2013-07-18

In-Class problems 2013-07-18

Today was buffers day in class so we looked at 294 different ways to use the Henderson-Hasselbalch equation. Remember, the Henderson-Hasselbalch equation is just a rearrangement of the Ka expression we use for understanding any acid... You can always plug directly into the Ka expression and get the same result you will get using Henderson-Hasselbalch. So the problems...

1. Combine 12.642g of chlorous acid with 15.372g of lithium chlorite, dilute to 500.0mL. What is the expected pH of this buffer? (Chlorous acid Ka = 1.12x10-2)
Plug into the Henderson-Hasselbalch equation...
And solve...

2. Prepare 500.0mL of a 0.650M HN3/N3-1 buffer at pH = 5.10 from HN3(s) and NaN3(s). (Hydrazoic acid Ka = 1.93x10-5)
Start off by solving for the ratio of conjugate acid to conjugate base using either the Henderson-Hasselbalch equation or just an unmodified Ka expression. I'll use H-H...
[N3-1] / [HN3] = 2.4297
[N3-1] = 2.4297[HN3]
Now that we know the ratio of these concentrations, we can solve for the actual concentrations by using the relationship...
0.650M = [HN3] + [N3-1]
0.650M = [HN3] + 2.4297[HN3] = 3.4297[HN3]
[HN3] = 0.1895M
[N3-1] = 0.650 – [HN3] = 0.650 – 0.1895 = 0.4605M
To make a solution that's 0.1895M HN3 at 500.0mL, we need...
(0.5000L)(0.1895M) = 0.09475mols HN3
(0.09475mols HN3)(43.029g/mol) = 4.077g HN3(s)
To make a solution that's 0.4605M N3-1 at 500.0mL, we need...
(0.5000L)(0.4605M) = 0.23025mols N3-1
(0.23025mols N3-1)(65.011g/mol) = 14.969g NaN3(s)
So we should be able to make the target buffer by combining 4.077grams of HN3 and 14.969g of NaN3 in enough water to make 500.0mL of solution.
NOTE: If you're actually making a buffer, be very careful about the order of addition of the components. Whenever you're combining a solid or concentrated solution with a solvent, it's usually a good practice to add the solid or concentrated stock to the larger volume of solvent slowly with very good mixing. Dissolving and/or mixing can liberate a LOT of heat in some cases that could be dangerous if the order of addition is reversed.
NOTE2: Hydrazoic acid is not a solid at room temperature, and the pure liquid is a non-trivial safety risk... We can talk about this type of a buffer on paper, but there's very little chance you (or I) will ever prepare or use a hydrazoic acid-based buffer.

3. What is Ka of a weak acid, “HA”, if a solution made by dissolving 0.316mol HA and 0.327mol A-1 in water and diluting to 750.0mL has a pH of 9.374?
Plug in to Henderson-Hasselbalch or the generic Ka expression...
9.374 = pKa + log (0.327 / 0.316)
pKa = 9.359
Ka = 4.374x10-10

4. What is Kb of a weak base, “B”, if a solution made by dissolving 0.143mol B and 0.158mol HB+1 in water and diluting to 400.0mL has a pH of 5.975?
Similar to the previous problem, plug in to Henderson-Hasselbalch or the generic Ka expression...
5.975 = pKa + log (0.143 / 0.158)
pKa = 6.018
pKb = 14 – 6.018 = 7.892
Ka = 1.043x10-8

Good luck.

2013-07-03

Rate Law and Integrated Rate Law Problem {2013-07-03}

Under some set of conditions, ammonia gas and fluorine gas react to form nitrogen trifluoride gas and hydrogen gas at 8.73ºC. What is the correct rate law expression (including the rate law constant) given the following data:
Rxn #
[NH3]0
[F2]0
Rate (M/min)
1
0.274
0.218
1.841x10-2
2
0.274
0.436
7.362x10-2
3
0.822
0.436
2.209x10-1
The rate law expression for this reaction is:
Rate0 = k[NH3]0x [F2]0y
Comparing Rxn #1 and #2:
y = 2, the reaction is 2nd order with respect to fluorine concentration
Comparing Rxn #3 and #2:
x = 1, the reaction is 1st order w.r.t. ammonia concentration
Plugging in values from Rxn #1 and solving for k...
1.841x10-2 M/min = k (0.274M)1 (0.218M)2
k = 1.42 M-2min-1

In Rxn #2, how much time must pass before [F2] = 0.324M?
Plugging in to the 2nd order integrated rate law expression...
t = 0.558 minutes

In Rxn #1, how much time must pass before [NH3] = 0.217M?
Plugging in to the 1st order integrated rate law expression...
t = 0.164 minutes


2013-07-02

Know Your Polyatomic Ions

I expect you to know polyatomic ions. They're part of the vocabulary of chemistry and if you have to look them up every time one pops up it will slow everything down. I was about to type up a post when I thought "Hmm, this seems like something I would have typed up before..." Sure enough just about a year ago...
http://chemistryingeneral.blogspot.com/2012/06/polyatomic-ions.html

Enjoy!

Colligative properties and gas law problems 2013-07-02

1. 12.64g of sodium sulfate is dissolved in 400.0mL of water. What are the boiling point and freezing point of the solution?
Na2SO4 = 142.041g/mol
12.64g / 142.041g/mol = 0.0889884mols Na2SO4
{NOTE: don't round sig figs in the middle of a problem...}
(0.0889884mols Na2SO4) / 0.4000kg water = 0.22247m Na2SO4
{NOTE: density of water is 1.0000g/mL...}
ΔTbp = (0.512 ºC/m)(0.22247m)(3mol particles / 1mol Na2SO4) = 0.342ºC
{NOTE: I think I used a different value for the boiling point elevation constant in class. This one is correct.}
{NOTE: When Na2SO4 dissolves in water, the result is 2 Na+(aq) ions and 1 SO4-2(aq) ion. 3 particles.}
Tbp = 100.000ºC + 0.342ºC = 100.342ºC

ΔTfp = (1.858 ºC/m)(0.22247m)(3mol particles / 1mol Na2SO4) = 1.240ºC
Tfp = 0.000ºC – 1.240ºC = -1.240ºC

2. A weather balloon is filled with 23.65L of an ideal gas at 28.73ºC and 1.042atm pressure. It is released and rises to an altitude where the temperature is -6.35ºC the pressure is 0.842atm. How many moles of gas are in the balloon and what is its volume when it reaches the described altitude?
Plugging in to the Ideal Gas Law:
PV = nRT
(1.042atm)(23.65L) = n(0.08206 L.atm/mol.K)(301.88K)
n = 0.9948 moles
{NOTE: Convert to kelvins! If you pay attention to the units on R you'll be less likely to forget...}

Now that we know how many moles of gas are present, the next part could be solved by plugging in to the regular Ideal Gas Law again:
PV = nRT
(0.847atm)V = (0.9948mols)(0.08206 L.atm/mol.K)(266.80K)
V = 25.7L
Or by using the comparative form of the Ideal Gas Law:
P1V1/n1T1 = P2V2/n2T2
{NOTE: Since “n” is not changing, we can drop it from the equation...
(1.042atm)(23.65L) / 301.88K = (0.847atm)V2 / 266.80K
V2 = 25.7L


Practice, practice, practice...