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Chapter10 PDF
Chapter10 PDF
Molecular
HCl(aq) + NaOH(aq) 6 NaCl(aq) + H2O(l)
Complete ionic
H+(aq) + Cl-(aq) + Na+(aq) + OH-(aq) 6H2O(l) + Na+(aq) + Cl-(aq)
Net Ionic
H+(aq) + OH-(aq) 6H2O(l)
The NaCl is just along for the ride, so what is the real reaction?
H+ + OH- 6 H2O
What is the K of this reaction?? (1/Kw = 1x10+14 a very strong reaction)
There are only four equations you need to know to describe this titration curve: The
initial point, 1 before the equivalence point, one for the equivalent point itself and one
for after the equivalence point.
1. Notice that the book concentrates on the problem of a Base being titrated with an
acid. You should be able to turn these equations around and to the same analysis for
an acid being titrated with a base.
2. While I will follow the approach used in the book, I will plug in slightly different
numbers just to show you how thing would change for a slightly different problem.
Let’s say we are titrating 49 mL. of .021 M NaOH with 0.097 M HCL
2
What is the definition of the equivalence point? (Where you have an equivalent
amount of the reactant and titrant.)
Reactant is NaOH, and we have
Moles=Molarity x volume
49(.021) or 1.029 mMoles of OH- initially
To be at the equivalence point we need an equivalent number of H+
So if
1.029mM=0.097 X
X=10.61 mL.
Inital pH
.021M NaOH
= .021 M Na+ and .021M OH-
pOH = -log(.021)
= 1.68
pH=14-1.68
=12.32
In this region the pH is determined by the excess of OH- that has not reacted
with HCl
RXN table
H+ + OH-6 H2O
Inital 0 1.029
Added .097 0
RXN -.097 -.097 +.097
Final 0 .932 .097
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RXN table
H+ + OH-6 H2O
Inital 0 1.029
Added 1.94 0
RXN -1.029 -1.029 +1.029
Final .911 0 +1.029
For this let’s use an example from the lab, KHP, Potassium acid phthalate
Our example will be a KHP, as the weak acid its structure is:
First what is the reaction that goes on when we dissolve KHP ? It goes to HP-
What is the K for this? Well it looks sort of like the acid reaction
HP- + H2O6P2- + H+
But it has an OH- instead of H+ and it has the water on the wrong side
What if we combine the above reaction with the reverse of the water dissociation:
H+ + OH- W H2O
We get the correct equation. This that in mine, what is the K of the reaction? K
= Ka ×1/Kw
=3.90x10-6 ×1/1x10-14 = 3.9x108
A very favorable reaction. I think you can safely say this is also a strong reaction.
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With this buildup its actually quite easy, you have seen all these calculations before!
1. Initial pH
This is just the pH of a dilute weak acid
[H+] = X; X2/(F-X) = Ka
In this example
X2/(.0783-X)=3.90x10-6
We will assume that X is small compared to .0783 so we get
X2 /.0783 = 3.90x10-6; X=5.526x10-4,
the assumption looks good; pH=3.25
If we do it the long way
X2/(.0783-X)=3.90x10-6; using the solver to get an exact solution
X=5.506x10-4 (original answer off by .02 or .3%)
pH= 3.26
Now you should recognize that in the region we have HA and A- in solution , what does
this mean?? BUFFER REGION - USE HH
This should be another easy one. You were already shown how to determine
the pH of A- earlier
it goes by the form of
X=[OH-]
X2/(F-X) = Kb=Kw/Ka
What is F now??
F=ForgX (Initial volume of HA/ Total volume at EQ point)
Here we have
F=0.07834 x (50/(50+39.17) = .05663M
2.564x10-9=X2/(.05663-X)
2.564x10-9(.05663) =X2
X=1.20x10-5;pOH=4.920, pH=9.080
(You get the same answer if you use the quadratic and solve exactly)
Say we are at 45 mL., 45-39.17 or 5.83 mL. past the equivalence point
[OH-]=.1(5.83/50+45)
=6.14x10-3 ; pOH=2.21, pH=11.79
Now that you have done a titration curve, what do you think would happen to
that titration curve is you had a weaker acid? (pK goes up, middle of curve rises)
Note that as the acid gets weaker and weaker, the center rises until the point where
you don’t have a clear endpoint (figure 10-10)
Another problem is what happens with concentration (also this figure) as the acid gets
more dilute, the curve gets shallower and shallower
Indicators
Most of this material was covered in the last chapter. Just as a reminder. You
want the pKa to match the pH of the equivalence point. And you want to add a
minimum amount of indicator. If either of these are off you may have indicator error,
and you may have to run a blank sample to eliminate this error
Using a pH electrode
While we have just calculated a titration curve, this is something that is usually
done experimentally in the lab. IF you are luck and have several thousands of dollars
you can by a machine that measures the amount of titrant added and the pH of the
solution automatically and makes pretty plots for you. If not, or you are in the lab, you
have to manually add some titrant, and read the pH off a pH meter.
When you do this you should get a nice curve like we have shown in our
theoretical plots. The first question is how do you locate the endpoint in these plots.
Notice most of the time there is a sharp rise in pH at the beginning. This is not
an equivalence point, it is just the buffer getting established
Next we have the sharp rise in pH at the end point. Which point in here is the
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true endpoint?? The one that has the largest slope. How do you find that?? Does the
term derivative sound familiar?
Derivative is the slope of the line
So if you have two point ,40.1 ml pH=8.71
And 40.2, pH 8.8, what is the derivative or slope?
)y/)x = (8.8-8.71)/(40.2-40.1)
Since this slope is between two point, you would plot it at the average of the two
points or at 40.15
When you plot the derivative you should get a plot like this
The peak here is the point with the largest slope, ie your end point.
If you want to get even more exact, what does the second derivative do?
(Will cross from + to - at the equivalence point)
This is an even better way to find the eq pt.
See Figure 10-4
Now if you’ve got a machine, this works out nicely, you can even get the
machine to calculate the derivative for you
But what about real manual data. Here you usually have errors, you read the pH
wrong, you read the volume wrong etc. This makes small errors in your pH vs. Vol plot,
but nothing too bad. What happens when you get to your derivative plot? The errors
get magnified and it looks worse than it does in the book.
If you get really lousy data (your amino acid in the lab) when you have a very
weak endpoint on top of noisy data these plots can be worthless, so we need another
approach
Volume of base X 10-pH vs volume of base you transform the data into a new form. In
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this plot the X intercept of the plot is your equivalence point and the slope of the plot
=Ka((HA/ (A-)
To get a good linear plot, you should use only the data within the last 10-20% fo
the titration, so if you have a titration where you think the endpoint is about 30 mls, you
should make this plot for 24-32 mls (20% of 30 is 6, 30-6=24, plus a few mls after the
suspected end point)
I think you will see in the lab how useful this plot can be.
10-7 Spreadsheets
While I like the idea of making a spreadsheet to calculate an entire titration
curve, the way he does it is to use some equations that he doesn’t get to until Chapter
12, so I think we will skip this as well.