Chem/Biochem 471 Half Exam 6 12/10/10

Page 1 of 2
Name:_________KEY______________

1. Let’s see how well the solution to the one-dimensional particle in a box Schrödinger equation
explains the absorption spectrum of a linear conjugated molecule, beta-carotene. The 22 pi
electrons (11 double bonds) in this molecule are delocalized over the conjugated system.

a) Assume  that  the  energy  level  solutions         E12  =  144  E0  

to  the  particle  in  a  box  each  correspond  to    
an  orbital  occupied  by  2  of  the  pi    
electrons  with  opposite  spins.  Label  the         E11  =  121  E0  
energy  levels  in  the  energy  level  diagram    
with  the  energy,  expressed  in  terms  of    
E0=h2/8ma2  (for  example,  E2  =  4E0)  and         E10  =  100  E0  
populate  these  energy  levels  with    
electrons  to  form  the  lowest  energy  state    
for  the  molecule.  Hint:  remember  to  first   En  =  n2E0  
fully  populate  the  lower  energy  levels    
(not  shown).    
 
b)  Calculate  the  energy  in  Joules  of  the  photon  that  will  excite  an  electron  from  your  highest  
occupied  energy  level  to  the  lowest  unoccupied  energy  level.  This  will  be  the  lowest  energy  
electronic  transition.  Use  18.3  Å    as  the  effective  length  of  the  box.  (Aside:  adding  up  the  C-­‐C  
lengths  would  give  29.4  Å,  but  we  are  simplifying  the  values  of  the  potential  energy  and  
neglecting  electron-­‐electron  repulsions).  
h2 (23)(6.626 ×10 −34 J sec)2 J 2 sec 2 −19
E photon = E12 − E11 = (144 −121)E0 = 23 2 = −31 −10 2 = 2 = 4.13×10 J
8ma (8)(9.11×10 kg)(18.3×10 m) kg ⋅ m
 
 
 
€ c)  Calculate  the  wavelength  in  nm  of  the  photon  of  part  b.  
hc
E photon =
λ
hc (6.626 ×10 −34 J sec)(3.0 ×10 8 m /sec)
λ= = = 480nm
E photon 4.13×10 −19 J

d) Sketch and give the equation for the wavefunction for the quantum number n=4.
⎛ 4 π ⎞
€ Ψ4 = ± 2 a sin⎜ x ⎟
⎝ a ⎠
 
Ψ

€ x
a
 Chem/Biochem 471 Half Exam 6 12/10/10
Page 2 of 2
Name:__________ KEY______________

2. The conversion of urea to ammonium follows the reaction

k1
urea + 2 H2O→ ← NH4+ + CO32- . E
k-1
A plot of the energy of the system as a function of progress of the urea reaction
reaction is shown at right. At 334K the forward rate constant k1 NH4+ + CO32-
equals 7.13 × 10-6 min-1.

a) If the activation energy barrier for the forward reaction is 127 kJ/mol, what is the forward rate
constant at 324K?

k2 E ⎛ 1 1 ⎞
ln = − A ⎜ − ⎟
k1 R ⎝ T2 T1 ⎠
⎡ E ⎛ 1 1 ⎞⎤ ⎡ 127kJ / mol ⎛ 1 1 ⎞⎤
k2 = k1 exp⎢− A ⎜ − ⎟⎥ = 7.13×10 −6 min −1 × exp⎢− ⎜ − ⎟⎥
⎣ R ⎝ T2 T1 ⎠⎦ ⎣ 8.3145 ×10 −3 kJ / molK ⎝ 324K 334K ⎠⎦
€ k2 = 1.74 ×10 −6 min −1

b) If the value of the reverse rate constant k-1at 334K is 1.02 x 10-7 min-1, what is the value of
€ equilibrium constant for the conversion of urea to ammonium and carbonate at this temperature?

k for 7.13×10 −6 min −1

K= = = 69.9
krev 1.02 ×10 −7 min −1

c) If a catalyst is introduced to the reaction, the rate constant k1 is found to increase by a factor
€ of 5000. Which of the following is true?

 k-1 decreases by a factor of 5000

 the Gibbs free energy change in the reaction becomes more positive
 the Gibbs free energy change in the reaction becomes more negative
 the activation energy barrier in the forward direction decreases
 the activation energy barrier in the reverse direction decreases

d) Sketch a curve for the catalyzed reaction on the plot above and calculate the change in the
activation energy for the forward reaction, in kJ/mol, at 334K.

kcat Ae−E Acat / RT ⎡ −(E Acat − E Auncat ) ⎤

= 5000 = −E Auncat / RT = exp⎢ ⎥⎦
kuncat Ae ⎣ RT
ΔE A = −(E Acat − E Auncat ) = RT ln(5000) = (8.3145 ×10 −3 kJ / molK )(334K )ln 5000 = 23.7kJ / mol
Curve for catalyzed reaction (dash line above) is shorter, with same start and end points.