THE FOLLOWING SALTS IN WATER SOLUTION WILL HAVE A pH

OF 7, -7(less than 7), +7(more than 7), OR INDETERMINATE

(I). FOR EACH PREDICT THE pH OF THE SOLUTION.
1. Na2CO3

2. FeCl3

3. KNO3

4. NH4C2H3O2

5. ZnSO4
6. Ba(NO3)2
7. RbF
8. CaBr2
FOLLOWING ARE TITRATION PROBLEMS. ASSUME THAT THE
pH INDICATOR WILL BE THE RIGHT ONE TO BALANCE THE
AMOUNT OF ACID AND BASE. SOME OF THE TITRATIONS ARE
NOT ACID - BASE TITRATIONS. AGAIN ASSUME THERE IS AN
INDICATOR THAT WILL TELL WHEN MOLAR AMOUNTS ARE
MATCHED.
21. 23.45 mL of 0.275 M sodium hydroxide was used to titrate
against mL of acetic acid. What was the concentration in M of
acetic acid?
22. 17.05 mL of 0.247 M barium hydroxide was used to titrate
against 10 mL of nitric acid. What was the concentration in M
of nitric acid?

8. CaBr2 is neutral because both Ca(OH)2 and HBr are strong.

pH = 7.

nowhere near five percent of the hydroxide ion available from

Ba(OH)2, and so:

Back to the Acid and Base math problems.

[(OH)-] = 2 [Ba(OH)2] = 2 (0.00372 M) = 0.00744 M

Now that we know the [(OH)-], this is only a pH box problem.
The answer is in pH, so it is rounded to one decimal place.

9. What is the pH of a 0.0115 M HCl solution?

The only two materials in the solution are water and HCl. The
water alone would provide 1 E-7 Molar hydrogen ion. The HCl
is a strong and soluble acid, so all of the acid is in the form of
ions, providing 0.0115 Molar hydrogen ion. There is no need
to consider the hydrogen ion from water as it is much less
than five percent of the total hydrogen ion concentration. The
concentration of hydrogen ion is adequately estimated at
0.0115 M. This is only a pH box problem. (Note the symbol
Chemtutor uses for pH box math.) As a final answer,
Chemtutor suggests rounding pH values to one decimal place.
Few pH meters are that accurate.

23. 35.79 mL of 0.275 M sodium hydroxide was used to titrate

against 15 mL of sulfuric acid. What was the concentration in
M of sulfuric acid?
Back to Acid and Base math problem #9.
24. 24.92 mL of 0.00199 M silver nitrate was used to titrate
against 5 mL of sodium chloride solution. What was the
concentration of NaCl?

Back to Acid and Base math problem #11.

12. Find the pH of 0.12 M HC2H3O2

The only two things in this solution are water and acetic acid,
a weak acid. The kA of acetic acid is 1.74 E-5. Water and
acetic acid could contribute hydrogen ion to this mixture. If
water were the only possible contributor, it would give 1 E-7
M hydrogen ion. If the acetic acid were the only contributor,
we could calculate it from the equilibrium expression. Since
the hydrogen ion from the acetic acid would be exactly the
same concentration as the acetate ion, [H+] = [(C2H3O2)-].
And we can simplify by substituting [H+]2 for [H+]
[(C2H3O2)-].

10. Find the pH of 0.0815 M NaOH solution.

THE FOLLOWING SALTS IN WATER SOLUTION WILL HAVE A pH

OF 7, -7(less than 7), +7(more than 7), OR INDETERMINATE
(I). FOR EACH PREDICT THE pH OF THE SOLUTION.
1. Na2CO3 is a basic salt because NaOH is a strong base and
H2CO3 is a weak acid. pH is above 7.
2. FeCl3 is an acid salt because Fe(OH)3 is weak base and HCl
is a strong acid. pH is less than 7.

The only two materials in the solution are water and NaOH.
The water alone would provide 1 E-7 Molar hydroxide ion. The
NaOH is a strong and soluble base, so all of the base is in the
form of ions, providing 0.0815 Molar hydroxide ion. The
hydroxide ion is most important in this problem. The
hydroxide ion from the dissociation of water is much less than
five percent of the hydroxide ion from sodium hydroxide, so
the concentration of hydroxide ion is 0.0815 M. This is only a
pH box problem. The answer has been rounded to one
decimal place.

3. KNO3 is a neutral salt. Both HNO3 and KOH are strong. pH

= 7.
4. NH4C2H3O2 is indeterminate. Both NH4OH and HC2H3O2
are weak. pH is actually only a very little above 7.
5. ZnSO4 is an acid salt. The first ionization of H2SO4 is
strong and Zn(OH)2 is weak. pH is less than 7.
6. Ba(NO3)2 is neutral because both Ba(OH)2 and HNO3 are
strong. pH = 7.
7. RbF is an alkaline salt because RbOH is strong and HF is
weak. pH is over 7.

Back to Acid and Base math problem #10.

Now we can substitute our numbers for the kA and

[HC2H3O2] to find that [H+] = the square root of (0.12 x 1.74
E-5). The [H+] due to acetic acid is 1.4450 E-3 M.

11. Find the pH of 0.00372 M Ba(OH)2 solution.

Ba(OH)2 is a strong base, that is, up to its solubility limits the
compound will be completely ionized in water solution. [(OH) -]
is twice the [Ba(OH)2] because for each mol of Ba(OH)2 there
are two mols of hydroxide ion. The ionization of water, the
only other possible source of hydroxide ions, produces

The [H+] from the acetic acid is less than five percent of the
[acetic acid], so there is no need to get a more accurate

answer by subtracting the [H+] from the [acetic acid]. After

finding the [H+], we calculate the pH by using the pH box. The
pH is 2.840134, rounded to 2.8.

Back to Acid and Base math problem #12.

13. Calculate the pH of 0.0000135 M H3BO3

Oh, no. We have a complication. H2CO3 has such a small kA
(5.37 E-10 for the first ionization) and the acid is in such small
concentrations that the [H+] from the acid will be not much
more than the [H+] from the ionization of water. The other
possible sources of [H+] are the second and third ionizations
of the boric acid, but they both have kA's that are far from
the first ionization, so they should not be of any significance.
What you would find, if you assume the ionization of water to
be negligible, is a silly answer. You try it. Use the standard
square root of ( kA times [H3BO3]). You get a pH OVER seven.
(pH = 7.1) Ridiculous. Boric acid is an acid and should result
in a pH of less than seven.
There are several ways to do this. One way is by successive
approximations. First use the ionization constant formula to
calculate the [H+] from the acid, then use that [H+] to find the
[OH-]. Since the [H+] from water equals the [OH-], you can add
that number back to the [H+] from the acid to get a first round
total [H+]. Use the first round total [H+] in the acid dissociation
equation to find the concentration of acetate ion and that
would be equal to the second round estimation of the [H +]
from acid. Keep going around that circle until you get three
stable significant digits for the total [H+].
Another way is by substitutions into known equations. Your
equations are the formula for the kw, the formula for the [H+]
of a weak acid, the equality of the [H +] from water with the
[OH-], and the statement that the total [H+] equals the [H+]
from water plus the [H+] from the ionization of the acid.

Now substitute the numbers and do the math.

Or you could substitute in for the [OH-] ion and solve for the
[H+].
Drop the numbers in and do the math. It is messy and tedious
and disgusting to have to use the quadratic equation, but it
will give you and answer of [OH-] = 6.6115 E-8 which results
in a pH of 6.8203, rounded to 6.8, a likely answer.

Back to Acid and Base math problem #14.

Back to Acid and Base math problem #13.

15. 0.578 M H3PO4
14. pH of 0.255 M NH4OH
The kB of NH4OH is 1.78 E-5.
The ionization equilibrium expression for NH4OH or any other
weak base is similar to the ionization equilibrium expression
for a weak acid, but this time the equation will be solved for
the hydroxide ion concentration.
The hydroxide ion is in excess. The two sources of hydroxide
ion are the [H+] and water, but the contribution from the
water is negligible.
The other assumption, that the amount of dissociated ion is
negligible, is also valid because the concentration of base is
so large. (Try it if you don't believe it.)

In a solution that has only water and phosphoric acid there

are four possible sources of hydrogen ion, the water and the
three ionizations of the phosphoric acid. Each ionization has a
different kA.
H3PO4
(H2PO4)- + H+
(
(HPO4)2- + H+
(HPO4)2(PO4)3- + H+

first ionization
kA = 6.92 E-3
second ionizaton kA = 6.17 E-8
third ionization
kA = 2.09 E-12

It is clear that the first ionization of phosphoric acid at this

concentration is much greater than the third ionization of
phosphoric acid, but the big questions are whether we need
to consider the second ionization of phosphoric acid or the
ionization of water.
The hydrogen ion concentration from the first ionization can
be calculated by the usual square root of ([acid]kA) to get an
initial estimate.

We can look up the kA. The [H+] is the same as the [HCl], and
the concentration of phosphoric acid is given. The [H2PO4]
will be equal to the concentration of hydrogen ion contributed
by the first ionization of the phosphoric acid.

From the initial estimate, the [H+] from the first ionization
(0.063243656 M) will be more than 5% of the acid
concentration (0.578 M). We will have to use the more
accurate form of the equation that includes the decrease in
unionized acid concentration by the ionized forms.
Will we have to also account for the second ionization? The
number we found as first estimate for the [H +] can also serve
as estimate of the [H2PO4)-], the anion in the first ionization.
But the anion of the first ionization is the original acid in the
second ionization and the estimate of the [H +] can also be
used in the second ionization equation. If we solve for the
anion of the second ionization equation, we would get an
estimate of the hydrogen ion that the second equation would
produce.

When you substitute the numbers, the math looks like:

As you can see when you do the math, the [H +] is

0.059878231, more than 5% different from the original
estimate. Now we can confidently change that [H+] to the pH
by the pH box.

If you are really sharp, you noticed that the original estimate
using the simplified method of calculating the [H +] produces
the number 0.063243656, and that the pH of that [H +] is the
SAME as the number from the more complex calculation when
rounded to one decimal point.
Back to Acid and Base math problem #15.

This is an interesting result. Notice the [H+] from the second

ionization is very close to the second kA when there is
nothing but water and phosphoric acid in the solution. What
would happen at other concentrations of phosphoric acid? At
other pH's whith the same initial concentration of phosphoric
acid?
The concentration estimate of the hydrogen ion from the
second ionization is far below 5% of the hydrogen ion from
the first ionization, so the second ionization does not need to
be considered. But we do need to consider the decrease in
acid concentration from ionization of the first reaction, so we
use the quadratic form of the equation substituted into the
quadratic equation.

So the pH depends only on the [HCl].

Back to Acid and Base math problem #16.

17. Find the pH of 1.25 M acetic acid and 0.75 M potassium

acetate.
Acetic acid kA = 1.74 E-5

16. What is the pH of 0.16 M HCl and 0.072 M phosphoric

acid?
There are five sources of hydrogen ion in this solution. Count
them. Water, HCl, and the three ionizations of the phosphoric
acid. Likely the water and the lesser two of the three
ionizations of phosphoric acid will not significantly contribute
to the hydrogen ion concentration.
Since the HCL is a strong acid, it contributes 0.16 Molar
hydrogen ion to the solution, but the phosphoric acid is a
weak acid and the [H+] from it can not calculated by the
square root of (kA [H3PO4]) because the [H+] is not equal to
the [H2PO4]. We must go back to the ionization equilibrium
equation for the first ionization of phosphoric acid.

pKA = 4.76.

This is a genuine buffer problem. Added to the water are a

weak acid and a salt containing the anion of the acid.
There are two good ways to work buffer problems, with the
Henderson- Hasselbach equation or with the ionization
equilibrium expression of the weak acid or base. I personally
have a mental block against the H-H equation because I can
never remember whether it uses a positive or negative log
and which concentration goes on top. You can use it if you
wish. Particularly if you need to calculate buffers often, you
should engrave it upon your gray matter. If you really need it
and can't remember it, you can derive it from the ionization
equlilbrium expression.
There are three cautions you need to observe with either
equation: (1) Make sure you are using the correct

concentration for each variable, (2) check to see if the

numbers you propose to use are going to be within the 5%
rule for simplification, and (3) estimate the answer from what
you know and make sure your final answer is reasonable.

The concentration of calcium lactate needs to be doubled (!)

to represent the lactate ion concentration because the
calcium is divalent and has two lactate ions per formula of
calcium lactate. The concenration of acid is more than 100
times the KA, so the concentration of acid is close enough to
the concentration of unionized species.

Before actually doing the problem, estimate the answer from

your own reasoning. In this case, the pkA of acetic acid is
4.76. The rule is that an equimolar buffer has a pH equal to
the pkA and in this problem there is less potassium acetate
than acetic acid, so the pH must be lower (more acid) than
the pkA within a pH unit or so. If the acetic acid were the only
solute, the pH estimate would be the square root of (acid
concentration times kA).

By the ionization equilibrium equation:

The answer of pH = 4.5 is a reasonable one by our estimation

because it is more acid than the pkA of 4.76.
The answer should be somewhere between pH of 2.3 and 4.8
The majority of the acetate ion will be from the potassium
acetate. Is it right that the total acetate ion concentration will
be equal to the concentration of the potassium acetate? Or
will the acetate ion concentration from the ionization of the
acetic acid contribute more than 5%? The potassium acetate
concentration is 0.75 M. The acetate ion concentration from
acetic acid would be 0.00466 M, less than 5% of 0.75 M even
without the common ion effect. We can safely use 0.75 as the
concentration of acetate ion.

It is a little easier to do this problem by the HendersonHasselbach equation, if you are sure you know it. You must
still make sure you are substituting correctly and that your
assumptions for simplification are valid (within 5%). The H-H
equation is not much good for solutions in which either the
acid or ion concentrations are more than ten times one
another or in which the concentration of either material is less
than one hundred times the kA because it doesn't easily
adapt to a quadratic form.

Or by the H-H equation, you get the same answer.

Will the concentration of unionized acid be a problem? The

measured concentration is 1.25 M and the ionized amount is
0.00466 M, far less than 5% of 1.25 M.
As threatened, we can use the ionization equilibrium
expression of acetic acid for the main equation for this
problem, substituting for the kA, substituting the
concentration of potassium acetate for the concentration of
acetate, substituting the concentration of acetic acid, and
solving for the hydrogen ion concentration to get the pH.

Back to Acid and Base math problem #18.

Back to Acid and Base math problem #17.

19. 0.590 M ammonium hydroxide and 1.57 M ammonium
chloride.
18. 0.788 M lactic acid and 1.27 M calcium lactate.

ammonium hydroxide kB = 1.78 E-5

Lactic acid kA = 8.32 E-4

Here we have a weak base and its conjugate cation. We can

use the ionization equilibrium expression, but it is different
from the acid ionization expression. The ammonium hydroxide
ionizes into hydroxide ion and ammonium ion, so it would be
best to find the concentration of the hydroxide ion.

pKA = 3.08.

Here is another acid - conjugate base buffer pair. This time

there is more conjugate anion than acid concentration, so we
expect the pH to be somewhat higher (more alkali) than the
pKA. As in the previous problem, there seems to be no
complication with either of the components being of too small
a concentration or the concentrations being too close to the
KA, so there should be no need for a quadratic equation.

pKB = 4.75.

The ionization equilibrium expression must have the kB rather

than a kA, or the Henderson- Hasselbach equation has to
have all its components adapted to alkali, but it is completely
analagous to the acid calculation. In either way of doing the

problem, you will have to change the answer to the pH by the

pH box.
Will we be able to use our standard shortcuts? The
concentration of base is more than 100 times the kA, so the
measured amount of ammonium hydroxide in solution is a
good enough number for the concentration of unionized
species. The concentration of weak base and conjugate ion
will be within 1:10 of each other, so the amount of conjugate
ion can be adequately estimated by the concentration of
ammonium chloride. There is high enough concentration of
the base so that the ionization of water does not significantly
change the hydroxide concentration.

20. Explain how to make 5 L of 0.15 M acetic acid-sodium

acetate buffer at pH 5.00 if you have 1.00 Molar acetic acid
and crystaline sodium acetate.

concentrated solution. The way to measure the sodium

acetate is to weigh it. We would need (54.7885 x 5 =
273.9425) ml of acetic acid and (82.04 x 0.0952115 x 5 =
39.055757) grams of sodium acetate.

Here is a problem you may have to actually use one day. In

biochemistry some enzymes need to be at a particular pH to
work at maximum. You would choose a weak acid with a pkA
close to the pH you need. (The pkA of acetic acid is 4.76.) The
osmolarity (the total molar amount of dissolved materials)
may be specified. (It is here. The total of acetic acid and
sodium acetate should be at 0.15 Molar.)
It is most convenient to use the Henderson - Hasselbach
equation for this, as it has a term that can be the ratio of the
two materials. The form of the H-H equation does not matter,
but the concentration of the conjugate ion will have to be
greater than the concentration of the acid because the pH is
greater than the pkA of the weak acid.

The real answer is that you need to weigh 39.1 g of sodium

acetate, measure 274 ml of the 1.00 Molar acetic acid and put
them into a 5 liter volumetric flask with enough water to
dissolve the sodium acetate. Then fill the volumetric flast to
the line with distilled water and mix the solution.
Back to Acid and Base math problem #20.
ANSWERS TO PROBLEMS
21. 1.29
M

Or by the H-H equation, you get the same answer.

What we get from the H-H equation is the ratio of the two
constituents. We can use that ratio as one of the equations in
a two - equation - two - unknown setup to substitute one into
the other and calculate the concentration of acetic acid, [HA],
and the concentration of sodium acetate, [A_].

Does the answer make sense? The combination is a base

buffer and the pH is slightly base. There is almost three times
the concentration of ammonium chloride than ammonium
hydroxide, so the pH of the mixture is more acidic than it
would be if the buffer had been equimolar. (pH = 9.25)
Back to Acid and Base math problem #19.
But we still have not answered the question, "Explain how to
make 5 L of pH 5, 0.15 M acetic acid-sodium acetate buffer."
We have a 1.00 Molar solution of acetic acid and crystals of
(solid) sodium acetate. The way we have to measure the
acetic acid is by measuring the volume of the more

<22.
23. 0.328
24. 9.92 E-3 M
0.842 M> M

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