MOC ACS Exam: Physical Chemistry Thermodynamics

1. The entropy of a system (degeneracy = W) is

(A) kBTlnW (B) -kBTlnW (C) kBlnW (D) kB/lnW

2. The Classius-Clapyeron equations assumes:

(A) constant T (B) constant P
(C) constant DH (D) a solid liquid phase transition

3. Select the partial derivative that equals the chemical potential of component i, mi.
Ê ∂G ˆ Ê ∂G ˆ Ê ∂G ˆ Ê ∂G ˆ
(A) mi = Á ˜ (B) mi = Á ˜ (C) mi = Á ˜ (D) mi = Á ˜
Ë ∂ni ¯ S,V,n' Ë ∂ni ¯ T,V,n' Ë ∂ni ¯ T,H,n' Ë ∂ni ¯ T,P,n'

4. Which combination is not dependent on the path over which a thermodynamic process
proceeds? (A) DH, DU, DS, DG (B) DU, q, DS (C) DU, DH, DG, w (D) q, w

5. DG = DH - TDS assumes:
(A) constant T (B) constant P (C) nothing (D) A and B

6. Which of the following equations is the equation of state for an ideal gas?
RT a RT
(A) P = - 2 (B) P =
V-b V V
RT aa (T) RT
(C) P = (D) P =
V - b V( V + b ) ea / VRT (V - b )

7. For a Carnot cycle the change in internal energy is _____ zero because the initial and final
states are the same.
(A) greater than (B) equal to (C) less than (D) never

8. A sample of an ideal gas expands irreversibly and adiabatically into a vacuum. The change
in entropy of the universe
(A) increases B) remains unchanged C) decreases D) none of these

9. A sample of an ideal gas expands irreversibly and adiabatically into a vacuum. The entropy
of the system will
(A) increase (B) remain unchanged (C) decrease (D) none of these

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10. A sample of an ideal gas expands irreversibly and adiabatically into a vacuum. The
entropy of the surroundings is
(A) positive (B) negative (C) zero (D) none of these

11. For the adiabatic compression of a gas, which is true?

(A) q=0 & DU>0 (B) q>0 & DU=0 (C) q=0 & DU<0 (D) q<0 &DU=0

12. A sample of an ideal gas expands reversibly and isothermally. The entropy of the universe
(A) increases (B) remains unchanged (C) decreases (D) none of these

13. A sample of an ideal gas expands reversibly and isothermally. The entropy of the system
(A) increases (B) remains unchanged (C) decreases (D) none of these

14. A sample of an ideal gas expands reversibly and isothermally. The entropy of the
surroundings
(A) increases (B) remains unchanged (C) decreases (D) none of these

15. For the reaction at a constant temperature NH3 (g) Æ N(g) + 3H(g) if DU is known, DH
is approximately (A) DU + 3RT (B) DU-3RT (C) DU+RT (D) zero

16. The mean ionic activity coefficient for Na3 PO4 would be given by
1/ 2 1/ 4 1/ 4
(A) g ± = (g + g - ) (B) g ± = (g +2 g 2- ) (C) g ± = (g + g 3- ) (D) g ± = (g +3 g - )

17. For the gaseous reaction at 457K and 1 bar, molecule CD is 10% dissociated according to
CD -> C + D. The equilibrium constant for this reaction is approximately
(A) 0.10 (B) 0.01 (C) 0.02 (D) 0.2

18. For the protein catalyzed electron transfer reaction (the cytochromes are proteins)
cytochrome b5 Fe(II) + cytochrome c Fe(III) -> cytochrome b5 Fe(III) + cytochrome c Fe(II)
DGo is related to the standard cell potential, Eo, by
(A) -FEo (B) FEo (C) -2FEo (dD) -FEo/2

19. A sample of an ideal gas is expanded isothermally. Heat is

(A) flowing out of the system (B) flowing into the system
(C) trapped in the surroundings (D) not flowing

20. Natural hydrogen contains approximately 0.015% deuterium (mass 2). Chlorine is a
mixture of isotopes mass 35, 75.53% and mass 37, 24.47%. What would be the mole fraction of
natural D37Cl?
(A) 3.67x10-5 (B) 1.13x10-4 (C) 0.2447 (D) 0.7552

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21. The partial vapor pressure of one component of a binary mixture is shown in the figure.
In which region is Raoult's law obeyed?

22. Consider the figure in the previous problem. In which region is Henry's law obeyed?

23. Which of the following statements are true concerning the Boltzmann distribution?
(A) The molecular partition coefficient is the numerator of the Boltzmann distribution.
(B) As temperature decreases, the Boltzmann distribution predicts that more energy states will be
populated.
(C) If energy is in cal/mol then R= 1.987 cal/mol•K can be substituted for Boltzmann's constant.
(D) The relationship between R and k b is kb = NAR.

24. When determining So graphically, you need heat capacity and temperature data and
(A) plot heat capacity vs. T and S o = the area under the curve
(B) average heat capacity and average T, then S o = Caverage/Taverage.
(C) plot C/T vs. T and So = the area under the curve
(D) plot C vs. V and So = the area under the curve.

25. Consider the Boltzmann distribution function. For a molecule with four different energy
states available (2.1, 2.2, 2.4, and 2.6 kcal/mol respectively), at which temperature will the
populations for each state be approximately equal?
(A) 25 K (B) 25°C (C) 300 K (D) 1000 K

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26. Assuming that no hydrolysis of Al3+ takes place, the ionic strength of 0.010 molal
Al2(SO4)3 is ____ molal.
(A) 0.005 (B) 0.010 (C) 0.050 (D) 0.15 (E) 1.5

27. The following thermochemical data are for 25°C and are independent of temperature over
a ±10° range of temperature.
DHof (kJ/mol) Cpo (J/mol•K)
H2O (l) -286.0 75.3
H+ (aq) 0 0
OH- (aq) -230.0 -148.0
For the self-ionization of water, H2O (l) -> H + (aq) + OH- (aq), the value of DHo at 35°C is ___
kJ/mol.
(A) 58.1 (B) 57.2 (C) 55.8 (D) 53.8 (E) 50.3

28. Which of the following corresponds to the correct units for molarity.
(A) moles solute/liter solution (B) moles solute/kg solvent
(C) moles solute/total moles (D) moles solute/liter solvent
(E) moles solute/kg solution

29. When a negative enthalpy of mixing if found for making a solution, which of the
following statements is true:
(A) The solution is ideal.
(B) The interactions between solute with solvent are the same as between solute with solute and
solvent with solvent.
(C) The interactions between solute with solvent are very different from those between solute
with solute and solvent with solvent.
(D) The change in free energy is zero.

P2
dP
30. What is the form of the following integral, Ú
P1
P
ÊPˆ ÊP ˆ
(A) P 2 - P1 (B) P1 - P2 (C) ln ÁÁ 1 ˜˜ (D) ln ÁÁ 2 ˜˜
Ë P2 ¯ Ë P1 ¯

nRT Ê ∂V ˆ
31. Given V( P,T) = what is Á ˜ ?
P Ë ∂T ¯ P
- nRT nR - nRT nR nRT nR
(A) (B) (C) + (D) -
P2 P P2 P P2 P

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32. If the standard enthalpy change, DHo , for a reaction is positive, the equilibrium constant
will
(A) be independent of T & P (B) increase with the increase of P
(C) increase with in increase in T (D) decrease with the increase in T
(E) decrease with the increase of P

33. For the reaction A<-> B, DH0298 = 418.0 kJ/mol and DGo298 =24.4 kJ/mol. At what
approximate temparature will the mole fractions of A and B be equal?
(A) 200 K (B) 317 K (C) 417 K (D) 1300 K

34. For a specific reaction, DH0298 < 0 and DSo298 > 0. Which of the following statements is
true about the equilibrium constant at 298 K for this reaction.
(A) K > 1 and increases with increasing temperature.
(B) K > 1 and decreases with increasing temperature.
(C) K < 1 and increases with increasing temperature.
(D) K < 1 and decreases with increasing temperature.

35. The entropy change for a liquid heated from T1 to T2 can be calculated from the area
under the curve by plotting
(A) DH as the ordinate and 1/T as the abscissa
(B) Cp as the ordinate and 1/T as the abscissa
(C) CP/T as the ordinate and T as the abscissa
(D) Cp /T as the ordinate and 1/T as the abscissa

36. When a transformation occurs spontaneously at constant temperature and volume, the
signs of DA for the system and DS for the universe are ____ and ____ respectively.
(A) positive, negative (B) negative, either positive or negative
(C) either positive or negative, negative, (D) negative, positive (E) negative, negative

37. What is the correct unit for the fugacity coefficient?

(A) same as pressure (B) dimensionless (C) same as concentration (D) same as
pressure/concentration (E) same as energy

38. Consider the equilibria for phosphoric acid.

H 3PO 4 ´ H + + H 2PO -4 pK1 = 2.15
H 2PO -4 ´ H + + HPO 2-
4 pK 2 = 7.21
HPO 2-
4 ´H
+
+ PO 3-
4 pK 3 = 12.3
What form(s) dominate at pH 5?
(A) H3 PO 4 (B) H 2 PO-4 (C) H3 PO 4 and H 2 PO -4 (comparable amounts)
(D) H 2 PO-4 and HPO 2-4 (comparable amounts) (E) HPO 2-
4
†

39. For the spontaneous process, ice (5°C) -> water (5°C), select the correct set of signs for
DSsystem, DSsurroundings , DSuniversie, respectively.
(A) +, -, 0 (B) -, +, 0 (C) +, -, + (D) -, +, + (E) -, +, -

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 40. A buffer of sodium acetate and acetic acid maintains a pH near its pK a, 4.760; the
concentrations of sodium, acetate, and nondissociated acetic acid are 0.01000 m . If a protein
with a charge of +2 is dissolved in the buffer solution to give a protein concentration of
1.000x10-5 m, what is the ionic strength of the solution?
(A) 2.006x10-2 m (B) 1.002x10-2 m (C) 2.000x10-2 m (D) 1.000x10-2 m

41. Hydrolysis of ATP provides -31 kJ/mol of free energy. Which of the following reactions
cannot be driven by the hydrolysis of ATP?
(A) D - glucose + phoshpate æhexokinase
æ ææÆ glu cose - 6 - phophate DG0' = 14.3kJ/ mol
æÆ fructose - 1,6 - bisphosphate DG 0' = 16.8kJ /mol
(B) fructose - 6 - phosphate + Pi æphosphofructokinase
æææ
(C) pyruvate + phosphate æpyruvate
æ ækinase
æÆ phosphoenolpyruvate DGo' = 62.4kJ / mol
æ
(D) 2phosphate æHæ 2O
Æ pyrophosphate DGo' = 33kJ / mol
(E) Neither C nor D can be driven by hydrolysis of ATP.
†

42. As the concentration of the ions increase, which of the following statements is true?
(A) The mean ionic activity coefficient decreases.
(B) The activity of each ion reaches the limit where activity equals concentration.
(C) The mean ionic activity coefficient increases.
(D) The mean ionic activity coefficient remains constant after a certain concentration is reached.

43. Molecular weight of a substance can be determined by dissolving it in water and

measuring the change in boiling point. Which of the following must be necessary for this
procedure to work.
(A) The substance must be an electrolyte.
(B) The substance must be insoluble in water.
(C) The activity of the substance must be equal to its concentration
(D) The substance must be nonvolatile.