Académique Documents
Professionnel Documents
Culture Documents
H
5 6 7 8 9
He
4.003 10
1.008 3
Li
13 14 15
Be
O
16
F
17
Ne
18
6.941 9.012
11
12
Na
21 22 23 24 25 26 27 28 29 30 31 32
Mg
Al
Si
P
33
S
34
Cl
35
Ar
36
22.99 24.31
19
20
K Mn
43 44 45 46 47 48 49
Ca
39 40 41 42
Sc
Ti Ni Zn
Cr
Fe
Co
Cu
Ga
Ge
50
As
51
Se
52
Br
53
Kr
54
39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.39 69.72 72.61 74.92 78.96 79.90 83.80
37
38
Rb Zr
72 73 74 75 76 77 78 79
Sr Mo
57
Nb
Tc
Ru
Rh
Pd
Ag
Cd
80
In
81
Sn
82
Sb
83
Te
84
I
85
Xe
86
(98) 101.07 102.91 106.42 107.87 112.41 114.82 118.71 121.76 127.60 126.91 131.29
55
56
Cs
Ba
La Hf Re Pt
Ta
Os
Ir
Au
Hg
Tl
Pb
Bi
Po
At
Rn
132.91 137.33 138.91 178.49 180.95 183.85 186.21 190.20 192.22 195.08 196.97 200.59 204.38 207.20 208.98 (209) (210) (222) 104 105 [106] [107] [108] [109] 87 88 89
Fr
Ra
Ac
Rf
Ha
(262) (263) (262) (265) (266) 58 59 60 61 62 63 64 65 66 67 68 69 70 71
Lanthanide seriesCe
Pr
Nd
Pm
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
140.12 140.91 144.24 (145) 150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97 100 101 102 103 90 91 92 93 94 95 96 97 98 99
Actinide series Th
Pa
Np
Pu
Am
Cm
Bk
Cf
Es
Fm
Md
No
Lr
232.04 231.04 238.03 237.05 (244) (243) (247) (247) (251) (252) (257) (258) (259) (260)
Harvard University
d)
(4/3)(2.16)3
e)
(14.3)(60)
f) (6.0+9.7+0.61)(1.113)
g)
6.95810 8 5.9110 12
h)
(1.17310 3) + 3.6
i) (1.1106 )(2.24610 10 )
Harvard University
b)
c)
A shipping channel is dredged to a depth of 4.5 fathoms. Calculate its depth in feet.
2.
Given the following conversion factors: 1 atm = 760 torr 1 torr = 0.01933 lb/in2 1 N = 0.225 lb 1 in = 2.54 cm 1 Pa = 1 N/m2 a) The pressure inside a laboratory vessel is 35 lb/in2. Calculate the equivalent pressure in atmospheres.
b)
A certain chemistry experiment takes place in a high-pressure chamber with a pressure of 2.7 atmospheres. Calculate the pressure in torr.
c)
The atmospheric pressure is measured to be 754 torr. Calculate the pressure in Pa.
Harvard University
b)
c)
A rectangular tank measures 1.0 5.0 2.0 meters. Calculate its volume in gallons.
2. A certain crystal of calcium chloride has a volume of 765.3 mm 3. a) Calculate the volume of this crystal in cubic inches (in 3).
b)
The density of CaCl2 is 2.51 g/cm3. Calculate the mass of this crystal.
Harvard University
b)
40Ca2+
c)
39K +
d)
39K
2.
Calcium chloride is an ionic substance. Determine the number of protons and electrons in a calcium ion (as found in calcium chloride).
3.
The chloride ion exists in two common isotopes: 35Cl and 37Cl. Determine the number of protons, neutrons, and electrons for both isotopes.
4. a)
The chemical formuls for ammonia is NH3. Please calculate the total number of protons, neutrons, and electrons in one molecule of NH 3. (Assume that the only isotopes present are 14N and 1H.)
b)
In aqueous solution, some of the ammonia is present as the ammonium ion, NH4+ . Calculate the total number of protons, neutrons, and electrons in one ammonium ion, NH4+. (Again, assume that the only isotopes present are 14N and 1H.)
Harvard University
Oxidation Numbers
1. Write the oxidation numbers of each atom in the following species:
BrO3
H3AsO3
AsH3
CrCl3
KClO3
S2O32
OF2
Na2O2
Fe3O4
2.
Identify whether oxidation and reduction is taking place in each of the following equations. If so, identify which species is being reduced and which is being oxidized.
N2 + 3 H2 2 NH3
Harvard University
Naming Compounds
1. a) b) c) d) e) f) g) h) i) j) k) l) Write the chemical formula for each of the following species: Copper (I) phosphide Iron (III) sulfate Potassium chlorate Aluminum chloride Chromium (VI) oxide Ammonium iodide Lithium nitride Aluminum carbonate Cesium phosphate Rhenium (VII) oxide Tin (IV) chloride Gallium fluoride
m) Silver (II) Fluoride n) o) p) 2. a) b) c) Potassium Nitrate Barium Phosphate Ammonium Sulfate Write an acceptable chemical name for each of the following species. SiCl4 Mn2O7 Mg3N2
Harvard University
b)
An unknown compound is discovered in a raid on a terrorist organization; it is believed that the compound is Sarin. When a 10.0-gram sample of this compound is completely combusted, 15.6 g CO2 and 6.4 g H2O are produced, along with other combustion products. Using numerical calculations, prove that this unknown compound can not be Sarin.
2.
A pulverized rock sample believed to be pure calcium carbonate is subjected to chemical analysis and found to contain 51.3% calcium, 7.7% carbon, and 41.0% oxygen by mass. Demonstrate that this natural sample cannot be pure CaCO 3.
Harvard University
b)
c) 2. a)
the exact molar mass Compound Z, which consists of only carbon, hydrogen, and oxygen, has just been isolated from a tropical plant. When 5.467 grams of compound Z are burned in excess oxygen, 15.02 grams of CO2 and 2.458 grams of H2O are produced. Determine the empirical formula of compound Z.
b)
Other experiments suggest that compound Z has a molar mass of approximately 250 g/mol. Calculate the true molar mass of compound Z.
3. a)
When bleach and ammonia are mixed, certain toxic compounds can be formed. One compound is isolated which contains only nitrogen, hydrogen, and chlorine. When a 1.376-gram sample of this compound is completely combusted, 0.478 g of H2O and 0.372 g of N2 are recovered. Determine the empirical formula of this compound.
b)
Other experiments suggest that the molar mass of this compound is about 50 g/mol. Determine the molecular formula of this compound.
Harvard University
b)
Ca3(PO4)2 (s) + SiO2 (s) + C (s) P 4 (g) + CaSiO3 (l) + CO (g) (Hint: Balance the P first)
2.
Photosynthesis (in plants) converts carbon dioxide and water into glucose (C6 H12O6 ) and oxygen. Write and balance the chemical equation for photosynthesis.
3.
Niobium metal will react with solid iodine to produce solid triniobium octaiodide. Write and balance the equation for this process.
4.
Write and balance the chemical equation for the complete combustion of octane, C8H18 (l).
Harvard University
Stoichiometry of Reactions
1. Sodium hypochlorite, the active ingredient in Clorox, can be made by the following reaction: 2 NaOH (aq) + Cl2 (g) NaCl (aq) + NaClO (aq) + H2O (l) If chlorine gas is bubbled continuously through a solution containing 60.0 g of NaOH, how many grams of NaClO can be produced, assuming the reaction goes to completion?
2.
For the following unbalanced chemical equation: NiS + O2 + HCl NiCl2 + H2 SO4 a) Write the balanced chemical equation for this reaction.
b)
10
Harvard University
b)
What mass of vanadium (II) oxide can be produced from a mixture of 100.0 grams of V2 O5 and 100.0 grams of Zn?
2. a)
Many binary compounds of phosphorus and sulfur have been prepared. Balance the following chemical equation for the preparation of P 4S5. (Hint: balance the S first.) P4S3 + Br2 P 4S5 + PBr3
b)
What is the maximum quantity of P4S5 that could be prepared from 100.0 g of P4S3 and 100.0 mL of liquid bromine? (Density of bromine is 3.12 g/mL)
11
Harvard University
Stoichiometry of Mixtures
1. Ferrous oxalate, FeC2 O4 , will decompose on heating: FeC2 O4 FeO + CO2 + CO The gaseous products (a mixture of CO2 and CO) are collected. Calculate the percent by mass of CO2 in this gaseous mixture.
2.
A certain mixture of CuO and Cu2 O weighs 10.50 grams total. Complete reduction of this mixture produces 8.66 grams of pure metallic Cu. Determine the amounts of CuO and Cu2 O in the original mixture.
3.
A certain mixture of CuS and Cu2 S weighs 10.80 grams total. Complete reduction of this mixture produces 8.06 grams of pure metallic Cu. Determine the amounts of CuS and Cu2 S in the original mixture.
12
Harvard University
Solutions: Molarity
1. A 10.0 mL sample of concentrated sulfuric acid contains 17.7 g of H2SO4. Determine the molarity of concentrated sulfuric acid.
2.
Pure acetic acid (C2H4O2) has a density of 1.049 g/mL. Calculate the molarity of pure (anhydrous) acetic acid.
3.
A hydrochloric acid solution is prepared by dissolving 1.97g of hydrogen chloride gas in 27.3 mL of water and then diluting that mixture to a total volume of 250.00 mL. Calculate the molarity of the resulting solution.
4.
The concentration of NaClO in Clorox is 0.705 M. Calculate the mass of NaClO present in 1.0 mL of Clorox.
5.
A solution is prepared by dissolving x grams of potassium nitrate in water and diluting to a total volume of 100.0 mL. Another solution is prepared by dissolving y grams of sodium chloride in water and diluting to a total volume of 500.0 mL. Both solutions are then mixed together, giving a final concentration of KNO3 of 0.073 M and a final concentration of NaCl of 0.128 M. Calculate x and y.
13
Harvard University
b)
You accidentally pour 1.0 mL of Clorox into a large bucket of ammonia solution. What mass of NCl3 can be produced if the reaction goes to completion? (Clorox is a 0.705-molar solution of NaClO in water.)
2.
A sample of calcium carbonate weighing 6.35 grams is placed in 500.0 mL of 0.31M hydrochloric acid and allowed to react to form calcium chloride and carbon dioxide gas. Calculate the maximum mass of carbon dioxide gas that can be produced.
14
Harvard University
2.
A student has dissolved 87.5 grams of sodium hydroxide in 1.53 liters of water. This strongly basic solution must be neutralized before disposal. What volume of 1.27 M HCl would be required to completely neutralize this solution?
3.
Phosphoric acid can be neutralized by sodium hydroxide according to the equation: H3PO4 + 3 NaOH Na3PO4 + 3 H2O What volume of 0.176 M NaOH would be required to neutralize 5.00 mL of concentrated (14.8 M) phosphoric acid?
15
Harvard University
2.
A 10.0-gram sample of an unknown solid monoprotic acid is dissolved in water and titrated with 0.789 M NaOH, requiring 40.6 mL to reach the endpoint. Determine the molar mass of the unknown acid.
3.
HX is a monoprotic acid; it has only one acidic proton per molecule. When 1.736 grams of HX are titrated with 1.334 M NaOH, the endpoint is reached with 10.92 mL of base. Calculate the molar mass of HX.
16
Harvard University
2.
Four individual solutions are prepared and mixed together in the following order: 1. Start with 100. mL of 0.100 M BaCl2 2. Add 50. mL of 0.100 M AgNO3 ; a precipitate of AgCl is formed. 3. Add 50. mL of 0.100 M H2 SO4 ; a precipitate of BaSO4 is formed. 4. Finally, add 250. mL of 0.100 M NH3 to neutralize the acid. Determine the concentrations of each of the following species in the resulting mixture: Ba2+ , Cl , NO3 , NH3 , NH4 + (Hint: What is the total volume?)
17
Harvard University
b)
What mass of Cl2 must be released into the classroom described above at 25C in order for humans to detect the odor of chlorine?
2.
It requires 0.182 mol of O2 gas to exert a pressure of 1.50 atm in a particular tank at 25C. What mass of O2 would be required to exert a pressure of 17.2 atm in the same tank at 100C? Neglect expansion of the tank itself.
18
Harvard University
2.
Ferrous oxalate, FeC2 O4 , will decompose on heating: FeC2 O4 (s) FeO (s) + CO2 (g) + CO (g) A 1.25-gram sample of FeC2 O4 is added to an evacuated 2.00-liter steel vessel. The vessel is heated to 400C, at which point all the FeC2 O4 is decomposed. Calculate the pressure inside the vessel at 400C.
3.
Ethylene, C2 H4 , will react with hydrogen gas under appropriate conditions to form ethane, C2 H6 . A 10.0-liter vessel is charged with 1.5 atm of hydrogen and 1.0 atm of ethylene at 25C. The reaction is allowed to proceed to completion. Determine the total pressure in the vessel at 25 at the completion of the reaction.
19
Harvard University
Mixtures of Gases
1. A 10.0-liter chamber contains a mixture of nitrogen and oxygen at a total pressure of 760. torr and a constant temperature of 25C. The mole fraction of oxygen in the mixture is 0.211. a) Calculate the number of moles of oxygen in the chamber.
b)
Gas is pumped out of the chamber until the total pressure is 0.100 torr. Calculate the new partial pressure of oxygen in the chamber.
c)
Pure nitrogen gas is added to the chamber until the total pressure is again 760. torr, then gas is pumped out of the chamber until the total pressure is 0.100 torr. Calculate the new partial pressure of oxygen after this process.
2.
A sample of the gas butane (C4H10), of unknown mass, is contained in a vessel of unknown volume, V, at 24.8C and a pressure of 560.0 torr. To this vessel 8.6787 g of Ne are added in such a way that no butane escapes. The total pressure of the vessel (at the same temperature) is 1420.0 torr. Calculate the volume of the vessel and the mass of the butane.
20
Harvard University
2.
Potassium chlorate, KClO3 , decomposes when heated: KClO3 (s) KCl (s) + 3 /2 O2 (g) 1.00 gram of potassium chlorate is completely decomposed and the oxygen is collected over water at 25C and 0.99 atm. Calculate the total volume of gas collected. (The vapor pressure of water at 25C is 23.8 torr).
3.
A 2.00-liter steel cylinder of oxygen gas has a pressure of 17.2 atm at 25C. You want to reduce the pressure in the cylinder to 15.5 atm, so you allow oxygen to escape from the cylinder and collect the escaping gas over water. What volume of gas should you collect at 25C and 1.00 atm in order to achieve the desired pressure in the cylinder? (The vapor pressure of water is 23.76 torr at 25C.)
21
Harvard University
2.
Ozone (O3) can be prepared in the laboratory by passing an electrical discharge through a quantity of oxygen gas (O2): 3 O2 (g) 2 O 3 (g) An evacuated steel vessel with a volume of 10.00 liters is filled with 32.00 atm of pure O2 at 25C. An electric discharge is passed through the vessel, causing some of the oxygen to be converted into ozone. As a result, the pressure inside the vessel drops to 30.64 atm at 25C. Calculate the final percent by mass of ozone in the vessel.
22
Harvard University
2.
Consider the reaction used to produce NaAlCl4: 2 Al2O3 (s) + 6 Cl2 (g) + 4 NaCl (l) 4 NaAlCl4 (l) + 3 O2 (g) An evacuated reaction vessel with a volume of 10.0 liters is filled with chlorine gas at 25C and a pressure of 1.00 atm. Al2O3 and NaCl are added, and the mixture is heated to 850C until the reaction is complete. The final total pressure in the vessel (at 850C) is 2.70 atm. a) What mass of Cl2 was present in the reactor initially?
b)
c)
23
Harvard University
b)
2.
A 2.00-liter steel cylinder of oxygen gas has a pressure of 17.2 atm at 25C. You want to reduce the pressure in the cylinder to 15.5 atm, so you drill a tiny pinhole and allow the oxygen to effuse into a vacuum. You know that, under identical conditions, this pinhole will allow 0.017 moles of argon gas to effuse every hour. a) Calculate the rms velocity of argon gas under these conditions.
b)
How long should you let the oxygen escape from this pinhole in order to reduce the pressure from 17.2 atm to 15.5 atm?
24
Harvard University
Heat
1. a) 50 g of marble chips (heat capacity 0.94 J/g K) are heated from 25C to 200C. How much heat is consumed in this process?
b)
The hot marble chips are placed in 500. g of cold (10C) water. Calculate the final temperature of the system.
2.
A coffee-cup calorimeter contains 150. g of water at 24.6C. A 110-g piece of molybdenum metal is heated to 100.C and placed in the water in the calorimeter. The system reaches equilibrium at a final temperature of 28.0C. Calculate the specific heat capacity of molybdenum metal. (The specific heat capacity of water is 4.184 J/gC).
25
Harvard University
2.
A sample of solid naphthalene, C10H8 , weighing 0.6037 g, is burned by O2 (g) under pressure to form CO2 (g) and H2 O (l) in a bomb calorimeter. The temperature rises by 2.270C. The heat capacity of the calorimeter and its contents is 10.69 kJ/K. Calculate H for the combustion of naphthalene. (For this calculation, assume that H E.)
3.
When a 0.235-gram sample of benzoic acid is burned in a calorimeter, a 1.642C rise in temperature is observed. When a 0.265-gram sample of caffeine (C8 H10O2 N4 ) is burned, a 1.525C rise in temperature is measured. Using the value 26.38 kJ/g for the heat of combustion of benzoic acid, calculate the heat of combustion per mole of caffeine at constant volume. (For this calculation, assume that H E.)
26
Harvard University
2.
With all the hot weather this past summer, everyone was drinking a lot of iced tea. (Iced tea sales increase dramatically when the temperature gets above 70F.) Given H for the melting of ice: H2O (s) H2O (l) H = +6.01 kJ/mol
Given 400.0 grams of hot tea at 80C, calculate the mass of ice at 0C which must be added to obtain iced tea at 10C. (The specific heat of the tea is 4.18 J/gC.)
27
Harvard University
Hess's Law
1. Given the following enthalpies of reaction: N2 O4 (g) 2 NO2 (g) NO (g) + 1/2 O2 (g) NO2 (g) Calculate the enthalpy of reaction for: 2 NO (g) + O2 (g) N 2 O4 (g) H = 57.20 kJ H = 57.07 kJ
2.
Given the following enthalpies of reaction: NH3 (g) NH3 (aq) HNO3 (g) HNO3 (aq) NH4NO3 (s) NH4NO3 (aq) NH3 (aq) + HNO3 (aq) NH4NO3 (aq) Calculate the enthalpy of reaction for: NH3 (g) + HNO3 (g) NH4NO3 (s) H = 34.10 kJ/mol H = 72.3 kJ/mol H = 26.4 kJ/mol H = 52.3 kJ/mol
28
Harvard University
2.
Given the following data for butane (C 4H10): Hf (C4H10 (g)) = 124.7 kJ/mol Hf (H2O (g)) = 241.8 kJ/mol Hf (CO2 (g)) = 393.5 kJ/mol Hvap(C4H10 (l)) = 22.9 kJ/mol Density of C4H10 (l) = 0.59 g/mL
and the balanced equation for the combustion of liquid butane: C4H10 (l) + 13/2 O2 (g) 4 CO 2 (g) + 5 H2O (g) Calculate the quantity of heat released by the combustion of 10.0 mL of liquid butane (the amount of butane in a cigarette lighter).
29
Harvard University
b)
Calculate the work w for the evaporation of one mole of methanol at its boiling point.
c)
Determine E for the evaporation of one mole of methanol at its boiling point.
Harvard University
b)
Using the following thermochemical data, and your answer to part (a) above, determine Hf for NH4NO3 (s). Hf (NH4+ (aq)) = 132.5 kJ/mol Hf (NO3 (aq)) = 205.0 kJ/mol
2.
Sodium azide will decompose explosively when heated; this reaction is the source of the gas used to inflate automobile air bags: 2 NaN3 (s) 2 Na (s) + 3 N 2 (g) a) A 10.0-gram sample of sodium azide is completely decomposed in a bomb calorimeter. If the heat capacity of the calorimeter and its contents is 2750. J/K, and the temperature increases from 25.78C to 27.20C, calculate H for the above reaction. (For this calculation, assume that H E.)
b)
31
Harvard University
Calculate the mass of CO2 (g) which would be produced in this reaction.
b)
Determine the final temperature inside the vessel after combustion; neglect any loss of heat to the vessel or surroundings. (The mixture of gases has an average molar heat capacity of 21 J/molC)
c)
Calculate the partial pressure of CO2 (g) in the vessel after combustion.
32
Harvard University
b)
c)
d)
33
Harvard University
b)
Light having a wavelength of 2.50 107 m falls upon a piece of chromium in an evacuated glass tube. Determine the minimum deBroglie wavelength of the emitted photoelectrons.
34
Harvard University
0.1 0 -0.1 5 10 15
a) b)
Identify each as representing R, R2 , or r2 R2 . Which of the following describes a place where the electron will never be found: (A) = 0, r = 2ao (C) = 90, = 45, r = 12ao (B) = 45, = 90, r = 6ao (D) = 55, = 0, r = 10ao
c)
Choose the most likely radius to find an electron: (A) r = 12ao (C) r = 6ao (B) r = 2ao (D) r = 10ao
2.
Which of the following could be a slice of the 4fz 3 orbital in the (x, z) plane:
35
Harvard University
Subshell 1s 3d 5p
2.
total # of e
Using the Rydberg equation: 1 1 E = (2.18 1018 J) 2 2 n nf i Calculate the energy of the radiation emitted by a hydrogen atom if an electron undergoes a transition from a 4px orbital to a 2s orbital.
36
Harvard University
Harvard University
Be+ : N : Al3+ : H : O2 :
2. Write the ground state electron configurations for the following ions. Use the noble-gas abbreviations if appropriate.
38
Harvard University
b)
Atomic Mass
c)
Atomic Radius
d)
Metallic Character
2. a)
Find the following on the periodic tables below, and indicate their identity: Most reactive metal b) Most reactive nonmetal
Identity: __________
Identity: __________
39
Harvard University
Ba F
Ti Al
Ra In
Li As
b)
2.
Circle the element from each set with the smallest ionization energy. Explain your choices. a)
Tl Cs
Po Ga
Se Bi
Ga Se
b)
3.
Circle the element with the most negative electron affinity. Explain your choice.
Be
4.
Circle the ion with the largest radius. Explain your choice.
Se2
O2
Rb+
40
Harvard University
b)
More energy is released upon adding an electron to Br than upon adding one to Se.
c)
The reaction of Rb with water is much more violent that the reaction of Na with water.
2. a)
Two of the most fundamental properties of any element are its ionization energy and electron affinity. Fluorine has an electron affinity of 332 kJ/molone of the most negative of any of the elements. Briefly explain why its electron affinity is more negative than that of oxygen. (One or two sentences should suffice.)
b)
This very negative electron affinity makes fluorine extremely reactive. Explain.
c)
The noble gas xenon has an ionization energy of 1170 kJ/mol. This substantial ionization energy helps to make xenon very unreactive. Explain.
d)
Xenons neighbor on the periodic table, iodine, also has a high ionization energy (1020 kJ/mol). Iodine is quite reactive, however, unlike xenon. Explain.
41
Harvard University
b)
Write the electron configurations of neutral Bi and the Bi+ cation. Please use the noble-gas abbreviations.
Bi : Bi+ :
c) What are the n and l quantum numbers of the electron removed when Bi is ionized to Bi+ ?
n=
d) (circle one):
l=
greater than equal to less than
Would you expect Element 113 to have an ionization energy which is greater than, equal to, or less than that of bismuth?
Explain briefly. (It is not enough to simply state a trend; you must provide an explanation for the trend in terms of atomic structure.)
42
Harvard University
CF4
OF2
HCN
CO
NSF
HNO3
43
Harvard University
SF3+
C22
NO2
PH2
CO32
BH4
44
Harvard University
BBr3
BeH2
AlF3
ClO2
NO2
NO
45
Harvard University
SeF4
XeF2
AsCl5
AsF6
XeF3+
BrF2
46
Harvard University
Bond Enthalpies
1. a) The enthalpy of formation Hf of acetylene (C2 H2 ) is 226.6 kJ/mol. Draw a correct Lewis structure for acetylene.
b)
Given the following additional information, determine the bond enthalpy of the CC triple bond in acetylene. Hsub (C (s)) = 717 kJ/mol DHH = 436 kJ/mol DCH = 415 kJ/mol
2. a)
Cyanogen, NCCN, is a highly toxic gas. Draw a correct Lewis structure for cyanogen
b)
Given the following average bond enthalpies: (in kJ/mol) CN 293 CO 358 CC 348 C=N 615 C=O 799 OO 146 CN 891 CO 1072 O=O 495 Estimate H for the complete combustion of cyanogen: NCCN (g) + 2 O2 (g) N 2 (g) + 2 CO2 (g)
47
Harvard University
CO2
ONF
BF3
ICl3
Harvard University
IF4
PCl4+
SeO32
I3
For extra practice in applying VSEPR theory, go back to the pages of Lewis structures and predict the geometries of each of those molecules or ions. 49
Harvard University
b)
CH3CCCO2
c)
50
Harvard University
H = 49.13 kJ
a)
The molecule S8 has eight sulfur atoms arranged in a ring, or circle. Draw a Lewis structure for S8. (Note that each sulfur atom should be identical.)
b)
Specify the hybridization, electron pair geometry, and molecular geometry around each sulfur atom in S8.
c)
The average SS single bond energy is 266 kJ/mol. Using the H given at the top of this page, calculate the S=S double bond energy in S2 (g).
51
Harvard University
b)
Explain the bonding in formaldehyde: describe each - and -bond in the molecule. (e.g. There are two -bonds between H s orbitals and C sp2 hybrid orbitals)
c)
Imagine that formaldehyde is positioned in the y,z plane as shown below. On this framework, draw a perspective sketch of the formaldehyde molecule in this orientation, showing all - and -bonding orbitals and the lone pairs on the oxygen atom.
H C H O
x-axis
z-axis
x y-a
2.
is
Give the hybridization of each carbon atom in the tetrolate ion, CH3CCCO2. Describe each of the - and -bonds in this molecule. (Dont forget the CH bonds, and include resonance!)
52
Harvard University
b)
c)
d)
e)
The molecule allene, H 2C=C=CH2, is similar to CO2 in several respects. Draw a complete Lewis structure for allene.
f)
For allene, determine the hybridization of: the central carbon atom: a terminal carbon atom:
g)
Allene is not planar; the two ends of the molecule are in different perpendicular planes as shown:
H H C C C H H
Draw -bonding orbitals on the above diagram, showing clearly why the two ends of the molecule must be perpendicular to one another.
53
Harvard University
a)
type of interaction:
b)
type of interaction:
c)
type of interaction:
d)
type of interaction:
e)
type of interaction:
54
Harvard University
b) O2
c) BN
2. a)
Consider the bonding in NO from the viewpoint of molecular orbital theory: Draw an energy-level diagram for the valence molecular orbitals of NO. Be sure to include the atomic orbitals of N and O as well as the molecular orbitals. (Note: The molecular orbitals of NO have the same energy order as those for O2.)
b)
The NO molecule can lose or gain an electron to form NO + or NO, respectively. Circle the single best choice for each of the following questions. Has a double bond Is diamagnetic Has the longest bond of the three species Is isoelectronic with CO 55 NO NO NO NO NO+ NO+ NO+ NO+ NO NO NO NO
Harvard University
2p
2s
2s
C
atomic orbitals a) b) c)
CO2
molecular orbitals
O
atomic orbitals
O
atomic orbitals
Fill in the appropriate number of valence electrons in the C, O, and O atomic orbitals in the diagram above. Use arrows ( or ) to indicate electron spin. Fill in the appropriate total number of valence electrons in the CO 2 molecular orbitals in the diagram above. Use arrows to indicate electron spin. What is the total number of bonds (total bond order) for CO2?
d)
or
diamagnetic
e)
You add an electron to CO2, forming the CO2 ion. Would the CO bond length become (circle one) shorter 56
or
longer
Harvard University
a)
b)
RuO2
insulator
semiconductor
conductor
c)
GaAs
insulator
semiconductor
conductor
d)
TaN
insulator
semiconductor
conductor
e)
Ta3N5
insulator
semiconductor
conductor
2.
The mineral wstite consists of iron (II) oxide in which some of the Fe 2+ has been replaced with Fe3+. Wstite is observed to be a semiconductor. Is it an intrinsic semiconductor, a n-type semiconductor, or a p-type semiconductor? (circle one)
intrinsic
n-type
p-type
57
Harvard University
Intermolecular Forces
1. a) For each of the following substances, circle the one intermolecular force which would predominate in the solid or liquid phase: Substance Al2O3 F2 H 2O Br2 ICl NaCl Intermolecular Forces (circle the predominant one) London Dispersion London Dispersion London Dispersion London Dispersion London Dispersion London Dispersion Dipole-Dipole Dipole-Dipole Dipole-Dipole Dipole-Dipole Dipole-Dipole Dipole-Dipole Hydrogen Bonding Hydrogen Bonding Hydrogen Bonding Hydrogen Bonding Hydrogen Bonding Hydrogen Bonding Ionic Ionic Ionic Ionic Ionic Ionic
b)
58
Harvard University
Phase Changes
1. Elemental sulfur exhibits five (5) common phases. There are two solid phases of sulfur, known as S(I) (s) and S(II) (s), a liquid phase S (l), and two gas phases, one consisting of molecules of S8 (g) and one consisting of molecules of S 2 (g). Here are the phases of sulfur at 1.0 atm pressure, with specific heats and the enthalpy of each phase transition: below 368 K 368 K transition 368 388 K 388 K transition 388 718 K 718 K transition 718 882 K 882 K transition above 882 K a) S(I) (s) specific heat = 0.73 J/gK S(I) (s) S(II) (s) H = 0.401 kJ/mol S(II) (s) S(II) (s) S (l) S (l) S (l) 1/8 S8 (g)
1/
specific heat = 0.78 J/gK H = 1.722 kJ/mol specific heat = 1.04 J/gK H = 45.08 kJ/mol
S8 (g) specific heat = 0.73 J/gK 1/ S (g) H = 49.13 kJ/mol 8 S 8 (g) 2 2 S2 (g) specific heat = 0.59 J/gK
Identify the normal melting point and normal boiling point of sulfur.
b)
Calculate the total quantity of heat required to heat 1.00 gram of sulfur from 25C to 150.C.
59
Harvard University
2.
Given that the heat of vaporization of water is roughly 42 kJ/mol, and knowing that water ordinarily boils at 100C, what would the pressure in a vacuum dome have to be in order for water to boil at room temperature, 25C?
60
Harvard University
Phase Diagrams
1. Given the following data for iodine: normal boiling pt. normal melting pt. triple pt. vapor pressure a) 184C 113C 68 torr at 106C 1.0 torr at 39C
Sketch a phase diagram for iodine in the space below. Observe the labeled axes (not drawn to scale).
760 P (torr)
68
Label the following on the above diagram: solid, liquid, gas, normal boiling point, normal melting point, triple point
c)
A quantity of iodine is introduced into an evacuated flask at 25C. Two phases are observed in equilibrium at this temperature. What are they?
d)
61
Harvard University
2.
Calcium metal crystallizes in a face-centered cubic unit cell. The density of the solid is 1.54 g/cm3. Calculate the radius of a calcium atom.
62
Harvard University
b)
c)
63
Harvard University
2.
Given the following thermodynamic information: Na(g) Na (s) Na (s) + C (s) + 1/2 N2 (g) HCN (g) 1/2 H 2 (g) + C (s) + 1/2 N 2 (g) H2 (g) CN (g) + e Na+ (g) + e Na (g) NaCN (s) H (g) + CN (g) HCN (g) 2 H (g) CN (g) IE = 496 kJ/mol Hsub = 108 kJ/mol Hf = 87 kJ/mol DCH = 502 kJ/mol Hf = 135 kJ/mol DHH = 436 kJ/mol EA = 382 kJ/mol
Construct a Born-Haber cycle to calculate the lattice energy of NaCN (s). (Hint: You will need to use all of the above information in your answer!)
64
Harvard University
b)
c)
d)
e)
65
Harvard University
b)
Predict the vapor pressure of water over this solution at 25.0C. (The vapor pressure of pure water at 25C is 23.76 torr.)
2.
A solution containing 0.674 g of one type of interferon in 157 mL of aqueous solution has an osmotic pressure of 4.15 torr at 25C. Calculate the molar mass of this type of interferon.
3.
A solution of Br2 in CCl4 has a total vapor pressure of 129 torr at 25C. Calculate the mole fraction of each component in the solution. (At 25C, P(Br2 ) = 209 torr; P(CCl4 ) = 109 torr)
66
Harvard University
b)
Predict the vapor pressure of water over this solution at 25C. (Hint: Consider whether you have a dissociating or non-dissociating solute, and be sure to calculate the mole fraction appropriately.) The vapor pressure of pure water is 23.76 torr.
2.
Sodium aluminum chloride, NaAlCl4, is soluble in water. One chemist suggests that, on dissolving, it completely dissociates into six individual ions: NaAlCl4 (s) Na+ (aq) + Al3+ (aq) + 4 Cl (aq) (proposal A)
Another chemist believes that it dissociates into only two ions: a sodium cation and the tetrachloroaluminate anion: NaAlCl4 (s) Na+ (aq) + AlCl4 (aq) (proposal B)
When 6.00 grams of NaAlCl4 are dissolved in 100. grams of pure water, the freezing point of the resulting solution is 3.5C. Do the results of this experiment support proposal A, proposal B, or neither? Provide calculations to support your choice.
67
Harvard University
Predict the freezing point of this solution. (Its density is 1.04 g/mL.) Note: Hypochlorous acid (HOCl) is a weak acid. HCl is a strong acid. Be sure to consider the total concentration of dissolved species.
2.
Consider the following solution: 0.500 moles of the weak acid HN3 plus 0.750 moles of the ionic compound NaN3 in a total of 1.00 liter of solution. The density of this solution is 1.02 g/mL. Calculate the vapor pressure of water over this solution at 25C. (The vapor pressure of pure water at 25C is 23.76 torr). (Hint: Be sure to consider ALL the moles of solute particles in your calculation; assume ideal behavior.)
68
Harvard University
b)
c)
Briefly discuss any discrepancy between the observed and expected vant Hoff factors.
2.
In aqueous solution, the metasilicate ion (SiO32) forms aggregates such as the following: n = 2: n = 3: n = 4: 2 SiO32 (aq) Si2O64 (aq) 3 SiO32 (aq) Si3O96 (aq) 4 SiO32 (aq) Si4O128 (aq) and so on . . . .
A chemist dissolves 0.0100 moles of Na2SiO3 in enough water to make 1.00 liter of solution. Using a semipermeable membrane that allows Na+ ions to pass freely but prevents the passage of the silicate ions, the osmotic pressure of this solution is found to be 0.011 atm at 25C. Determine the average aggregation state (n) for the silicate ions under these conditions. (Hint: the osmotic pressure is due to the concentration of the silicate ions only.)
69
Harvard University
Rate Laws
1. Using the following data, write a rate law for the reaction 2A + B + C P. [A], M 0.01 0.02 0.01 0.01 [B], M 0.01 0.01 0.03 0.01 [C], M 0.01 0.01 0.01 0.04 initial rate, Ms1 0.3 1.2 0.9 0.3
2.
Nitrogen (II) oxide, NO, also called nitric oxide, reacts with chlorine according to the following reaction: 2 NO (g) + Cl2 (g) 2 NOCl (g) The following initial rates of reaction have been obtained: Experiment 1 2 3 a) [NO], M 0.50 1.00 1.00 [Cl2 ], M 0.50 0.50 1.00 rate, M/hr 1.14 4.56 9.12
Write the rate law for this reaction. What is the overall order? the order with respect to each reactant?
b)
c) What rate would you expect if the initial concentration of NO is 2.0 mol/L and the initial concentration of Cl2 is 1.50 mol/L?
70
Harvard University
First-Order Kinetics
1. The decomposition of SO2Cl2 is first-order with a half-life of 245 minutes at 600K. SO2Cl2 (g) SO2 (g) + Cl2 (g) An evacuated flask is filled with SO2Cl2 at a pressure of 9.00 atm at 600 K. Calculate the partial pressure of each gas after 6.0 hours have elapsed.
2.
Colorless N2O4 will decompose to form brown NO2: N2O4 (g) 2 NO2 (g) The half-life for this rapid first-order decomposition is 1.3 105 seconds. An evacuated flask is charged with 17.0 torr of N2O4. After how many seconds will the pressure of NO2 reach 1.3 torr?
71
Harvard University
Higher-Order Kinetics
1. Some reactions are so rapid that they are diffusion-controlled; that is, the reactants will react as quickly as they can collide. The neutralization of H3 O+ by OH is one such example; this reaction has a second-order rate constant of 1.3 10 11 M1s1 at room temperature. a) If equal volumes of 2.0 M HCl and 2.0 M NaOH are mixed instantaneously (affording a solution 1.0 M in each), calculate the time required for 99.999% of the acid to be neutralized.
b)
Under normal laboratory conditions, would you expect the rate of acid-base neutralization to be limited by the rate of the reaction or the speed of mixing?
2.
The reaction:
Under the condition that [NO] = 2[O2], the rate law integrates to yield: 1 1 = 8kt + [O2]2 ([O2]o)2 An experiment begins with [NO] = 0.020 M and [O2] = 0.010 M. Determine the concentrations of NO, O2, and NO2 after 100. seconds.
72
Harvard University
2.
A certain industrial chemical process has an activation energy of 65 kJ/mol. If this process can produce 1.0 kg per hour at 100.C, what temperature would be required in order to produce 2.0 kg per hour?
3.
You have seen several factors that can affect reaction rates. Consider the firstorder decomposition of SO2Cl2 at 600 K: SO2Cl2 (g) SO2 (g) + Cl2 (g) Predict the change in the rate of decomposition of SO 2Cl2: If you: i) add more SO2Cl2 Rate of decomposition of SO2Cl2 will:(circle) speed up slow down slow down slow down slow down slow down remain same remain same remain same remain same remain same
ii) decrease the volume of the flask speed up iii) lower the temperature iv) add a catalyst v) add some Cl2 speed up speed up speed up
73
Harvard University
b)
c)
In Experiment No. 1, after how many seconds will [N2 O4 ] reach 0.002 M?
d)
e)
74
Harvard University
Introduction to Mechanisms
1. Write a rate law for each of the following elementary reactions: Cl2 + H HCl + Cl
C3H6N2 C3H6 + N2
2.
k1 = rate const. of forward rxn k1 = rate const. of reverse rxn k2 = rate const. of forward rxn
B + C D
Write the rate law for the reaction under each of the following assumptions: a) The first step is rate-determining.
b)
c)
75
Harvard University
Advanced Mechanisms
1. For the gas-phase reaction: CO + Cl2 COCl2 the following mechanism has been proposed: Cl2 2 Cl fwd. rate const. k1 , reverse rate const. k1 Cl + CO COCl fwd. rate const. k2 , reverse rate const. k2 COCl + Cl2 COCl2 + Cl fwd. rate const. k3 a) Assume that the first step is in equilibrium, [COCl] is steady-state, and the final step is rate-determining, and derive the rate of formation of product (COCl2).
b)
Show that if k3 is very small, the rate law simplifies to the form k[CO][Cl2 ]3/2 .
2.
Given the following mechanism for the reaction: A + 2B + D F A+B C fwd. rate const. k1 , reverse rate const. k1 C+D E fwd. rate const. k2 E+B F fwd. rate const. k3 Assuming that the first step is in rapid equilibrium, and that the intermediate E is in steady state, derive the rate law for the formation of the product F.
76
Harvard University
b)
c)
2. a)
Write the equilibrium constant expression (Kc) for these chemical equations. The numerical value of the equilibrium constant is given in each case: H2 (g) + CO2 (g) CO (g) + H2O (g) Kc = 0.771
b)
Kc = 8.12
c)
Kc = ????
d)
Given the data from parts (a) and (b), above, calculate the numerical value of the equilibrium constant for the reaction in part (c).
3.
The equation:
has an equilibrium constant Kc of 6.1 10 3 at 25C. Calculate the equilibrium constant for the related reaction: NO2 (g) 1/2 N2O4 (g)
77
Harvard University
b)
On a certain day, the partial pressures of NO, O2, and NO2 were as follows: PO2 = 152 torr PNO2 = 3.6 105 torr PNO = 1.1 105 torr
Calculate the value of Q , and determine if NO 2 will be produced or consumed under these conditions.
2.
The decomposition of NOBr has an equilibrium constant Kp = 0.028 at 350 K: NOBr (g) NO (g) + 1/2 Br2 (g) a) Calculate the value of Kc for this reaction at 350 K.
b)
A 2.00-liter flask contains 0.50 mol NOBr, 0.40 mol NO, and 0.20 mol Br2 at 350 K. Calculate the reaction quotient Q, and determine if NOBr will be produced or consumed under these conditions.
78
Harvard University
Le Chteliers Principle
1. Consider the decomposition of SO2Cl2 at 600 K. SO2Cl2 (g) SO2 (g) + Cl2 (g) H = +67 kJ/mol
Predict the change in SO2Cl2 concentration at equilibrium if: If you: i) add more SO2 Concentration of SO2Cl2 will: (circle) increase decrease decrease decrease decrease decrease remain same remain same remain same remain same remain same
ii) decrease the volume of the flask increase iii) raise the temperature iv) add some inert Argon gas v) add a catalyst 2. increase increase increase
Consider the following exothermic reaction, used to obtain lead from its ore: 2 PbS (s) + 3 O2 (g) + 2 CO (g) 2 Pb (l) + 2 SO2 (g) + 2 CO2 (g) Assume that this reaction is at equilibrium. Given each of the following changes to the system, will the quantity of lead increase, decrease, or remain the same: If you: i) add more lead sulfide ii) add more carbon monoxide iii) remove some oxygen iv) compress the entire system v) add argon (an inert gas) vi) increase the temperature Total quantity of lead will: (circle) increase increase increase increase increase increase decrease decrease decrease decrease decrease decrease remain same remain same remain same remain same remain same remain same
3. a)
What conditions (high vs. low temperature, high vs. low pressure) would you use to increase the yield of products in the following reactions: 2 NOCl (g) 2 NO (g) + Cl2 (g) endothermic
b)
exothermic
79
Harvard University
2.
2 NOCl 2 NO + Cl2
2.00 moles of NOCl (g) were heated at 225C in a 400.-liter steel reaction vessel. After reaching equilibrium, the total pressure in the vessel was 0.246 atm. Calculate Kp for this reaction at this temperature.
3.
At 500C, fluorine gas (F2) is stable and does not dissociate. However, at 840C, some dissociation to fluorine atoms occurs: F2 (g) 2 F (g) A flask is filled with 0.600 atm F2 at 500C. The temperature is raised to 840C, and the pressure is measured to be 0.984 atm (at 840C with dissociation). Calculate the equilibrium constant Kp for the dissociation of fluorine gas at 840C.
80
Harvard University
A 1.00-liter evacuated flask is filled with 0.183 moles of SO2Cl2 at 600 K. Calculate the moles of each gas at equilibrium, and the total pressure.
2.
Given the following equilibrium: Br2 (g) + F2 (g) 2 BrF (g) K = 54.7 at 300. K
An evacuated flask is charged with 2.2 atm of Br2 and 2.2 atm of F2. Calculate the final pressure of BrF once equilibrium is reached at 300. K.
3.
At 1800 K, oxygen dissociates slightly into individual atoms: O2 (g) 2 O (g) Kp = 1.2 1010 at 1800 K
You place 1.0 mol of O2 in a 10.0-liter flask and heat it to 1800 K. How many single atoms of oxygen (O) will be present in the flask at equilibrium?
81
Harvard University
b)
0.020 M HBr
c)
1.0 10 3 M Ba(OH)2
d)
1.0 10 9 M KOH
3. a)
A solution is prepared by mixing 500. mL of 0.10 M NaOH with 500. mL of 0.0400 M H2SO4. Write the equation for the chemical reaction which will take place.
b)
82
Harvard University
Weak Acids
1. Calculate the pH of a 0.100 M solution of HF (Ka = 6.8 104)
2.
83
Harvard University
Weak Bases
1. Calculate the pH of a 0.117 M solution of CH3NH2. (Kb = 4.3 104)
2.
Calculate the pH of a 0.075 M solution of sodium benzoate (C7H5O2Na). (Ka of C7H5O2H = 6.46 105)
3.
Many home pools are disinfected by adding calcium hypochlorite, Ca(OCl) 2. The hydrolysis of the hypochlorite ion yields hypochlorous acid. Given that Ka for HOCl = 3.0 108, calculate the pH of an 0.100 M solution of calcium hypochlorite, Ca(OCl)2.
84
Harvard University
2.
3.
Calculate the pH of a 0.100 M solution of Na 2C2O4. For the conjugate acid H2C2O4, Ka1 = 5.9 102
85
Harvard University
2.
A solution is prepared by dissolving 0.0030 moles of Cu(NO3)2 in 500. mL of distilled water. Calculate the pH of this solution. Ka (Cu(H2O)42+ ) = 1.0 108
86
Harvard University
2.
Sulfur dioxide is quite soluble in water. It dissolves according to the equation: SO2 (g) + H2O (l) H2SO3 (aq) The H2SO3 thus produced is a weak, diprotic acid: Ka1 (H2SO3) = 1.54 102 Ka2 (H2SO3) = 1.02 107 [H SO ] K = P2 3 = 1.33 SO2
A sulfur dioxide solution is prepared by continuously bubbling SO 2 at a pressure of 1.00 atm into pure water. Calculate the pH of this solution, and the concentrations of H2SO3, HSO3, and SO32.
87
Harvard University
An Introduction to Buffers
1. Calculate the pH of a solution which is 0.050 M in HF and 0.112 M in NaF. Ka for HF = 6.8 104
2.
You are given two burettes. One is filled with 0.10 M acetic acid. The other is filled with 0.15 M sodium acetate. How much of each would you mix together to produce a total of 20.0 mL of solution with a pH of 4.70? You may not add any water to the solution.
3. a)
A buffer is prepared by dissolving 0.500 moles of HN3 and 0.750 moles of NaN3 in enough water to make 1.00 liter of solution. (K a for HN3 = 1.9 105) Calculate the pH of this buffer solution.
b)
You prepare 1.00 L of 0.100-molar HN3. How will the following changes affect the quantity of HN3 present at equilibrium: If you: add 1 gram of solid NaN3 dilute the solution with water add 1 gram of solid NaOH add 1 gram solid NaCl lower the pH with HCl Quantity of HN3 at equilibrium will: (circle) increase increase increase increase increase 88 decrease decrease decrease decrease decrease remain same remain same remain same remain same remain same
Harvard University
2. a)
4.00 mL of 0.100 M NH4Cl are mixed with 1.00 mL of 0.100 M Na2CO3. (The total volume of solution is 5.00 mL.) The resulting solution has [NH3] = 0.0200 M and [NH4+ ] = 0.0600 M. Calculate the pH of this buffered solution. (Kb (NH3) = 1.8 105)
b)
Calculate the concentrations of H 2CO3, HCO3, and CO32 at this pH once equilibrium is reached. Note that the carbonate species must add up, that is: [H2CO3] + [HCO3] + [CO32] = 0.0200 M. (Hint: Apply the Henderson-Hasselbalch equation to each acid-base pair.) Ka1 (H2CO3) = 4.3 107 Ka2 (H2CO3) = 5.6 1011
89
Harvard University
Titrations
1. What volume of 1.00-molar ammonium chloride must be added to 1.00-liter of 0.100-molar LiOH in order to achieve a pH of 9.4? (Kb (NH3) = 1.8 105)
2.
Calculate the pH that would result if 60.0 mL of 1.00-molar H3PO4 is added to 1.00 liter of 0.100-molar LiOH. For H3PO4, Ka1 = 7.5 103 Ka2 = 6.2 108 Ka3 = 4.2 1013
90
Harvard University
b)
2. a)
The Ksp for silver sulfate (Ag2SO4) is 1.2 10 5. Calculate the solubility of Ag2SO4 in pure water.
b)
3.
The solubility product constant of calcium fluoride is 3.9 1011. How many moles of solid NaF must be added to 1.00 L of 0.100 M CaCl2 in order to precipitate CaF2?
91
Harvard University
b)
92
Harvard University
Calculate the concentrations of Cu2+ , NH3, and Cu(NH3)22+ , if 0.020 moles of Cu(NO3)2 are dissolved in 1.0 liter of 1.00 M NH3. (Ignore the basicity of NH 3.)
2.
In a test tube, 1.00 mL of 0.100 M Mn(NO3)2 is mixed with 3.00 mL of 0.100 M Na2CO3 and 1.00 mL of 0.882 M H2O2. Dark brown MnO2 (s) precipitates according to the following equilibrium: Mn2+ (aq) + 2 CO32 (aq) + H2O2 (aq) MnO2 (s) + 2 HCO3 (aq) [HCO3]2 = 6 1038 [Mn2+ ][CO32]2[H2O2] Calculate the concentration of Mn2+ at equilibrium. (Neglect the effect of the hydrolysis of the ions in water.) K=
93
Harvard University
2.
Chromium (III) hydroxide, Cr(OH)3, is practically insoluble (K sp = 6.3 1031). However, chromium hydroxide will dissolve in excess base due to the formation of a complex ion: Cr3+ (aq) + 4 OH (aq) Cr(OH)4 (aq) Kf = 8.0 1029
94
Harvard University
b)
Aluminum phosphate is actually more soluble than your answer to part (a) might indicate, due to hydrolysis of the ions involved. The actual dissolving of AlPO4 in water can be represented: AlPO4 (s) + 6 H2O (l) Al(H2O)5(OH)2+ (aq) + HPO42 (aq) Given the following information: Ksp (AlPO4) = 9.8 1021 Ka (Al(H2O)63+ ) = 1.1 105 Ka (H3PO4) = 7.5 103 Ka (H2PO4) = 6.2 108 Ka (HPO42) = 2.2 1013
Calculate the solubility of AlPO4 in pure water, including the effect of hydrolysis as represented above. Recall that Al 3+ (aq) is actually Al(H2O)63+ (aq).
95
Harvard University
An Introduction to Thermodynamics
1. a) Consider the evaporation of methanol, CH3 OH. Using the Useful Information (below): Calculate the heat of vaporization of methanol.
b)
c)
Harvard University
Would you expect the entropy change to be positive or negative? Briefly explain your reasoning.
b)
At 25C, G for this reaction is +16.5 kJ/mol. Calculate S for the reaction, and compare it with your prediction.
2.
When HF (aq) dissociates in water, one might expect an increase in entropy when the neutral HF molecule dissociates into ions. In fact, however, S for this dissociation is negative (88 J/mol K). Consider carefully the issues of order and disorder in the solution, and speculate briefly why this must be so. HF (aq) + H2 O (l) H3 O+ (aq) + F (aq) S = 88 J/mol K
97
Harvard University
b)
Calculate H at 25C.
c)
Calculate S at 25C.
d)
Calculate G at 60C.
e)
S (J/molK) 92 152
Harvard University
G and Keq
1. Gadolinium (III) is used in medical imaging (MRI) applications. Because Gd3+ is itself toxic, gadolinium (III) is usually administered as a complex of DTPA5: (DTPA5 is a chelating, or complexing, agent) Gd3+ + DTPA5 Gd(DTPA)2 a) Determine G for the above reaction at 25C. Kf = 2.9 1022 at 25C
b)
Calculate Kf for the above reaction at 37C (normal body temperature), given that its H is 32.6 kJ/mol.
2.
Consider the following equilibrium, and the Useful Information (below): N2 O4 (g) 2 NO2 (g) a) At what temperature will an equilibrium mixture of 1.00 atm total pressure contain twice as much NO2 as N2 O4 ?
b)
At what temperature will an equilibrium mixture of 1.00 atm total pressure contain equal amounts of the two gases?
Harvard University
G at Nonstandard Conditions
1. a) The vapor pressure of water at 27C is 27 torr. Calculate the standard free energy of vaporization Gvap for water at 27C.
b)
Calculate the nonstandard G for the evaporation of water at 27C if the partial pressure of water vapor is 11 torr.
2.
Methanol, CH3 OH, can be synthesized by reacting CO and H 2 directly: CO (g) + 2 H2 (g) CH3 OH (l) a) Using the Useful Information (below), calculate G and K for this reaction at 25C.
b)
Calculate the nonstandard G if the pressure of H2 is 3.0 atm and the pressure of CO is 5.0 atm.
Harvard University
b)
c)
Hf (kJ/mol) 46.19
S (J/molK) 192.5
Harvard University
b)
2.
Consider the reaction between xylenol orange (H4Q) and aluminum ion (Al3+ ), which you studied in the laboratory: Al3+ (aq) + H4Q (aq) AlQ (aq) + 4 H+ (aq) at 55C: K = 7.6 105 at 90C: K = 6.5 104 a) Calculate G for this reaction at 55C.
b)
c)
102
Harvard University
b)
2. a)
Using the Useful Information (below): Calculate G for the evaporation of mercury at 25C.
b)
c)
Substance: TiCl4 (g) TiCl4 (l) C2H5OH (g) C2H5OH (l) Hg (g)
Harvard University
b)
Calculate the enthalpy of ionization (H) for butyric acid between 10C and 50C.
2.
Consider the first step of the reaction between phosphoric acid and hydroxide ion: H3PO4 (aq) + OH (aq) H2PO4 (aq) + H2O (l) Given that, at 25C, Ka1 for phosphoric acid is 7.5 103, and Kw = 1.0 1014, calculate G for the above reaction at 25C.
104
Harvard University
Applications: Buffers
1. A buffer is prepared by dissolving 0.500 moles of HN3 and 0.750 moles of NaN3 in enough water to make 1.00 liter of solution. HN3 (aq) + H2O (l) H3O+ (aq) + N3 (aq) a) Calculate G for the above reaction at 25C. Ka = 1.9 105 at 25C
b)
Calculate G (nonstandard) for the above reaction at 25C under the given buffer conditions (above), but at pH 7.0.
2.
Consider the equilibrium dissociation of HN3: HN3 (aq) + H2O (l) H3O+ (aq) + N3 (aq) Ka = 1.9 105 at 25C H = +14.7 kJ/mol For the same buffer system used above (0.500 M HN 3 plus 0.750 M NaN3), calculate the pH at 50C.
105
Harvard University
b)
c)
d)
e)
HSO4 (aq) + As4 (s) + Pb3O4 (s) PbSO 4 (s) + H3AsO4 (aq)
f)
106
Harvard University
b)
c)
d)
e)
f)
107
Harvard University
108
Harvard University
b) c) d)
Identify the anode and cathode. What is the oxidizing agent? the reducing agent? Using the table of Standard Reduction Potentials, calculate E for this cell.
2.
Calculate the standard cell potential for the following cell: Mn (s) | Mn2+ || Co2+ | Co (s)
3. a)
An electrochemical cell is set up by connecting a standard Cu/Cu2+ half-cell with a standard Ag/Ag+ half-cell. A voltmeter is connected to this system in such a way as to read a positive voltage. What voltage would it display?
b)
While keeping the copper electrode connected to the voltmeter, the Ag/Ag + halfcell is replaced with a Zn/Zn2+ half-cell. What would the voltmeter read now? (Be sure to consider the sign.)
109
Harvard University
2.
For the following unbalanced half-reaction: SF6 (g) + e H 2SO3 (aq) + HF (aq) a) Balance this half-reaction in acidic solution.
b)
Harvard University
Determine the standard reduction potential for the following half-reaction: S4O62 + 12 OH 4 SO32 + 6 H2O + 6 e E = ???
2. a)
For the unbalanced reduction half-reaction: Balance this half-reaction in acidic solution.
b)
Using the table of Standard Reduction Potentials, determine E for this halfreaction.
111
Harvard University
2.
Using the table of Standard Reduction Potentials, show that Fe2+ can be spontaneously oxidized to Fe3+ by O2 (g) at 25C assuming the following (reasonable) environmental conditions: [Fe2+ ] = [Fe3+ ] = 1 107 M a) pH = 7 PO2 = 160 torr
b)
112
Harvard University
Concentration Cells
1. A cell is constructed as follows: On the left is a solution of 0.010 M AgNO3 with a silver electrode. On the right is a solution of 1.0 M AgNO3 with another silver electrode. The cells are separated by a salt bridge and the electrodes are connected through a voltmeter. a) Identify the anode and cathode.
b)
c)
Water is added to the left half-cell, reducing the Ag+ concentration. The new cell potential is 0.210 volts. Calculate the new Ag+ concentration in the left half-cell.
113
Harvard University
Write the anode and cathode reactions and the overall cell reaction. Label each clearly.
b)
c)
d)
e)
Calculate E if the actual concentrations are [Pb 2+ ] = 1.5 M and [Sn2+ ] = 0.10 M.
114
Harvard University
2.
A fuel cell is powered by hydrogen and oxygen: H2 (g) + 1 O2 (g) H2O (l) 2 A certain such fuel cell, given excess oxygen, consumes at most 0.370 grams of pure hydrogen gas per hour at 25C. Calculate the maximum current which can be produced by this fuel cell.
3. a)
Aluminum is produced by the electrolytic reduction of alumina, Al2O3. Given a current of 1.0 105 amps, how many hours would it take to produce 1000. kg of aluminum?
b)
The anode in the above reaction is graphite (carbon), which is oxidized to CO2 (g) during the reaction. What mass of graphite must be consumed in order to produce 1000. kg of aluminum?
115
Harvard University
2.
For the following unbalanced half-reaction: BaCrO4 (s) + e Ba2+ (aq) + Cr3+ (aq) a) Balance this half-reaction in acidic solution.
b)
Using the following data, and the table of Standard Reduction Potentials, determine E for this reduction half-reaction.
Ksp (BaCrO4) = 2.1 1010 Substance: CrO42 (aq) Cr2O72 (aq) H+ (aq) H2O (l) Gf (kJ/mol) 727.75 1301.1 0 237.18 116
Harvard University
a)
Carbon-11 decays by
b)
c)
d)
e)
f)
g)
Two atoms of 12C can react inside a star to produce 20Ne and 6 10
h)
beta particles.
117
Harvard University
Radioactive Dating
1. The age of wine can be determined by measuring its radioactive tritium content. Tritium (3H, an isotope of hydrogen) is formed in the upper atmosphere and comes down to the Earth in rainwater. Once the wine is bottled, the tritium content decays by a first-order process with a half-life of 12.5 years. a) You are offered a valuable vintage wine which has only 20% of the tritium activity of a freshly bottled sample. Calculate the age of this wine.
b)
Once the tritium activity has decayed to 1% of its original activity, this dating technique is no longer reliable. What is the maximum age of wine that could be dated using this technique?
118
Harvard University
2.
A cancer treatment called boron neutron-capture therapy works as follows: A drug containing boron-10 is injected into the patient; this drug selectively binds to cancer cells. Irradiating the affected area with neutrons induces the following reaction:
10B
+ 1n 4He + 7Li +
The alpha radiation kills the cancer cells, leaving the surrounding tissue unharmed. In this nuclear reaction, the alpha particle and 7Li together have a total kinetic energy of 2.31 MeV. The reactants (the boron atom and the neutron) have essentially no kinetic energy. Calculate the energy of the gamma photon released in this process. (Masses of relevant nuclides are given above.) (1 MeV = 1.60 1013 J)
119
Harvard University
Radiation Dose
1. Potassium-40 decays by beta emission with a half-life of 1.28 10 9 years; the emitted beta particles have an average kinetic energy of 0.55 MeV. A person weighing 70.0-kg contains about 0.020 grams of 40K. Determine the total dose of radiation absorbed per year from this decay of 40K. (1 MeV = 1.60 1013 J)
2. a)
Cobalt-57 decays with a half-life of 271 days. An individual with a mass of 70.0 kg ingests 8.0 1010 grams of 57Co. Calculate the mass of 57Co remaining in this person after one year.
b)
Each atom of 57Co releases 0.122 MeV of gamma radiation when it decays. Calculate the total dose of gamma radiation (in rad) absorbed by this person during the first year after ingestion. (Hint: how many atoms of 57Co decayed in that time?)
120
Harvard University
b)
Carbon-14 has a mass of 14.003242 amu. The isotope produced when 14C decays has a mass of 14.003074 amu., and a beta particle a mass of 0.000549 amu. Calulate the energy released when one atom of carbon-14 decays by the above process.
c)
Virtually all the energy from the above decay goes into the kinetic energy of the ejected electron. What would be the velocity of the electron ejected from a decaying atom of carbon-14?
d)
The Shroud of Turin, long believed to be Christs burial shroud, was probably made around 1320 A.D. Carbon-14 dating played an important role in the determination of its age. What fraction of the 14C present in 1320 is still present today? The half-life of 14C is 5730 years.
121
Harvard University
c)
Na2[Fe(CO)4]
d) [IrF6]3
e)
K3[Fe(CN)6]
f) [PtCl2(NH3)2]
122
Harvard University
b)
[Pt(NH3)2Cl2Br2]
2.
When the octahedral complex [Co(NO2)3(NH3)3] is treated with HCl, one can isolate a complex [CoCl2(NH3)3(OH2)]1+ in which the two chloride ligands are trans to one another. a) Draw the two possible stereoisomers of the starting material [Co(NO2)3(NH3)3]. (The NO2 ligands are all bound through the nitrogen atom.)
b)
Assuming that the NH3 groups remain in place, which of the two starting isomers could give rise to the observed product?
123
Harvard University
Co
Co
Co
chiral achiral
chiral achiral
chiral achiral
Co
Co
Co
chiral achiral
chiral achiral
chiral achiral
124
Harvard University
c)
[Fe(CN)6]4
d) W(CO)6
2.
The three complexes [Co(NH3)6]3+ , [Co(NH3)5(OH2)]3+ , and [CoF6]3 are colored red, yellow, and blue (but not in that order). Match each complex with its color, and explain your reasoning.
3.
125
Harvard University
b)
For the complex [Fe(CN)5NO]2, give the electronic configuration of the dorbitals (e.g. t2g3eg1), indicate whether the complex is high-spin or low-spin, and give the number of unpaired electrons.
c)
The [Fe(CN)5NO]2 complex is red-violet in color (ruby red), while the similar complex [Fe(CN)6]3 is red-orange in color (bright red). The CN ligand is a strong-field ligand. By comparison, the NO ligand is: (circle one) much weaker slightly weaker slightly stronger much stronger
Briefly explain your choice using the language of crystal field theory.
d)
Would you expect NO to dissociate rapidly from the complex [Fe(CN) 5NO]2? Briefly explain your answer.
126
Harvard University
2.
Ethanol (an alcohol with the molecular formula C2H6O) is metabolized in the liver through a two-step oxidation process. The initial product has the formula C2H4O, and is responsible for the red flushed appearance which often accompanies alcohol consumption. This is then oxidized again to the final product, which has the molecular formula C 2H4O2.
a) b)
Draw the structure of ethanol: Draw the structure of each product, and name the functional groups. Structure Functional Group
127
Harvard University
Polyalanine (a polypeptide)
H N H C CH3 O C N H H C CH3 O C N H H C CH3 O C
2.
A a) b) c) What is the functional group in molecule A? What is the functional group in molecule B?
Draw a portion of the polymer chain which would be formed. The polyester is formed by condensation polymerization. Include at least 4 monomers: A-B-A-B.
128
Dimensional Analysis II: Volume and Density a) 3.6 102 bushels b) 54 hogsheads a) 4.670 102 in3 b) 1.92 g b) 20 protons, 20 neutrons, 18 electrons d) 19 protons, 20 neutrons, 19 electrons
37Cl: 17 protons, 20 neutrons, 18 electrons
Atoms, Molecules and Ions a) 18 protons, 22 neutrons, 18 electrons c) 19 protons, 20 neutrons, 18 electrons 20 protons, 18 electrons
35Cl: 17 protons, 18 neutrons, 18 electrons
Oxidation Numbers
2.
N2 is reduced, H2 is oxidized FeCl3 is reduced, KI is oxidized No oxidation or reduction is taking place. Cl2 is being oxidized (to ClO3) and reduced (to Cl)
6.
Naming Compounds 1. a) Cu3P e) CrO3 i) Cs3PO4 m) AgF2 2. b) Fe 2(SO4) 3 f) NH4I j) Re2O7 n) KNO3 c) KClO3 g) Li3N k) SnCl4 o) Ba3(PO4) 2 d) AlCl3 h) Al 2(CO3) 3 l) GaF3 p) (NH4) 2SO4
129
7.
Chemical Formulas: Percent Composition 1. a) C: 34.3% H: 7.2% P: 22.1% O: 22.8% F: 13.6% b) If we combust 10.0 grams of Sarin, we'd get 12.6 g CO2 and 6.5 g H2O. This does not agree with the results obtained for the unknown compound; thus it can't be Sarin. 2. Pure CaCO3 would have 40% calcium, 12% carbon, and 48% oxygen. This does not agree with the analysis of the rock sample. a) C9H12O a) C5H4O b) C18H24O2 c) 272.39 g/mol
8.
9.
a) CO(NH2) 2 + 6 HOCl 2 NCl3 + CO2 + 5 H2O b) 2 Ca3(PO4) 2 + 6 SiO2 + 10 C P4 + 6 CaSiO3 + 10 CO 6 CO 2 + 6 H2O C6H12O6 + 6 O2 3 Nb + 4 I2 Nb3I 8
C8H18 + 25/2 O2 8 CO2 + 9 H2O 10. Stoichiometry of Reactions 55.9 g NaClO a) NiS + 2 O 2 + 2 HCl NiCl2 + H2SO4 b) 0.654 g NiCl2 11. Stoichiometry with Limiting Reagents 1. 2. a) V2O5 + 3 Zn V2O2 + 3 ZnO b) 68.25 g V2O2 a) 5 P4S3 + 12 Br2 3 P4S5 + 8 PBr 3 b) 77.47 g P 4S5 61.1% CO2 by mass 7.46 g CuO, 3.04 g Cu2O 6.55 g Cu2S, 4.25 g CuS 18.0 M 17.47 M 0.216 M 0.052 g x = 4.4 g KNO3 y = 4.49 g NaCl
14. Solution Stoichiometry I: Simple Examples a) 3 ClO (aq) + NH3 (aq) NCl3 (l) + 3 OH (aq) b) 0.028 g NCl3 2.79 g CO 2
130
15. Solution Stoichiometry II: Acid/Base Neutralizations 1. 2. 3. 1. 2. 3. 1. 2. 71.2 mL 1.72 L 1.26 L 1.22 g 312 g/mol 119.2 g/mol 0.0119 M Ba(NO3) 2 Ba2+ : 0.011 M NH3: 0.033 M 18. The Ideal Gas Law 1. 2. 1. 2. 3. 1. a) 6.0 105 L b) 0.348 g Cl2 53.4 g O2 2.66 atm 0.480 atm total pressure = 1.5 atm a) 0.0863 mol O2 b) 0.0211 torr O2 c) 2.78 106 torr O2 2. 1. 2. 3. 1. 2. 1. 2. 16.3 g butane 0.109 g H2 0.312 L collected 3.51 L should be collected 21. Collecting Gases Over Water 19. Reactions Involving Gases: Simple Examples Cl: 0.033 M NH4+ : 0.022 M NO3: 0.011 M
PCl5 = 0.054
12.8% O3 by mass 21.3 g NaN3 a) 29.0 g Cl2 b) 1.07 atm O2
PCl3 = 0.473
Cl2 = 0.473
1.63 atm Cl 2
131
24. Kinetic-Molecular Theory of Gases 1. 2. a) CO2: 752 m/s a) 431 m/s b) 7.3 hours 25. Heat 1. 2. 1. 2. 3. 1. 2. 1. 2. 1. 2. 1. a) 8.2 kJ of heat consumed b) Final temp. = 14.2C Specific heat = 0.269 J/gC H = 27 kJ/mol H = 5152 kJ/mol H = 4219 kJ/mol Final temp. = 27.08 C 311 g of ice H = 171.34 kJ/mol H = 185.1 kJ/mol H = 64.9 kJ/mol 268 kJ of heat released a) +37.4 kJ/mol b) 2800 J/mol c) +34.6 kJ/mol 31. Putting It Together: Calorimetry, Hesss Law, and Hf 1. 2. a) H = 25.3 kJ/mol b) Hf (NH4NO3(s)) = 362.8 kJ/mol a) H = 50.8 kJ/mol for the reaction as written (i.e. consuming 2 mol NaN3) b) Hf (NaN3) = 25.4 kJ/mol 32. Putting It Together: Stoichiometry, Thermochemistry, and Gas Laws 1. a) 3.74 g CO 2 b) 7938C c) 14.3 atm CO 2 26. Calorimetry I: Simple Examples H2O: 1176 m/s N2: 943 m/s b) Kinetic energies of all gases are the same at any given temp: 2.07 1020 J/molecule
132
33. Energy, Particles, and Waves: A Chain Problem 1. a) 7.09 1017 s1 b) 4.23 1010 m c) 1.72 106 m/s d) 1.35 1018 J 34. The Photoelectric Effect 1. a) 1.09 1015 s1 b) 1.80 109 m 35. Orbitals and Wavefunctions 1. a) The first graph is R2, the second one is R, and the third is r 2 R2 . b) B and C. c) A. 2. C. 36. Orbitals and Quantum Numbers 1. Subshell 1s 3d 3 5p 5 2. 1. n 1 2 1 l 0 10 6 total # of e 2
37. Electron Configurations of Neutral Atoms Mg: [Ne]3s2 Mn: [Ar]4s23d5 Se: Cu: Xe: Ba: Os: Pb: [Ar]4s23d104p4 [Ar]4s13d10 (Remember that Cr and Cu are well-known exceptions to the usual order!) [Kr]5s24d105p6 [Xe]6s2 [Xe]6s24f145d6 [Xe]6s24f145d106p2
133
38. Electron Configurations of Ions 1. Be+ : 1s 22s1 N : 1s22s22p4 Al3+ :1s22s22p6 H : 1s2 O2: 1s 22s22p6 2. Zn2+ : [Ar] 3d10 W6+ : [Xe] 4f 14 Cu2+ : [Ar] 3d9 Gd3+ : [Xe] 4f7 Se2: [Ar] 4s23d104p6 39. Periodic Properties I: Overview 1. a) b) c) d) 2. High ionization energy: upper right Low ionization energy: lower left High atomic mass: lower right Low atomic mass: upper left Big atomic radius: lower left Small atomic radius: upper right Most metallic: lower left "Least metallic" (most non-metallic): upper right a) Most reactive metal: Francium (Fr) b) Most reactive non-metal: Fluorine (F) 40. Periodic Properties II: Multiple Choice 1. a) Radium is the largest of the group; its valence electrons are in the 7s orbital, which is far from the nucleus. b) Indium is the largest of the group; its valence electrons are in the 5p orbital, whereas the others are in lower-energy orbitals. 2. a) Thallium has the lowest ionization energy of the group; its valence electrons are in a higher energy orbital than those of Ga or Se, and it has a smaller effective nuclear charge than Po. b) Cesium has the lowest ionization energy of the group; its valence electrons are in a higher energy orbital than those of Ga or Se, and it has a smaller effective nuclear charge than Bi. 3. 4. Fluorine has the most negative electron affinity because when it gains an electron, it forms the fluoride ion with a stable, complete octet. Se2 is the largest ion of the group. Of course it will be larger than the 2nd-period ions O2 and F . Plus, since it is isoelectronic with Rb+ , it has the same number of electrons but three fewer protons, meaning that the effective nuclear charge is less and the radius will be larger.
134
41. Periodic Properties III: Explanations 1. a) Se: . . . 4s24p4 As: . . . 4s24p3 has 2 electrons in one of its p-orbitals each p-orbital has one electron
Because it is somewhat unfavorable for two electrons to occupy the same orbital, Se is relatively willing to give up its p-electron to achieve an electron configuration in which each p-electron is in its own orbital. Note that this goes against the usual trend for ionization energy. b) Adding an electron to Br results in a complete octet (which is particularly stable, and thus quite favorable). c) When Rb and Na react with water, they each lose an electron to form their respective cations. Since Rb has a lower ionization energy, more total energy can be released in the reaction. 2. a) When an electron is added to fluorine, its octet is completed. b) When fluorine reacts, it almost always accepts an electron, forming fluoride ion and releasing a tremendous amount of energy (the electron affinity). This large energy release make fluorine very reactive. c) Xenon can't gain an electron (because it already has a full octet). It also can't readily lose an electron, because its ionization energy is so high. Thus it is unwilling to participate in chemical reactions. d) Although iodine can't readily lose an electron, it can readily gain an electron (unlike xenon) and form a stable, complete octet. This is the usual mode of reactivity for iodine. 42. Putting It Together: Quantum Mechanics and Electronic Structure 1. a) wavelength = 1.70 107 m b) Bi: [Xe] 6s24f145d106p3 Bi+:[Xe] 6s24f145d106p2 c) n=6, l=1 d) Element 113 would have a lower ionization energy than Bi. Element 113 would lie below thallium (Tl) on the periodic table. Its valence electrons would be in the 7p subshell (more energetic than the 6p valence electrons of Bi). Thus those 7p valence electrons would be easier to ionize. 43. Lewis Structures I: The Octet Rule
F F F F F O F N C O S O F O N H O O O N H O
F F S F C C
+ 2
135
Xe F
Cl Cl
Cl Cl
47. Bond Enthalpies 1. 2. a) HCCH b) D CC = 813 kJ/mol a) :NCCN: b) 1017 kJ/mol 48. Molecular Geometry I: Neutral Molecules
F O C O O N F F B Cl F I Cl Cl
linear linear sp no
136
50. Polycentric Molecules and Ions 1. trig. bipy. see-saw sp3d tetrahedral bent sp3
F F
S F
O H 3C C C C O
linear linear sp
linear linear sp
I
I I I I
b) Hybridization: sp3 Electron pair geometry: tetrahedral Molecular geometry: bent c) DS=S = 434 kJ/mol
137
52. Hybridization and Multiple Bonding: and Bonds 1. a) Trigonal planar; sp2 hybridization b) 2 -bonds between H s orbitals and C sp 2 hybrid orbitals 1 -bond between O orbital and C sp2 hybrid orbital 1 -bond between O p-orbital and C p-orbital c) Theres a good drawing in your textbook, section 9.6, p. 327 (in the 8th edition). 2. From left to right: sp3, sp, sp, sp2 (Refer to page 59, above, for further explanation) 3 -bonds between C and H 1 -bond between C sp 3 hybrid and C sp hybrid 1 -bond between C sp hybrid and C sp hybrid 2 -bonds between C p orbitals and C p orbitals (these three bonds together make up the CC triple bond) 1 -bond between C sp hybrid and C sp2 hybrid 2 -bonds between C sp2 hybrids and O orbitals 1 -bond which is shared (by resonance) between the C p orbital and the two O p orbitals (these three bonds together make up the CO2 resonance portion of the molecule)
1.
e) H g)
H H C C C H H
Each p-orbital must be perpendicular to the sp2hybrid plane, and the two -bonds must thus be perpend. to each other.
54. Covalent Bonding and Orbital Overlap 1. a) 2p and 3s making bonding orbital b) 2p and 2p making bonding orbital c) 3d and 2p making * antibonding orbital d) 3p and 1s making * antibonding orbital e) 3d and 3d making bonding orbital
138
55. Molecular Orbital Theory I: Introduction 1. a) (2s) 2(*2s) 2(2p) 2 b) (2s) 2(*2s) 2(2p) 2(2p) 4(*2p) 3 c) (2s) 2(*2s) 2(2p) 4 2. a) Bond order = 1 Paramagnetic Bond order = 1.5 Paramagnetic Bond order = 2 Diamagnetic
2p
2s
2s
N
atomic orbitals
b) Double bond: Diamagnetic: Longest bond: Isoelectronic w/CO: NO NO+ NO NO+
NO
molecular orbitals
O
atomic orbitals
139
2p
2s
2s
C
atomic orbitals
c) 4 d) diamagnetic e) longer 57. Band Theory and Semiconductors 1.
CO2
molecular orbitals
O
atomic orbitals
O
atomic orbitals
a) insulator. Si4+ and O2 are the oxidation states, so no extra valence electrons. b) conductor. Ru4+ and O2, but Ru4+ does have extra valence electrons, so it can conduct. c) semiconductor. No extra valence electrons, so not a conductor. But these large atoms have weak bonding and will have a smallish band gap. d) conductor. Ta3+ and N3. The Ta3+ has extra valence electrons, so it can conduct. e) insulator. This time it's Ta5+ , which has no extra valence electrons.
2.
p-type. The Fe3+ has one fewer valence electron, so it provides a "hole" which can allow electricity to flow.
140
58. Intermolecular forces 1. a) Al2O3 Ionic F2 H2O Br2 ICl NaCl 59. Phase Changes 1. a) MP: 115C (388 K) BP: 445C (718 K) b) total of 169.4 joules required 60. The Clausius-Clapeyron Equation 1. 2. 1. +42.2 kJ/mol 25.1 torr a) and b) London Dispersion Hydrogen Bonding London Dispersion Dipole-Dipole Ionic Al2O3, NaCl, H2O, ICl, Br2, F 2
760 P (torr)
solid
melting pt.
liquid
boiling pt.
100
triple pt.
gas
c) Solid and gas phases will be observed at equilibrium at 25C. d) Solid iodine is more dense than liquid; this is why the s/l line slopes to the right on the diagram. 62. Bonding in Crystalline Solids 1. 2. 1. 7.60 g/cm3 radius = 1.97 a) They must be n1 = 4 and n2 = 6. (These are the only combinations which give a reasonable value for the radius of the Po atom!) b) 3.34 c) 9.28 g/cm3
141
64. Lattice Energy: The Born-Haber Cycle 1. 2. 1. Lattice enthalpy = +5400 kJ/mol Lattice enthalpy = +728 kJ/mol a) 41.9% maltose b) 2.11 m c) maltose = 0.037 d) H2O = 0.963 e) 38.3 M water 66. Colligative Properties I: Non-Dissociating Solutes 1. 2. 3. 1. 2. a) 100.71C b) 23.2 torr 19200 g/mol
2. 1. 2.
n = 22.2 (Silicate ions tend to form long chains and rings in solution.) rate = k [A]2 [B] a) rate = k [NO]2 [Cl2] b) k = 9.12 M2 hr1 c) 54.7 M hr1
142
71. First-Order Kinetics 1. P(SO2Cl2) = 3.25 atm P(SO2) = 5.75 atm P (Cl2) = 5.75 atm 2. 1. 2. t = 7.31 10 7 sec a) 7.7 107 sec b) This reaction is so fast that the speed of mixing would actually be the limiting factor. [NO] = 0.0115 M [O 2] = 0.00577 M [NO 2] = 0.00845 M 73. Temperature and Rate 1. 2. 3. Ea = 62.7 kJ/mol 386 K i) speed up ii) speed up iii) slow down iv) speed up v) remain same 74. Putting It Together: Macroscopic Kinetics 1. a) rate = k [N2O4] b) k = 5.5 104 sec1 c) t = 7.11 10 5 sec d) half-life = 4.62 10 6 sec e) Ea = 51.9 kJ/mol 75. Introduction to Mechanisms 1. 2. rate = k [Cl2][H] rate = k [C3H6N2] a) rate = k1 [A] k k b) rate = k1 2 [A][C] 1 k 1k 2[A][C] c) rate = k + k [C] 1 2 k 1/2 k k [CO][Cl2] 3/2 a) rate = 1 1/22 3 k 1 (k2 + k3[Cl2]) k 1/2 k k b) The term in the denominator with k3[Cl2] would vanish, leaving k = 1 1/2 2 3 k 1 k2 k 1k 2[A][B][D] rate = k 1 72. Higher-Order Kinetics
2.
143
77. Writing Equilibrium Constants [PCl3][Cl ] 1. a) Kc = [PCl ] 2 5 b) Kc = [NH3][HCl] 2. c) Kc = [H2O(g)] [CO][H2O] a) Kc = [H ][CO ] 2 2 b) Kc = c) Kc = d) 13.7 Kc = 13 a) Kc = 5.9 1013 b) Q p = 5.4 101, so reaction goes to right, and NO2 will be produced under these conditions. 2. a) Kc = 5.2 103 b) Q c = 0.25, so reaction goes to left, and NOBr will be produced under these conditions. 79. LeChteliers Principle 1. i) increase ii) increase iii) decrease iv) remain same v) remain same 2. i) remain same ii) increase iii) decrease iv) increase v) remain same vi) decrease 3. a) high temperature, low pressure b) low temperature, high pressure 80. Calculating Equilibrium Constants 1. Kc = 0.10 2. 3. Kp = 0.0196 Kp = 0.077 [H 2O] 2 [H 2] 2 [CO2] 2 [CO] 2
3. 1.
144
81. Determining Final Equilibrium Concentrations 1. SO2Cl2: 0.0052 moles SO2: 0.178 moles Cl2: 0.178 moles Total pressure: 17.8 atm 2. 3. 1. Pressure of BrF: 3.5 atm 1.7 1018 individual oxygen atoms in the flask a) HN3 is the acid, NH2OH is the base b) B(OH)3 is the acid, CN is the base c) Si(OH)4 is the acid, C6H5O is the base 2. a) 12.43 b) 1.70 c) 11.30 d) 7.00 3. a) H2SO4 + 2 NaOH Na2SO4 + 2 H2O b) 12 83. Weak Acids 1. 2. 1. 2. 3. 1. 2.10 1.39 11.84 8.53 10.41 [H 3PO4] = 0.0761 M [H 2PO4] = 0.0239 M [HPO 42] = 6.2 108 M [PO43] = 1.1 1018 M [H + ] = 0.0239 M [OH ] = 4.2 1013 M 2. 3. 1. 2. 1.23 8.60 2.93 5.11
145
87. Putting It Together: Aqueous Acid Equilibria 1. 2. 1.59 pH = 0.84 [H 2SO3] = 1.33 M [HSO 3] = 0.143 M [SO32] = 1.02 10 7 M 88. An Introduction to Buffers 1. 2. 3. 3.52 12.5 mL of 0.10 M acetic acid 7.5 mL of 0.15 M sodium acetate a) pH = 4.90 b) (in order from top to bottom) increase, decrease, decrease, remain same, increase 89. Calculating Concentrations in Buffered Solutions 1. 2. [NH 4+ ] = 0.360 M a) b) pH = 8.78 [H 2CO3] = 7.44 10 5 M [HCO3] = 0.0193 M [CO32] = 6.53 10 4 M 90. Titrations 1. 172 mL 2. 7.51 91. Solubility and Ksp 1. 2. 3. 1. a) 3.58 103 M b) Ksp = 2.29 108 a) 0.0144 M b) 0.0012 M must add at least 2.0 10 5 moles of NaF a) 10.46 b) 1.2 103 M 93. Other Aqueous Equilibria: Dealing With Large Ks 1. [Cu 2+ ] = 5.6 1015 [NH 3] = 0.92 [Cu(NH3) 4+ ] = 0.020 2. 1. 2. [Mn2+ ] = 4 1038 [Ag+ ] = 4.5 109 0.0033 M 94. Solubility and Complex Ion Formation 92. Solubility of Metal Hydroxides
146
95. Putting It Together: Solubility and Acid/Base Behavior 1. 2. 1. 9.9 1011 M 7.0 107 M a) +37.4 kJ/mol b) +110.8 J/molK c) 64.4C 97. Molecular Interpretation of Entropy 1. 2. a) S should be negative; the system is becoming more ordered. b) S = 279 J/molK Ions in water are surrounded by waters of hydration; these water molecules are highly ordered. Thus the two ions produced each have a lot of well-ordered water molecules surrounding them and the total order is increased. a) +240 kJ/mol b) +76.2 kJ/mol c) 550 J/molK d) +259 kJ/mol e) +223 J/molK 99. G and Keq 1. 2. a) 128 kJ/mol b) 1.74 1022 a) 60C b) 45C 100. G at Nonstandard Conditions 1. 2. a) +8.32 kJ/mol b) 2.24 kJ/mol a) G = 29.0 kJ/mol b) 38.4 kJ/mol 101. Calculating K at Different Temperatures 1. a) H = 92.38 kJ/mol b) K = 6.9 105 c) K = 0.71 S = 198.2 J/molK G = 33.32 kJ/mol K = 1.2 105
147
102. Applications: Determining G, H, and S from Keq 1. 2. a) 104.9 kJ/mol b) 228 J/molK a) +25.9 kJ/mol b) +60.7 kJ/mol c) +106.1 J/molK 103. Applications: Phase Changes 1. 2. a) 35.3C b) 60.7 torr a) +31.76 kJ/mol b) +9.63 kJ/mol c) +77.34 J/molK 104. Applications: Acid/Base Equilibria 1. 2. 1. 2. 1. a) [H + ] = 0.00126 M [Bu ] = 0.00126 M b) 4.4 kJ/mol 67.7 kJ/mol a) +26.9 kJ/mol b) 12.0 kJ/mol pH = 4.70 a) 20 H+ (aq) + S4O62 (aq) + 6 Al (s) 4 H2S (aq) + 6 Al3+ (aq) + 6 H2O (l) b) 14 H+ (aq) + 6 S 2 O3 2 (aq) + Cr2 O7 2 (aq) 3 S4 O6 2 (aq) + 2 Cr3+ (aq) + 7 H2O (l) c) 18 H2O + 14 ClO3 (aq) + 3 As2 S3 (s) 14 Cl (aq) + 6 H2 AsO4 (aq) + 9 SO4 2 (aq) + 24 H + (aq) d) 3 H2O + 7 IO3 (aq) + 6 Re (s) 6 ReO4 (aq) + 7 I (aq) + 6 H+ (aq) e) 30 H+ (aq) + 30 HSO 4 (aq) + As4 (s) + 10 Pb3O4 (s) 30 PbSO4 (s) + 4 H3AsO4 (aq) + 24 H 2O f) 3 HNO2 (aq) NO3 (aq) + 2 NO (g) + H2O + H+ (aq) 107. Balancing Redox Reactions: Basic Solution 1. a) 3 C 4H4O62 (aq) + 5 ClO3 (aq) + 18 OH (aq) 12 CO32 (aq) + 5 Cl (aq) + 15 H2O (l) b) 11 Al (s) + 3 BiONO3 (s) + 11 OH (aq) 3 Bi (s) + 3 NH3 (aq) + 11 AlO2 (aq) + H2O (l) c) 4 H2 O2 (aq) + Cl2 O7 (aq) + 2 OH (aq) 2 ClO 2 (aq) + 4 O2 (g) + 5 H2O (l) d) Tl2O3 (s) + 4 NH2OH (aq) 2 TlOH (s) + 2 N2 (g) + 5 H2O (l) e) Cu(NH3 ) 4 2+ (aq) + S2 O4 2 (aq) + 4 OH (aq) 2 SO3 2 (aq) + Cu (s) + 4 NH3 (aq) + 2 H2O (l) f) 3 Mn(OH) 2 (s) + 2 MnO 4 (aq) 5 MnO2 (s) + 2 OH (aq) + 2 H2O (l) 108. Standard Reduction Potentials at 25C 106. Balancing Redox Reactions: Acidic Solution 105. Applications: Buffers [HBu] = 0.0987 M
148
109. Voltaic Cells: Calculating Cell Potential 1. a) Overall: 2 Fe3+ (aq) + 2 I (aq) 2 Fe2+ (aq) + I2 (s) Reduction: Fe3+ Fe2+ Oxidation: 2 I I 2 b) Anode: I / I2 Cathode: Fe3+ / Fe 2+ c) Oxidizing agent: Fe3+ Reducing agent: I d) E = 0.235 V 2. 3. 0.903 V a) 0.462 V b) 1.100 V 110. Cell Potential and Free Energy 1. 2. 91.3 kJ/mol a) 2 H+ (aq) + 3 H2O (l) + SF 6 (g) + 2 e H2SO3 (aq) + 6 HF (aq) b) 2.60 V 111. Reduction Potentials of Half-Reactions 1. 2. 0.803 V a) 9 H+ (aq) + HSO4 (aq) + 8 e H2S (g) + 4 H2O (l) b) 0.303 V 112. Nonstandard Conditions: The Nernst Equation 1. 2. 1.23 V a) 4 H+ (aq) + 4 Fe 2+ (aq) + O2 (g) 4 Fe3+ (aq) + 2 H2O (l) b) 0.036 V a) Anode: cell on the left (0.010 M Ag + ) b) 0.118 V c) New [Ag + ] = 0.00028 M 114. Putting It Together: Electrochemistry, G, and Keq 1. a) Anode: Sn Sn2+ + 2 e b) 0.010 V c) 1.9 kJ/mol d) K = 2.2 e) 0.045 V 115. Electrolysis: Faraday's Law 1. 2. 3. 0.296 g 9.85 amps a) 30 hours b) 334 kg graphite Cathode: Pb2+ + 2 e Pb Cathode: cell on the right (1.0 M Ag+ )
149
116. Putting It Together: Electrochemistry and Solubility 1. 2. 1.7 1010 a) 8 H+ (aq) + BaCrO4 (s) + 3 e Ba2+ (aq) + Cr3+ (aq) + 4 H2O (l) b) 1.28 V a) positron b) 15C c) 90Zr d) 226Ra e) 247Es f) 143Xe g) 4He ( particle) h) 4 beta particles 118. Radioactive Dating 1. a) 29 years b) 83 years 119. Energy Changes in Nuclear Reactions 1. 2. 1. 2. 1.34 1013 J 7.8 1014 J 0.0205 rad a) 3.14 1010 g b) 0.143 rad 121. Putting It Together: Nuclear Chemistry 1. a) 14C 14N + b) 2.51 1014 J c) 2.35 108 m/s d) 92 % 122. Coordination Complexes: Introduction 1. a) Pt(II), d8, tetraammineplatinum(II) perchlorate b) Re(VII), d0, nonahydridorhenate(VII) c) Fe(-2), d 10, sodium tetra(carbonmonoxide)ferrate(2) or sodium tetracarbonylferrate(2) d) Ir(III), d6, hexafluoroiridate(III) e) Fe(III), d5, potassium hexacyanoferrate(III) f) Pt(II), d 8, diamminedichloroplatinum(II)
150
both achiral
b)
NH3 Br Pt Cl Cl Cl NH3 Br
Cl trans achiral
Br trans achiral
NO2
NH3
a)
O2N
Co N H3 NH3
N H3 NO2
b) Since the Cl groups are replacing the NO2 ligands, and the Cl's end up trans in the product, there must be a trans pair of NO2 ligands in the starting material. Thus the isomer on the left must have been the starting material. 124. Geometry and Isomerism II: Chelates 1.
Cl N Co N Cl O H2 N OH2 N Co Cl OH2 N Cl OH2 Cl N Co Cl Cl Cl OH2 OH2 OH2 H2 O Co N N
Cl trans achiral
151
125. Electronic Structure of Coordination Compounds 1. a) d 6 high-spin; 4 "downstairs" and 2 "upstairs"; 4 unpaired electrons. b) d8 (high/low doesn't matter); 6 "downstairs" and 2 "upstairs"; 2 unpaired electrons c) d 6 low-spin; 6 "downstairs"; no unpaired electrons. d) d6 low-spin; 6 "downstairs"; no unpaired electrons. 2. [Co(NH3) 6] 3+ strongest ligands largest o absorbs violet appears yellow 3. [Co(NH3) 5(OH 2)]3+ intermediate intermediate o absorbs green appears red [CoF 6] 3 weakest ligands smallest o absorbs orange appears blue
FeF63 is d5 high-spin electron configuration with 5 unpaired electrons, all spin "up". In order to promote an electron from the lower to the higher energy level, its spin would have to "flip," which is forbidden. Thus the d5 high-spin configuration is usually colorless. (This isn't a problem for d6 Co(III)). a) Sodium pentacyanonitrosylferrate (III) b) d5 low spin; 5 "downstairs"; one unpaired electron. c) NO must be slightly weaker than CN. The complex with the NO ligand absorbs light of slightly lower energy (absorbs yellow-green) in comparison with the all-CN complex (absorbs green-blue). Thus the splitting must be less when there is an NO ligand, and we conclude that the NO ligand is slightly weaker than the CN ligand. (If it were much weaker we would have seen a much more dramatic change of color.) d) Since the complex has 5 electrons in the more stable downstairs (t2g) orbitals, and no electrons in the upstairs (eg) orbitals, it will be very stable, kinetically inert, and thus the ligands will dissociate slowly.
H2 C O
(cis+trans isomers)
152
2.
a) H3C
C H2
OH C H O O , which is an aldehyde.
C OH
Monomer:
F C C F F
condensation
Polyalanine (a polypeptide)
H N H C CH3 O C N H H C CH3 O C N H H C CH3 O C
N H
C CH3
2.
153
H
5 6 7 8 9
He
4.003 10
1.008 3
Li
13 14 15
Be
O
16
F
17
Ne
18
6.941 9.012
11
12
Na
21 22 23 24 25 26 27 28 29 30 31 32
Mg
Al
Si
P
33
S
34
Cl
35
Ar
36
22.99 24.31
19
20
K Sc
39 40 41 42 43 44 45 46 47 48 49
Ca
Ti Mn Ni Zn
Cr
Fe
Co
Cu
Ga
Ge
50
As
51
Se
52
Br
53
Kr
54
39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.39 69.72 72.61 74.92 78.96 79.90 83.80
37
38
154 Y Zr
72 73 74 75 76 77 78 79
Rb Mo
57
Sr
Nb
Tc
Ru
Rh
Pd
Ag
Cd
80
In
81
Sn
82
Sb
83
Te
84
I
85
Xe
86
(98) 101.07 102.91 106.42 107.87 112.41 114.82 118.71 121.76 127.60 126.91 131.29
55
56
Cs
Ba
La Hf Re Pt
Ta
Os
Ir
Au
Hg
Tl
Pb
Bi
Po
At
Rn
132.91 137.33 138.91 178.49 180.95 183.85 186.21 190.20 192.22 195.08 196.97 200.59 204.38 207.20 208.98 (209) (210) (222) 104 105 [106] [107] [108] [109] 87 88 89
Fr
Ra
Ac
Rf
Ha
(262) (263) (262) (265) (266) 58 59 60 61 62 63 64 65 66 67 68 69 70 71
Lanthanide seriesCe
Pr
Nd
Pm
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
140.12 140.91 144.24 (145) 150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97 100 101 102 103 90 91 92 93 94 95 96 97 98 99
Actinide series Th
Pa
Np
Pu
Am
Cm
Bk
Cf
Es
Fm
Md
No
Lr
232.04 231.04 238.03 237.05 (244) (243) (247) (247) (251) (252) (257) (258) (259) (260)