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Recitation 1 Problem 1

a) Sulfuric acid is special given it can deprotonate twice. The first deprotonating is strong
and occurs readily, while the second is weaker. Draw out sulfuric acid (full structure) in
all three protonation states and explain why this is:

b) Because it can deprotonate twice, and the second deprotonation is weak, one could make
a sulfate buffer system.

Note: When base reacts with sulfuric acid, it works by stripping two protons off the sulfate with
two moles of NaOH. Write this reaction out to help you visualize this

For a 1 L solution at 5 mM H2SO4 (pKa2 = 1.99):


o Determine the pH of the solution alone (include all deprotonating steps).
o Determine the pH of the solution after the addition of 15 mL of 500 mM NaOH.
Is this solution a buffer?
o Determine the pH of the solution after the addition of 21 mL of 500 mM NaOH.
Is this solution a buffer?

Problem 2
From Fall 2008, Dr. Elliot Chem 102 @ University of Illinois at Urbana-Chamaign

Problem 3
You plan to purify a protein degredation machine from Escherchia coli. Previously you have
found that E. coli can degrade whey proteins (caesin) without currently known degredation
machines being present. This activity has been shown to be ATP dependent
a) Describe an assay you can use to track the activity of this protein.

Problem 1
a) Sulfuric acid is special given it can deprotonate twice. The first deprotonating is
strong and occurs readily like HCl, while the second is weak. Draw out sulfuric acid
(full structure) in all three protonation states and explain why this is:

During the first deprotonation step the resulting charge is spread over three atoms (through
resonance), greatly stabilizing it. However, the second proton cannot leave as easily, because
it places a second charge on the sulfate. This is unstable because it brings two charges like
charges within a small proximity.
b) Because it can deprotonate twice, and the second deprotonation is weak, one could
make a sulfate buffer system.
-

For a 1 L solution at 5 mM H2SO4 (pKa2 = 1.99):


o Determine the pH of the solution alone (include all deprotonating steps).

After figuring out how much H+ is released (0.005 M), do an ICE table for the second step.

I
C
E

0.005
-x
0.005-x

0
x
x
(

After algebra to make the quadratic:

x = -0.018, 0.0028

0.005
x
0.005+x

[H+] = 0.0078, pH = 2.11

o Determine the pH of the solution after the addition of 15 mL of 500 mM NaOH.


Is this solution a buffer?
Start by analyzing the rxn (note that for each mole of H2SO4 two moles of NaOH are required).
First, calculate the number of moles of NaOH (0.015 L * 0.500 M = 0.0075 mol).
H2SO4
0.005 mol
-0.00375
0.00125

B
C
A

2 NaOH
0.0075
-0.0075
0

SO420
+0.00375
0.00375 mol

H2 O
N/A
N/A
N/A

Because there is still sulfuric acid left over, we must calculate the concentration of H+. Some will
come from initial deprotonation, the rest for the resulting buffer. Now we need the current
concentrations of the sulfuric acid species and acid contributed by initial deprotenation, since all
H2SO4 gives off one proton:
[H+] = 0.00125mol/1.015L = 0.00123 M
[HSO4-] = 0.001232 M
[SO42-] = 0.00370 M
Now do an ICE table to find the final conc of H+:

I
C
E

0.001232
x
0.001232+x
(

After the algebra for the quadratic:

x=-0.000499, 0.0154

0.00370
-x
0.00370-x
) (

0.001232
-x
0.001232-x
)

[H+] =0.001232+0.000499 = 0.001731


pH = 2.76
This solution is a buffer, since both acid and base are present in similar quantities.

o Determine the pH of the solution after the addition of 21 mL of 500 mM NaOH.


Is this solution a buffer?

First, find the moles of NaOH added:


0.021L*(0.500 M)= 0.0105 mol
Now see how much acid is eaten up:
H2SO4
0.005 mol
-0.005
0

B
C
A

2 NaOH
0.0105
-0.0100
0.0005

SO420
+0.0050
0.005 mol

H2 O
N/A
N/A
N/A

To find pH, stick to the strategy of the last part, and calculate the concentrations for the acid
dissociation:
[NaOH] = 0.0005 mol/1.021 L = 0.00049 M
[H+]= Kw/[NaOH] = 1*10-14/0.00049 = 2.042*10-11 M
[HSO4-] = 0 (tripped all sulfates of their protons with enough base)
[SO42-]= 0.005mol/1.021 L = 0.0049 M

0
x
x

I
C
E
(

Using algebra to set up a quadratic:

2.042*10-11
-x
2.042*10-11-x

0.0049
-x
0.0049-x
) (

x = 6.7*10-12, -0.015
[H+]= 2.042*10-11-6.7*10-12 = 1.37*10-11M
pH = 10.86
Problem 2