1. What is the concentration of C after? (a) 10 s, (b) 10 min when the reactants are mixed with initial...
Colorless nitric oxide, NO, combines with oxygen to form nitrogen dioxide, NO2, a brown gas. 2NO(g) + O2(g) 2NO2(g); H = 114 kJ What is the enthalpy change per gram of nitric oxide?
Determine the values of x = ((x2) - (x)2)1/2 and p = ((p2) (p)2)1/2 for (a) A particle in a box of length L and (b) A harmonic oscillator. Discuss these quantities with reference to the uncertainty...
Propose structures for compounds that fit the following 1H NMR data: (a) C5H10O 0.95 (6 H, doublet, J = 7 Hz) 2.10 (3 H, singlet) 2.43 (1 H, multiplet) (b) C3H5Br 2.32 (3 H, singlet) 5.35 (1 H,...
Mannose, one of the eight essential monosaccharide?s (Section 25.7), is biosynthesized as its 6-phosphate derivative from fructose 6-phosphate. No enzyme cofactor is required. Propose a mechanism....
Each of the following reactions has been reported in the chemical literature. Predict the product in each case, showing stereochemistry where appropriate. (a) CHs CH hea (b) (CH3)2(-C(CH3): T -...
Calculate the pressure differential of ethanol across the surface of a spherical droplet of radius 220 nm at 20e. The surface tension of ethanol at that temperature is 22.39 mN m-1
Which of the following pairs of structures represent resonanceforms? (b) :0: (a) :0: and and (d) :: (c) :0: :0: and and
Name the followingcompounds: NH2 (b) (a) (c) -NHCH2CH3 -CH2CH2NH2 Br Br (e) (f) H2NCH2CH2CH2CN (d) C N-CH2CH2CH3 CH
Propose mechanisms and show the expected products of the following reactions. (a) 2, 4-dinitrochlorobenzene + sodium methoxide (NaOCH3) (b) 2, 4-dimethylchlorobenzene + sodium hydroxide, 350 oC (c)...
Show that l, and 12 both commute with the Hamiltonian for a hydrogen atom. What is the significance of this result?
R. Eujen, B. Hoge, and D.J. Brauer (Inorg. Chem. 36, 1464 (1997» prepared and characterized several square-planar Ag (III) complex anions. In the complex anion [trans-Ag (CF3)2 (CN), 2|-, the...
The 1H NMR spectrum of bullvalene at 100 C consists only of a single peak at 4.22 ?. Explain. Bullvalene
Sketch the appearance of the IH-NMR spectrum of diethyl ether using J = 6.97 Hz and the data in Exercise 15.9b in a spectrometer operating at (a) 350 MHz, (b) 650 MHz.
Rhenium forms a series of solid oxides: Re2O7 (yellow), ReO3 (red), Re2O5 (blue), and ReO2 (brown). One of them has a crystal structure with the following unit cell: a. How many rhenium atoms (gray...
Using 1,2-dimethylcyclohexene as your starting material, show how you would synthesize the following compounds. (Once you have shown how to synthesize a compound, you may use it as the starting...
Ozone absorbs ultraviolet radiation in a part of the electromagnetic spectrum energetic enough to disrupt DNA in biological organisms and that is absorbed by no other abundant atmospheric...
Spin angular momentum is conserved when a molecule dissociates into atoms. What atom multiplicities are permitted when? (a) An 02 molecule (b) An N, molecule dissociates into atoms?
The preparation of cis-4-tert-butylcyclohexanol from its trans stereoisomer was carried out by the following sequence of steps. Write structural formulas, including stereochemistry, for compounds A...
In Problem 10.27, we saw that Doppler shifts of atomic spectral lines are used to estimate the speed of recession or approach of a star. From the discussion in Section 13.3a, it is easy to see that...
Two products, A and B, are obtained from the reaction of 1-bromobutane with NH3. Compound A reacts with acetyl chloride to form C, and B reacts with acetyl chloride to form D. The IR spectra of C and...
Chromic acid oxidation of an alcohol (Section 11-2A) occurs in two steps: formation of the chromate ester, followed by an elimination of H+ and chromium. Which step do you expect to be rate-limiting?...
The following 1H NMR signals are for three molecules with ether functional groups. All the signals are singlets (single, sharp peaks). Propose structures for these compounds, (a) C3H8O2, ( = 3.3 and...
Compounds A through H are isomeric bromoalkanes with the molecular formula C5H11br. With your team, draw all eight constitutional isomers. Indicate any stereo-center) (s), but do not label it (them)...
What pressure difference must be generated across the length of a 15 cm vertical drinking straw in order to drink a water-like liquid of density 1.0 g cm-3?
Normalize the molecular orbital A + B in terms of the parameter and the overlap integral S.
A solution contains 4.25 g of ammonia per 250.0 mL of solution. Electrical conductivity measurements at 25C show that 0.42% of the ammonia has reacted with water. Write the equation for this reaction...
Unknown X, C5H9Br does not react with bromine or with dilute KMnO4 Upon treatment with potassium tert-butoxide, X gives only one product, YC5H8, Unlike X, Y decolorizes bromine and changesKMnO4 from...
Thermodynamic considerations suggest that the copper monohalides CuX should exist mainly as polymers in the gas phase, and indeed it proved difficult to obtain the monomers in sufficient abundance to...
After treatment with peroxyformic acid, the peptide hormone vasopressin is partially hydrolyzed. The following fragments are recovered. Propose a structure for vasopressin. Phe-Gln-Asn...
Norbornadiene (Problem 14.41) can be prepared by reaction of chloroethylene with 1, 3-cyclopentadiene, followed by treatment of the product with sodium ethoxide. Write the overall scheme, and...
Show how you would accomplish the following syntheses. You may use whatever additional reagents you need. (a) (b) (c) (d) (e) (f) CHO CH,OH CHO CHO CH,Br Ph of CH, CH cth CH CH CHC-Ph 0 BrCH,CH,CCH...
The pKa values of oxaloacetic acid are 2.22 and 3.98. a. Which carboxyl group is more acidic? b. The amount of hydrate present in an aqueous solution of oxaloacetic acid depends on the pH of the...
What is the volume of 255.0 g of uranium if uranium has a density of 19.05 g/cm3?
Explore the conditions under which the 'integral' approximation for the translational partition function is not valid by considering the translational partition function of an Ar atom in a cubic box...
The ground-state electron configurations listed here are incorrect. Explain what mistakes have been made in each and write the correct electron configurations. Al: 1s22s22p43s23p3 B: 1s22s22p5 F:...
A 1.00-mole sample of an ideal gas in a vessel with a movable piston initially occupies a volume of 5.00 L at an external pressure of 5.00 atm. a. If Pex is suddenly lowered to 2.00 atm and the gas...
a. How many hydrogen and oxygen atoms are present in 1 molecule of H2O? b. How many moles of hydrogen and oxygen atoms are present in 1 mol H2O? c. What are the masses of hydrogen and oxygen in 1.0...
Explain why pressure substantially affects the solubility of O2 in water but has little effect on the solubility of NaCl in water?
What states of (a) Anthracene, (b) Coronene (24) may be reached by electric dipole transitions from their (totally symmetrical) ground states? 24 Coronene
The two isomers cis- and trans-4-tert-butyl-2-methylcyclohexanone are inter-converted by base treatment. Which isomer do you think is more stable, and why?
Ethyl triflate is much more reactive than ethyl mesylate toward nucleophiles in SN2 reactions. (a) Give the structures of all of the products formed when each compound reacts with potassium iodide in...
Consider the thermal decomposition of CaCO3: CaCO3(s) CaO(s) + CO2(g) The equilibrium vapor pressures of CO2 are 22.6 mmHg at 700C and 1829 mmHg at 950C. Calculate the standard enthalpy of the...
The photo shows physics instructor Marshall Ellenstein walking barefoot on broken glass bottles in his class. What physics concept is Marshall demonstrating, and why is he careful that the broken...
Xylitol is a sweetener that is used in sugarless chewing gum. Starting with an appropriate monosaccharide, outline a possible synthesis of xylitol.a OH OH HO OH OH Xylitol
Propose a mechanistic pathway for the biosynthesis of caryophyllene, a substance found in cloveoil. Caryophyllene H3C-
The molar mass of benzoic acid (C6H5COOH) determined by measuring the freezing-point depression in benzene is twice what we would expect for the molecular formula, C7H6O2. Explain this apparent...
A technique called photoelectron spectroscopy is used to measure the ionization energy of atoms. A sample is irradiated with UV light, and electrons are ejected from the valence shell. The kinetic...
A 6-kg piece of metal displaces 1 L of water when submerged. Show that its density is 6000 kg/m3. How does this compare with the density of water?
The simplest a, -unsaturated aldehyde Acrolein is prepared by heating glycerol with an acid catalyst. Suggest a mechanism for this reaction.
Calculate the fractions of molecules in a gas that have a speed in a range t. v at the speed ne relative to those in the same range at c itself? This calculation can be used to estimate the fraction...
What atomic terms are possible for the electron configuration np1ndl? Which term is likely to lie lowest in energy?
Ethers can be cleaved by treatment with strong acids. Show all of the steps in the mechanism for this reaction and explain why these products are formed rather than iodomethane and2-methyl-2-butanol:...
The total mass that can be lifted by a balloon is given by the difference between the mass of air displaced by the balloon and the mass of the gas inside the balloon. Consider a hot-air balloon that...
Using toluene as the ultimate source of all the carbon atoms, along with any necessary inorganic reagents, show how you could prepare each of the following: (a) Benzoyl chloride (f) Benzyl cyanide...
Henry's law constant for CO2 at 38C is 2.28 10-3 mol/L ? atm. Calculate the pH of a solution of CO2 at 38C in equilibrium with the gas at a partial pressure of 3.20 atm.
The reaction A- + H+ --7 P has a rate constant given by the empirical expression k2 = (8.72 x 1012)e-(6134KI/T dm-3 mol-1 s-1 Evaluate the energy and entropy of activation at 25C.
The green color observed in aurora borealis is produced by the emission of a photon by an electronically excited oxygen atom at 558 nm. Calculate the energy difference between the two levels involved...
Write appropriate structural formulas for (a) A cyclic molecule that is a constitutional isomer of cyclohexane, (b) Molecules with the formula C6H12 that contain one ring and that are enantiomers of...
Three students (A, B, and C) are asked to determine the volume of a sample of ethanol. Each student measures the volume three times with a graduated cylinder. The results in milliliters are: A (87.1,...
List the following compounds in order of decreasing acidity: CH3CHCH2OH CH3CH2CH2OH CH CH CH OH CH CHCH,OH Cl CI
(a)Write one or more appropriate Lewis structures for the nitrite ion, NO2- (b) With what allotrope of oxygen is it iso-electronic? (c) What would you predict for the lengths of the bonds in NO2-...
Norlutin® and Enovid® are ketones that suppress ovulation. Consequently, they have been used clinically as contraceptives. For which of these compounds would you expect the infrared carbonyl...
Give the general classification of each compound. (a) glyceryl tripalmitate (b) (c) (d) (e) (f) CH3(CH210 CH2 Na CH3 (CH21C (CH216-CH3 tetradecyl octadecanoate CH3 CH HoC caryophyllene (from cloves)...
Consider the reaction of all pairs of the following compounds in water solution: Ba(OH)2, Pb(NO3)2, H2SO4, NaNO3, MgSO4. a. Which pair (or pairs) forms one insoluble compound and one soluble compound...
Bone was dissolved in hydrochloric acid, giving 50.0 mL of solution containing calcium chloride, CaCl2. To precipitate the calcium ion from the resulting solution, an excess of potassium oxalate was...
Bronze is an alloy made of copper (Cu) and tin (Sn). Calculate the mass of a bronze cylinder of radius 6.44 cm and length 44.37 cm. The composition of the bronze is 79.42 percent Cu and 20.58 percent...
The internal engine of a 1200-kg car is designed to run on octane (C8H18), whose enthalpy of combustion is 5510 kJ/mol. If the car is moving up a slope, calculate the maximum height (in meters) to...
Estimate each of the bond angles and order the bond lengths (smallest first) for each of the following molecule. (a) a) (b) d) Br:
What volume of 3.99 M H2SO4 is needed to obtain 4.61 mol of H2SO4?
There is a gaseous interstellar cloud in the constellation Ophiuchus that is illuminated from behind by the star Ophiuci. Analysis of the electronic-vibrational-rotational absorption lines obtained...
Chlorine dioxide oxidizes iodide ion in aqueous solution to iodine; chlorine dioxide is reduced to chlorite ion. 2ClO2(aq)+ 2I(aq) 2ClO2(aq) + I2(aq) The order of the reaction with respect to ClO2...
Use Newman projection formulas for ethylene glycol (1,2-ethanediol) and butane to explain why the gauche conformer of ethylene glycol is expected to contribute more to its ensemble of conformers than...
Eagle Corporation issued $ 10,000,000, 6.5 percent bonds dated April 1, 2015. The market rate of interest was 7 percent, with interest paid each March 31. The bonds mature in three years, on March...
How many moles are present in 334 L of H2 at STP?
Predict the products of the following Diels-Alder reactions. Include stereochemistry where appropriate. (a) (b) (c) (d) (e) (f) COOCH COOH , H CN H CN CN H CN
What is the maximum possible concentration of Ni2+ ion in water at 25oC that is saturated with 0.10 M H2S and maintained at pH 3.0 with HCl?
Draw a perspective structure or a Fischer projection for the products of the following SN2 reactions. (a) trans-1-bromo-3-methylcyclopentane + KOH (b) (R)-2-bromopentane + KCN (c) (d) (e) (f) CH Br-H...
At a particular temperature, a 3.0- L flask contains 2.4 moles of Cl2, 1.0 mole of NOCl, and 4.5 10-3 mole of NO. Calculate K at this temperature for the following reaction. 2NOCl(g) 2NO(g) + Cl2(g)
(a) A compound U (C9H10O) gives a negative iodoform test. The IR spectrum of U shows a strong absorption peak at 1690 cm-1. The 1H NMR spectrum of U gives the following: Triplet...
An unknown compound gives the following mass, IR, and NMR spectra. Propose a structure, and show how it is consistent with the spectra. Show the fragmentations that give the prominent peaks at m/z...
When the first compound shown here is treated with sodium methoxide, the only elimination product is the trans isomer. The second diastereomer (blue) gives only the cis product. Use your models and...
Thiophene is a liquid compound of the elements C, H, and S. A sample of thiophene weighing 7.96 mg was burned in oxygen, giving 16.65 mg CO2. Another sample was subjected to a series of reactions...
A sample of a bright blue mineral was weighed in air, then weighed again while suspended in water. An object is buoyed up by the mass of the fluid displaced by the object. In air, the mineral weighed...
Ethanol, CH3CH2OH, is known as grain alcohol and is the alcohol found in alcoholic beverages. Calculate the mole fraction of ethanol in a solution that contains 4.76 g of ethanol dissolved in 50.0 g...
The shape of a spectral line, J(w), is related to the free induction decay signal G(t) by where a is a constant and 'Re' means take the real part of what follows. Calculate the lineshape...
R. Viswanathan, R.W. Schmude, Jr., and K.A. Gingerich (J. Phys. Chem. 100,10784 (1996)) studied thermodynamic properties of several boron-silicon gas-phase species experimentally and theoretically....
Using benzene or toluene as the only aromatic organic starting material, devise a synthesis for each of the following compounds. Name the product. CH CH3 Cl CH3 Cl a. b. C. d. Br NO2 NO2
Which of the following molecules have sets of nuclei that are chemically but not magnetically equivalent? (a) CHZ=C=CP1, (b) cis- and trans-[Mo (CO) 4(PHJ) 2]
Show how ethyl phenyl ketone (C6H5COCH2CH3) could be synthesized from each of the following: (a) Benzene (b) Benzonitrile, C6H5CN (c) Benzaldehyde
The homologous series of primary amines, CH3(CH2)nNH2, from CH3NH2 to CH3(CH2)13 NH2 all have their base (largest) peak at m/z 30. What ion does this peak represent, and how is it formed?
How would you convert 2-nonyne into (E)-2-nonene?
Show how you would use the acetoacetic ester synthesis to make the following compounds. (a) (b) (c) CH-CHC CH CHCH3 CH3
A mixture contained calcium carbonate, CaCO3, and magnesium carbonate, MgCO3. A sample of this mixture weighing 7.85 g was reacted with excess hydrochloric acid. The reactions are CaCO3(g) + 2HCl(aq)...
Hydrogen peroxide, H2O2, is a colorless liquid whose solutions are used as a bleach and an antiseptic. H2O2 can be prepared in a process whose overall change is H2(g) + O2(g) H2O2(l) Calculate the...
For each of the following molecules or ions of sulfur and oxygen, write a single Lewis structure that obeys the octet rule, and calculate the oxidation numbers and formal charges on all the atoms:...