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chemistry
physical chemistry
Questions and Answers of
Physical Chemistry
Using thermodynamic data from Appendix 4, calculate ΔGo at 25oC for the process 2SO2(g) + O2(g) → 2SO3(g) w here all gases are at 1.00 atm pressure. Also calculate ΔGo at 25oC for this same
Consider the reaction 2NO2(g) ⇌ N2O4(g) For each of the following mixtures of reactants and products at 25oC, predict the direction in which the reaction will shift to reach equilibrium. Use
Using data from Appendix 4, calculate ΔG for the reaction 2H2S(g) + SO2(g) ⇌ 3S(s) + 2H2O(g) for the following conditions at 25oC: PH2S = 1.0 × 10–4 atm PSO2 = 1.0 × 10-2 atm PH2O = 3.0 ×
Using data from Appendix 4, calculate ΔHo, ΔSo, and K (at 298 K) for the synthesis of ammonia by the Haber process: N2(g) + 3H2(g) ⇌ 2NH3(g) Calculate ΔG for this reaction under the following
One of the reactions that destroys ozone in the upper atmosphere is NO(g) + O3(g) ⇌ NO2(g) + O2(g) Using data from Appendix 4, calculate ΔGo and K (at 298 K) for this reaction.
Hydrogen sulfide can be removed from natural gas by the reaction 2H2S(g) + SO2(g) ⇌ 3S(s) + 2H2O(g) Calculate ΔGo and K (at 298 K) for this reaction. Would this reaction be favored at a high or
Consider the autoionization of water at 25oC: H2O(l) ⇌ H+(aq) + OH-(aq) Kw = 1.00 × 10-14 a. Calculate ΔGo for this process at 25oC. b. At 40oC, Kw = 2.92 × 10-14. Calculate ΔGo at 40oC.
How can one estimate the value of K at temperatures other than 25oC for a reaction? How can one estimate the temperature where K = 1 for a reaction? Do all reactions have a specific temperature where
The standard free energies of formation and the standard enthalpies of formation at 298 K for difluoroacetylene (C2F2) and hexafluorobenzene (C6F6) areFor the following reaction: C6F6(g)
Consider the reaction Fe2O3(s) + 3H2(g) → 2Fe(s) + 3H2O(g) Assuming ΔHo and ΔSo do not depend on temperature, calculate the temperature where K = 1.00 for this reaction.
The Ostwald process for the commercial production of nitric acid involves three steps:2NO(g) + O2(g) 2NO2(g) 3NO2(g) + H2O(l) 2HNO3(l) + NO(g) a. Calculate ÎHo,
Consider the following reaction at 800. K: N2(g) + 3F2(g) → 2NF3(g) An equilibrium mixture contains the following partial pressures: PN2 = 0.021 atm, PF2 = 0.063 atm, and PNF3 = 0.48 atm. Calculate
Consider the following reaction at 298 K: 2SO2(g) + O2(g) → 2SO3(g) An equilibrium mixture contains O2(g) and SO3(g) at partial pressures of 0.50 atm and 2.0 atm, respectively. Using data from
For the reaction A(g) + 2B(g) ⇌ C(g) the initial partial pressures of gases A, B, and C are all 0.100 atm. Once equilibrium has been established, it is found that [C] = 0.040 atm. What is ΔGo for
Consider the following diagram of free energy (G) versus fraction of A reacted in terms of moles for the reaction 2A(g) B(g).Before any A has reacted, PA = 3.0 atm and PB = 0. determine
Calculate ΔGo for H2O(g) + 12 O2(g) ⇌ H2O2(g) at 600. K, using the following data: H2(g) + O2(g) ⇌ H2O2(g) K = 2.3 × 106 at 600. K 2H2(g) + O2(g) ⇌ 2H2O(g) K = 1.8 × 1037 at 600. K
Cells use the hydrolysis of adenosine triphosphate, abbreviated ATP, as a source of energy. Symbolically, this reaction can be represented as ATP(aq) + H2O(l) → ADP(aq) + H2PO4-(aq) where ADP
Carbon monoxide is toxic because it bonds much more strongly to the iron in hemoglobin (Hgb) than does O2. Consider the following reactions and approximate standard free energy changes: Hgb + O2 →
One reaction that occurs in human metabolism isFor this reaction ÎGo = 14 kJ at 25oC. a. Calculate K for this reaction at 25oC. b. In a living cell this reaction is coupled with the
At 25.0oC, for the reaction 2NO2(g) ⇌ N2O4(g) the values of ΔHo and ΔSo are –58.03 kJ/ mol and –176.6 J K-1mol-1, respectively. Calculate the value of K at 25.0oC. Assuming ΔHo and ΔSo are
Consider the relationshipThe equilibrium constant for some hypothetical process was determined as a function of temperature (in kelvins) with the results plotted below. From the plot, determine the
a. Use the equation in Exercise 86 to determine ÎHo and ÎSo for the autoionization of water: H2O(l) H+(aq) + OH-(aq)b. Estimate the value of ÎGo for
The equilibrium constant K for the reaction 2Cl(g) ⇌ Cl2(g) was measured as a function of temperature (in kelvins). A graph of ln(K) versus 1/ T for this reaction gives a straight line with a slope
The equilibrium constant for a certain reaction decreases from 8.84 to 3.25 × 10-2 when the temperature increases from 25oC to 75oC. Estimate the temperature where K = 1.00 for this reaction.
A sample of a monatomic ideal gas at 1.00 atm and 25oC expands adiabatically and reversibly from 5.00 L to 12.5 L. Calculate the final temperature and pressure of the gas, the work associated with
A sample of 1.75 moles of H2 (Cv = 20.5 J K-1mol-1) at 21oC and 1.50 atm undergoes a reversible adiabatic compression until the final pressure is 4.50 atm. Calculate the final volume of the gas
A 1.50-mole sample of an ideal gas is allowed to expand adiabatically and reversibly to twice its original volume. In the expansion the temperature dropped from 296 K to 239 K. Calculate ΔE and ΔH
Consider 1.00 mole of CO2(g) at 300. K and 5.00 atm. The gas expands until the final pressure is 1.00 atm. For each of the following conditions describing the expansion, calculate q, w, and ΔE. Cp
Consider 1.00 mole of CO2(g) at 300. K and 5.00 atm. The gas expands until the final pressure is 1.00 atm. For each of the following conditions ΔEscribing the expansion, calculate ΔS, ΔSsurr, and
Monochloroethane (C2H5Cl) can be produced by the direct reaction of ethane gas (C2H6) with chlorine gas or by the reaction of ethylene gas (C2H4) with hydrogen chloride gas. The second reaction gives
Given the following illustration, what can be said about the sign of ÎS for the process of solid NaCl dissolving in water? What can be said for ÎH about this process?
Discuss the relationship between wmax and the magnitude and sign of the free energy change for a reaction. Also discuss wmax for real processes.
The enthalpy of vaporization of chloroform (CHCl3) is 31.4 kJ/ mol at its boiling point (61.7oC). determine ΔSsys, ΔSsurr, and ΔSuniv when 1.00 mole of chloroform is vaporized at 61.7oC and 1.00
Two crystalline forms of white phosphorus are known. Both forms contain P4 molecules, but the molecules are packed together in different ways. The a form is always obtained when the liquid freezes.
In the text the equation ΔG = ΔGo + RT ln(Q) was derived for gaseous reactions where the quantities in Q were expressed in units of pressure. We also can use units of mol/ L for the quantities in
Many biochemical reactions that occur in cells require relatively high concentrations of potassium ion (K+). The concentration of K+ in muscle cells is about 0.15 M. The concentration of K+ in blood
Consider the following system at equilibrium at 25oC: PCl3(g) + Cl2(g) ⇌ PCl5(g) ΔGo = –92.50 kJ What will happen to the ratio of partial pressure of PCl5 to partial pressure of PCl3 if the
Consider the reaction H2(g) + Br2(g) ⇌ 2HBr(g) where ΔHo = 2103.8 kJ. In a particular experiment, 1.00 atm of H2(g) and 1.00 atm of Br2(g) were mixed in a 1.00-L flask at 25oC and allowed to reach
At 1500 K the processis not spontaneous. However, the process is spontaneous at 1500 K. Explain.
Using the following data, calculate the value of Ksp for Ba(NO3)2, one of the least soluble of the common nitrate salts.
Consider the reactions Ni2+(aq) + 6NH3(aq) → Ni(NH3)62+(aq) (1) Ni2+(aq) + 3en(aq) → Ni(en)32+(aq) (2) Where en = H2NOCH2OCH2ONH2 The ΔH values for the two reactions are quite similar, yet
The deciding factor on why HF is a weak acid and not a strong acid like the other hydrogen halides is entropy. What occurs when HF dissociates in water as compared to the other hydrogen halides?
The third law of thermodynamics states that the entropy of a perfect crystal at 0 K is zero. In Appendix 4, F-(aq), OH-(aq), and S2-(aq) all have negative standard entropy values. How can S8 values
Calculate the entropy change for the vaporization of liquid methane and hexane using the following data:Compare the molar volume of gaseous methane at 112 K with that of gaseous hexane at 342 K. How
The standard entropy values (So) for H2O(l) and H2O(g) are 70. JK-1mol-1 and 189 JK-1mol-1, respectively. Calculate the ratio of Vg to Vl for water using Boltzmann’s equation. (See Exercise 22.)
Calculate the values of ΔS and DG for each of the following processes at 298 K: H2O(l,298 K) → H2O(g, V = 1000. L/mol) H2O(l,298 K) → H2O(g, V = 100. L/mol) The standard enthalpy of vaporization
Calculate the changes in free energy, enthalpy, and entropy when 1.00 mole of Ar(g) at 27oC is compressed isothermally from 100.0 L to 1.00 L.
Consider the isothermal expansion of 1.00 mole of ideal gas at 27oC. The volume increases from 30.0 L to 40.0 L. Calculate q, w, ΔE, ΔH, ΔS, and ΔG for two situations: a. a free expansion b. a
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
One mole of an ideal gas with a volume of 6.67 L and a pressure of 1.50 atm is contained in a vessel with a movable piston. The external pressure is suddenly increased to 5.00 atm and the gas is
Consider a 2.00-mole sample of Ar at 2.00 atm and 298 K. a. If the gas sample expands adiabatically and reversibly to a pressure of 1.00 atm, calculate the final temperature of the gas sample
Consider 1.0 mole of a monatomic ideal gas in a container fitted with a piston. The initial conditions are 5.0 L and P = 5.0 atm at some constant T. a. If the external pressure is suddenly changed to
One mole of an ideal gas undergoes an isothermal reversible expansion at 25oC. During this process, the system absorbs 855 J of heat from the surroundings. When this gas is compressed to the original
At least some of what is in the following quoted statement is false. Change the incorrect statements so that they are correct and defend your answer. What is correct in the statements? What is wrong?
You have a 1.00- L sample of hot water (90oC) sitting open in a 25oC room. Eventually the water cools to 25oC, whereas the temperature of the room remains unchanged. Calculate ΔSuniv for this
If wet silver carbonate is dried in a stream of hot air, the air must have a certain concentration level of carbon dioxide to prevent silver carbonate from decomposing by the reaction Ag2CO3(s) ⇌
Using data from Appendix 4, calculate ΔHo, ΔGo, and K (at 298 K) for the production of ozone from oxygen: 3O2(g) ⇌ 2O3(g) At 30 km above the surface of the earth, the temperature is about 230. K
One mole of a monatomic ideal gas (for which So = 8.00 JK-1mol-1 at 273.0oC) was heated at a constant pressure of 2.00 atm from 273.0oC to 27.0oC. Calculate ΔH, ΔE, w, q, ΔS due to the change in
Consider the system A(g) → B(g) at 25oC. a. Assuming that GoA = 8996 J/mol and GoB = 11,718 J/ mol, calculate the value of the equilibrium constant for this reaction. b. Calculate the equilibrium
Liquid water at 25oC is introduced into an evacuated, insulated vessel. Identify the signs of the following thermodynamic functions for the process that occurs: ΔH, ΔS, ΔG, ΔTwater, ΔSsurr,
Consider 1.00 mole of an ideal gas that is expanded isothermally at 25oC from 2.45 × 10-2 atm to 2.45 × 10-3 atm in the following three irreversible steps: Step 1: from 2.45 × 10-2 atm to 9.87 ×
Consider 1.00 mole of an ideal gas at 25oC. a. Calculate q, w, ΔE, ΔS, ΔH, and ΔG for the expansion of this gas isothermally and irreversibly from 2.45 × 10-2 atm to 2.45 × 10-3 atm in one
Consider the reaction 2CO(g) + O2(g) → 2CO2(g) a. Using data from Appendix 4, calculate K at 298 K. b. What is ΔS for this reaction at T = 298 K if the reactants, each at 10.0 atm, are changed to
Calculate ΔHo and ΔSo at 25oC for the reaction 2SO2(g) + O2(g) → 2SO3(g) at a constant pressure of 1.00 atm using thermodynamic data in Appendix 4. Also calculate ΔHo and ΔSo at 227oC and 1.00
Although we often assume that the heat capacity of a substance is not temperature dependent, this is not strictly true, as shown by the following data for ice:Use these data to calculate graphically
Consider the following Cp values for N2(g):Assume that Cp can be expressed in the form Cp = a + bT + cT2 Estimate the value of Cp for N2(g) at 900. K. Assuming that Cp shows this temperature
Benzene (C6H6) has a melting point of 5.5oC and an enthalpy of fusion of 10.04 kJ/mol at 25.0oC. The molar heat capacities at constant pressure for solid and liquid benzene are 100.4 JK-1mol-1 and
Impure nickel, refined by smelting sulfide ores in a blast furnace, can be converted into metal from 99.90% to 99.99% purity by the Mond process. The primary reaction involved in the Mond process is
The initial state of an ideal gas is 2.00 atm, 2.00 L. The final state is 1.00 atm, 4.00 L. The expansion is accomplished isothermally. a. If the expansion is a free expansion, calculate w, q, ΔE,
Define the following. a. Spontaneous process b. Entropy c. Positional probability d. System e. Surroundings f. Universe
Table 10.1 shows the possible arrangements of four molecules in a two-bulbed flask. What are the possible arrangements if there is one molecule in this two-bulbed flask or two molecules or three
Consider the following illustration of six molecules of gas in a two-bulbed flaska. What is the most likely arrangement of molecules? How many microstates are there for this arrangement? b. Determine
Consider the following energy levels, each capable of holding two objects:Draw all the possible arrangements of the two identical particles (represented by X) in the three energy levels. What total
Do Exercise 15 with two particles A and B that can be distinguished from each other.Consider the following energy levels, each capable of holding two objects:
Which of the following involve an increase in the entropy of the system under consideration? a. Melting of a solid b. Evaporation of a liquid c. Sublimation d. Freezing e. Mixing f. Separation g.
Describe how the following changes affect the positional probability of a substance. a. Increase in volume of a gas at constant T b. Increase in temperature of a gas at constant V c. Increase in
Phosphate buffers are important in regulating the pH of intracellular fluids at pH values generally between 7.1 and 7.2. a. What is the concentration ratio of H2PO4- to HPO4-2 in intracellular fluid
Carbonate buffers are important in regulating the pH of blood at 7.40. If the carbonic acid concentration in a sample of blood is 0.0012 M, determine the bicarbonate ion concentration required to
When a person exercises, muscle contractions produce lactic acid. Moderate increases in lactic acid can be handled by the blood buffers without decreasing the pH of blood. However, excessive amounts
Consider the acids in Table. Which acid would be the best choice for preparing a pH = 7.00 buffer? Explain how to make 1.0 L of this buffer.Table
Consider the bases in Table. Which base would be the best choice for preparing a pH = 5.00 buffer? Explain how to make 1.0 L of this buffer.Table
Consider the following pH curves for 100.0 mL of two different acids with the same intital concentration each titrated by 0.10 M NaOH:a. Which plot represents a pH curve of a weak acid, and which
An acid is titrated with NaOH. The following beakers are illustrations of the contents of the beaker at various times during the titration. These are presented out of order. Note: Counter-ions and
Consider the titration of a generic weak acid HA with a strong base that gives the following titration curve:On the curve indicate the points that correspond to the following. a. the equivalence
Sketch the titration curve for the titration of a generic weak base B with a strong acid. The titration reaction is B + H+ ⇌ BH+ On the curve indicate the points that correspond to the
Draw the general titration curve for a strong acid titrated with a strong base. At the various points in the titration, list the major species present before any reaction takes place and the major
Consider the following four titrations: i. 100.0 mL of 0.10 M HCl titrated with 0.10 M NaOH ii. 100.0 mL of 0.10 M NaOH titrated with 0.10 M HCl iii. 100.0 mL of 0.10 M CH3NH2 titrated with 0.10 M
The following plot shows the pH curves for the titrations of various acids with 0.10 M NaOH (all of the acids were 50.0-mL samples of 0.10 M concentration).a. Which pH curve corresponds to the
The figure in the preceding exercise shows the pH curves for the titrations of six different acids with NaOH. Make a similar plot for the titration of three different bases with 0.10 M HCl. Assume
Repeat the procedure in Exercise 65 for the titration of 25.0 mL of 0.100 M propanoic acid (HC3H5O2, Ka = 1.3 × 10-5) with 0.100 M KOH.
Repeat the procedure in Exercise 65 for the titration of 25.0 mL of 0.100 M NH3 (Kb = 1.8 × 10-5) with 0.100 M HCl.
Repeat the procedure in Exercise 65 for the titration of 25.0 mL of 0.100 M pyridine (Kb = 1.7 × 10–9) with 0.100 M hydrochloric acid. Do not do the points at 24.9 mL and 25.1 mL.
Calculate the pH at the halfway point and at the equiva-lence point for each of the following titrations. a. 100.0 mL of 0.10 M HC7H5O2 (Ka = 6.4 × 10–5) titrated with 0.10 M NaOH b. 100.0 mL of
You have 75.0 mL of 0.10 M HA. After adding 30.0 mL of 0.10 M NaOH, the pH is 5.50. What is the Ka value of HA?
What is an acid–base indicator? Define the equivalence (stoichiometric) point and the endpoint of a titration. Why should you choose an indicator so that the two points coincide? Do the pH values
Two drops of indicator HIn (Ka = 1.0 × 10–9), where HIn is yellow and In- is blue, are placed in 100.0 mL of 0.10 M HCl.
A certain indicator HIn has a pKa of 3.00 and a color change becomes visible when 7.00% of the indicator has been converted to In-. At what pH is this color change visible?
Which of the indicators in Fig. could be used for doing the titrations in Exercises 61 and 63?Fig
Which of the indicators in Fig could be used for doing the titrations in Exercises 62 and 64?Fig
Which of the indicators in Fig. could be used for doing the titrations in Exercises 65 and 67?Fig
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