Cs) + COLg) = 2CO(g) 7. AH for the reaction shown above is greater than zero. Assuming AH is independent of tempera- [Al [Bl Initial Rate ture, which of the following statements about the percent yield of CO(g) is true? 0.50M 0.50M 10Ms" (A) Itinereases as the amount of C(s) increases. 0.50M 1.00M 20Ms" (B) Itincreases as the temperature increases. 0.25M 0.50M 5Ms! (C) Itdecreases as the temperature increases. (D) Itdoubles when the initial partial pressure of CO, is doubled. @ Mrinereaves when the total pressure ofthe 8. The initial rates given above were determined reaction system increases. for the reaction A + 2B — AB,. Whatis the overall rate law for this reaction? (A) Rate = K[APIBP (B) Rate = k{AP[B] (C) Rate = k[A][BP (D) Rate = k{A][B] (E) Rate = k 1.00M 1.00M 40Ms?15. The half-life of 'C is 5,730 years. All of the following are true for the method of carbon dating EXCEPT: (A) MC undergoes B-decay to produce '4N. (B) The ''C content of an organism decreases after it dies. (C) The “c/?C ratio is the same in living terrestrial organisms as in the atmosphere. (D) The 'c/'?C ratio can be used to date a sample from a dead organism. (E) Carbon dating is equally useful for samples that are millions of years old as for samples that are about 10,000 years old.PP Rr 200 400 600 P (bar) 16, Thecurve shown aboveilustrtes the PV tehuvior of areal gas, where V isthe molar ‘olume: According tote van der Waals model for nonidel gas behavior, the values of PV/RT ‘greater than 1.0 at high pressures are due to (A) the effoets of incressed rats of collision ofthe ‘molecules with the walls of the container (B) the effects of dissociation of individual gas molecules (©) the effects of the volume cecupied by the ‘molecules themselves (D) the effects of forces of attraction between molecules (E) ideal gas behavior inthis pressure region 18, In an isolated hydrogen atom, the 2p, orbital has the same principal quantum number, 7, as which of the following orbitals? 12s IL 2p, Il. 3p, (A) Lonly (B) only (©) Monly (D) Land Ionly () Wand I only25. When 1.0 kJ of heat is added to 5.0L of an ideal gas, the gas expands against a constant external pressure of 1.0 bar to a final volume of 8.0 L. What is the change in internal energy, AU for the gas? (1.0 L-bar = 0.10 kJ) (A) 0.30 KI (B) 0.70 KI (©) LOK (D) 13k (BE) 18kI 33. Two cylinders, one containing 1 mole of CyHyy gas at 1 atm and the other containing 1 mole of CH, gas at 1 atm, are at 288 K. If each gas absorbs 100 J of heat under conditions of constant, volume, which of the following is tue? (A) The temperature of the CH, increases more than the temperature of the C,Hyo. (B) The internal energy of both the CH, and the CyHio decreases. (C) The heat capacity of the C,Hyo is less than the heat capacity of the CH,. (D) The entropy of both the CH, and the CsHyo decreases. (E) The heat transferred to the C,Hyo is greater than the heat transferred to the CH,. 26. Which of the following must be true for adiabatic processes? (A) Cy = Cp (B) AH =0 (© au =0 (D) as =0 ()q¢ 34. Which of the following statements is true about a pure substance above its critical point? (A) One fluid phase is present. (B) Solid, liquid, and gas are in equilibrium. (C) Only liquid and gas are in equilibrit (D) A liquid forms. (E) A solid forms- J vicow(ode =0 35. If two wavefunctions y(x) and ys(x) satisfy the condition given above, the two wavefunctions are (A) orthogonal (B) degenerate (©) normalized (D) continuous (E) symmetrical 43. Which of the protons indicated will be observed as a doublet in the 'H NMR spectrum of the molecule shown above? (A) a (B) b (ec a © e For a system at thermal equilibrium, which of the following is the Boltzmann distribution 4 s expression for the probability, p,, that a single molecule is in the ith energy state with energy &;? (A) p, =e /KT ® patent ©) p= (eeury eit © y= ee") ms © Pp St 2 A= a y = sink 36. For the equation Ay = ay, where A and y are shown above, all of the following are true EXCEPT: (A) y_ isaneigenfunction of A (B) a isan eigenvalue. (©) a isan observable. (D) A isan operator corresponding to the observable. (E) A isaneigenfunction of a. 3 ). Which of the following expressions involving fugacity, f, is correct as P > 0? (A) f=P 1 ®) f=5 © f=l 1 O fay ® f=v51. Sodium acetate spontaneously crystallizes out 52. If ideal gas behavior is assumed, for which of of a supersaturated solution on standing or on the the following reactions does AH equal AU? addition of a seed crystal. Which of the following is true for the thermodynamic quantities of this (A) N,0,(8) > 2NOx(g) system for this process? (B) CHA(g) + 20g) > CO) + 2H,00 (A) AS <0, AH<0 1 (B) AS <0, AG>0 (©) SO,(g) + 5 Ox(g) > SOAg) (©) AS>0, AH>0 (D) Br) + 3 Ch(g) > 2 BrCl;(g) (D) AS>0, AG<0 &) Ch) + Fug) > 20K) (BE) AG<0, AH>0 QU) __p,7(aP' sion of vi, = psr(). 59. The heat of fusion of ice 333.5 J/g. The entropy change for the water when freezing 5.0 g of water 58. Given the expression above, what is the value of at 0°C and I atm pressure is : _ (A) 610K (), for an ideal gas undergoing isothermal ® 125K expansion? (PV = nRT for an ideal gas.) © 0 (D) -12/K (A) ap ak (BE) -6.10/K (B) mR ©) -P «) __vis} @)1 rile = + (ST © 0 60. Many enzyme reactions follow the Michaelis- ‘Menten rate law shown above, where V and K,, are constants and [S] is the concentration of substrate that is undergoing a catalyzed reaction. When [$]>>K,,, what is the apparent order of the reaction? (A) Zero order (B) One-half order (C) First order (D) Second order () Third orderatlii. within v— 69. A high-resolution infrared absorption spectrum, of a heteronuclear diatomic molecule is shown above. Information about which of the following kinds of energy levels of the diatomic molecule can be obtained from this spectrum? I. Electronic IL. Vibrational TI. Rotational (A) Lonly B) Honly (C) Wonly (D) Hand Il only (B) 1,1, and Il 71. All of the following are true about lasers EXCEPT: (A) The light does not diverge significantly. (B) The light is emitted only in pulses. (C) The light waves are in phase. (D) The light is essentially all the same wavelength. (E) The light is essentially all the same frequency. 70. The ionization energy of a ground state H_atom is 13.6 eV. Given the equation shown above, how much energy is needed to excite an electron in an H atom from a state with quantum number n= 1 toastate with n = 2? (A) (1/8) 13.6 eV B) (1/4) 13.6 eV (© (12) 13.6eV @) G/4) 13.6eV (E) 13.6eV So 72, Consider the ground electronic state Sy. the ‘excited singlet stale 5,, and the triplet state 7, ‘ofa molecule. shown above. The Sy — Sg transition corresponds to (A) a forbidden transition (B) fluarescence (C) phosphorescence (D) photoionization (B) vibrational relaxation74. The experimental technique most suited for the determination of the three-dimensional structure of a crystalline solid is (A) UV-visible spectroscopy (B) X-ray diffraction (C) measurement of colligative properties (D) polarimetry (E) Fourier transform mass spectrometry ky +0, —25 2NO, 84. Consider the mechanism shown above for oxidation of NO by O;. Based on the steady state approximation, which of the following conditions is true for this mechanism? dINO3] _ 5 alNz0}] dt dt d\NO> B) “2 =0 ® Th {NO} _ Ona 7° (D) [N,0,]=0 © h=k+k, (A) A — Products 83. For the reaction shown above, the experimental rate law is rate = K[AJ?. Which of the following is the integrated rate law for this reaction? [Aly A) tak (A) TA] [Alo _ ® mapa (©) [A] [Alp = (D) [AP [Aj = kr 1 (E) TAN TAR kt k= 10k at f= 0: [Bl = IC] =0 85. Given the information above, the concentrations ‘of B and C and the control (thermodynamic or ‘Kinetic) ofthe system at short and long times are described by which of the following? ‘Shor Time Long Time ~® BL> IC) [1 > ‘Kinetic thermodynamic ® (C)> BI (B} > (C) ‘Kinetic thermodynamic © Bia [cl] > (BI thermodynamic ‘kinetic ©) (Cl> BI (B] > IC} thermodynamic Kinetic ® B> (B] > () Kinetic Kinetic92. Which of the following is a wavefunction, w(r,9,0), for an 5 electron? 2 “ wp - a 2 a =a (B) Nre2# cosd a (© Nre* sindcos¢ oe ©) Nre sindsing “a () Nie (3c0s*@ 1) E,, = 7 1?/8mL? 103. For a particle of mass m in a one-dimensional box of length L, the energy of the particle is giver by the equation shown above. How much energy is required to promote the particle from the state with quantum number n= 2 to the state with quantum number n= 3°? (A) 91° /8m1? (B) Sh?/8m1> (©) 4h?8mL? (D) W/L? (&) 0 93. Due to electron-electron interactions, it is not possible to obtain exact solutions to the Schrédinger equation for many-electron atoms. ‘One approach that addresses this difficulty uses (A) the rigid-rotor approximation (B) the harmonic oscillator approximation (C) the principle of corresponding states (D) effective nuclear charges (E) the Franck-Condon principle ‘94. Of the following linear combinations of atomic orbitals centered on two atoms, A and B, which best represents the ground-state molecular orbital for the hydrogen molecule, H ? (A) vy = N(Isy + Isp) (B) y = Nlsy — Isp) (© y= NUsy + 2pp) (D) w = N(ls, — 2pp) ©) v= Np, + 2pp—) 104, A large activation energy implies which of the following about a reaction? A I (B) Itis highly endothermic. (C) Itis at equilibrium. (D) Itis very rapid. (E) It has a highly temperature-dependent ‘rate constant.106. In an experiment to test the de Broglie hypothesis, abeam of high-energy electrons with momenta p=mv=6x 107 ke-mis ‘would be scattered by a nickel crystal with a pattern similar to that of which of the following? (A) X-rays of wavelength 2= hip (B) Electromagnetic radiation with wavelength A=plh (C) A beam of protons with velocity. v (D) Billiard balls undergoing perfectly elastic collisions (B) Visible light with a mixture of frequencies frequently characterized as “white” he rate constant for a first-order reaction R > P is 0.010s", The concentration of R decreases to one-half of its initial value after 2s 0.010 In2 ®) do (a) © xo00* 1 ©) Zoo0I0* (E) 5(0.010)s 107. Which of the following is true about the quantum 114. yield for photodecomposition of a chromophore? (A) It depends on the intensity of the light source used for the photolysi: (B) It depends on the duration of the light source used for the photolysis. (C) Itis the reciprocal of the fluorescence lifetime. (D) Ithas a value of either 0 or I, reflecting the quantum nature of photons. (E) Itis the ratio of the number of chromophores. decomposed to the number of photons absorbed. The activated-complex theory (or transition state theory) assumes that an equilibrium exists, between the (A) activated complex and reactants only (B) activated complex and products only (C) products and reactants only (D) reactants, activated complex, and products (E) system (reaction) and surroundings