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0 x 103 M solution of

codeine has a pH of 9.95. Calculate the value of K b for this substance.

Comment: note that I will use B to symbolize the weak base. No one cares what the

specific base is because the technique to be explained works for all weak bases. What

happens is that some teachers will use the name of a specific weak base while others

go the generic route.

Solution:

1) Write the ionizaton equation for the base. Remember, we will use B to symbolize

the base.

B + H2O <===> HB+ + OH

2) Write the equilibrium expression:

Kb = ( [HB+] [OH] ) / [B]

3) Our task now is to determine the three concentrations on the right-hand side of the

equilibrium expression since the Kb is our unknown.

a) We will use the pH to calculate the [OH]. We know pH = -log [H +], therefore [H+]

= 10pH

[H+] = 109.95 = 1.122 x 1010 M

I've kept a couple guard digits; I'll round off the final answer to the proper number of

significant figures.

Knowing the [H+] allows us to get the [OH]. To do this, we use K w = [H+] [OH], so

we have this:

1.00 x 1014 = (1.122 x 1010) (x)

x = [OH] = 8.9125 x 105 M

(See note at bottom of this soluton for a different way to get the [OH].)

b) From the ionization equation, we know there is a 1:1 molar ratio between [HB +]

and [OH]. Therefore:

[HB+] = 8.9125 x 105 M

c) the final value, [B] is given in the problem. In the example being discussed, 5.0 x

103 M is the value we want. Some teachers will use 5.0 x 10 3 M, while others would

say to first subtract the 8.9125 x 105 value from 5.0 x 103 M. Let's do both.

c1) Kb = [(8.9125 x 105) (8.9125 x 105)] / 5.0 x 103

Kb = 1.59 x 106

c2) Kb = [(8.9125 x 105) (8.9125 x 105)] / (5.0 x 103 minus 8.9125 x 105)

Kb = 1.62 x 106

In reality, it makes very little difference if we use the unmodified concentration of the

acid (the 5.0 x 103 value) or if we do the subtration. In the above example, both

values round off to 1.6 x 106. In the end, you do what your teacher recommends. So,

ask your teacher if you're not sure.

A different path to the [OH]:

pH = 9.95

pH + pOH = pKw = 14.00

pOH = 14.00 - 9.95 = 4.05

[OH] = 10pOH = 104.05 = 8.9125 x 105 M

In this example, I'll use a generic acid and made-up numbers that lead to the K b for the

base.

Before that, a comment: one reason teachers might tend to avoid real substances in

this type of question is that you can just look up the answers on the Internet. K a and

Kb values for many weak acids and bases are widely available.

Problem #2:

A 0.0135 M solution of a weak base (generic formula = B) has a pH of 8.39. Calculate

the Kb for this weak base.

To remind you, here is the ionization equation:

B + H2O <===> HB+ + OH

Solution:

a) [H+] = 10pH = 108.39 = 4.0738 x 109 M

b) [OH] = Kw / [H+] = 1.00 x 1014 / 4.0738 x 109

[OH] = 2.4547 x 106 M

Remember, due to the 1:1 molar ratio that [HB +] = [OH]

c) I will use 0.0135 M for [B].

Kb = [(2.4547 x 106) (2.4547 x 106)] / 0.0135 = 4.46 x 1010

Problem #3: A student prepares a 0.15 M solution of a monoprotic weak acid and

determines the pH to be 11.68. What is the Kb of this weak base? The answer. In the

answer, I plan to follow a slightly different path to the hydroxide ion concentration.

Comment: if you don't know the formula of the weak base, that's OK. Simply use B as

the formula. It does not matter what the anion portion is, it only matters that the base

is weak.

Also, with regard to bases, keep in mind that the proper generic chemical equation to

use is:

B + H2O <===> HB+ + OH

As a reminder, here is the proper generic equation for weak acids:

HA <===> H+ + A

Problem #4: A 0.15 mol/L solution of the ascorbate ion, HC6H6O6, has a pH of 8.65.

Calculate the Kb for the ascorbate ion.

Solution:

1) Ascorbate ion reacts as follows:

HC6H6O6 + H2O <===> H2C6H6O6 + OH

Kb = ([H2C6H6O6] [OH]) / [HC6H6O6]

3) Substituting values and solving:

Kb = [(4.4668 x 106) (4.4668 x 106)] / 0.15

Kb = 1.33 x 1010

Comment: use the pH to calculate the [H +]. Then use Kw and the [H+] to calculate the

hydoxide ion concentration.

Important note: all constants refered to: Kc, Kw, Ka, and Kb are temperature-dependant.

All discussions are assumed to be at 25 C, i.e. standard temperature.

The typical weak acid problem to solve in high school classes looks like this:

What is the pH of a 0.100 M solution of acetic acid? K a = 1.77 x 105

Some facts of importance:

1) you know this is a weak acid for two reasons:

a) you memorized a short list of strong acids. (You did, didn't you?) Everything else is

weak.

b) The Ka value of small. strong acids have very large K a values, as in 105 or 107.

2) The solution technique explained below applies to almost all weak acids. The only

things to change are the concentration and the K a, if doing another acid.

You've seen these equations:

HAc + H2O <==> H3O+ + Ac

Ka = ( [H3O+] [Ac] ) / [HAc] = 1.77 x 105

The key quantity we want is the [H3O+]. Once we have that, then the pH is easy to

calculate. Since we do not know the value, let's do this:

[H3O+] = x

I hope that, right away, you can see this:

[Ac] = x

This is because of the one-to-on molar ratio between [H 3O+] and [Ac] that is created

as HAc molecules dissociate.

So now, we have all but one value in our equation:

1.77 x 105 = {(x) (x)} / [HAc]

All we have to do is figure out [HAc] and we can calculate an answer to 'x.'

In this problem, the [HAc] started at 0.100 M and went down as HAc molecules

dissociated. In fact, due to the one-to-one ratio, it went down by 'x' amount and wound

up at an ending value of 0.100 - x.

So, here's the final set-up:

Now, that is a quadratic equation and can easily be solved with the quadratic formula.

However, there is a trick we can use to make our calculation easier.

You don't know it, but Ka values are very difficult to figure out.There's a whole bunch

of variables that are difficult to control. The end result is that K a are approximate and

most are in error about 5%.

There is a brief discussion of the 5% Rule here.

So that means, if we stay within 5% of the answer using the quadratic, we can use

approximate techniques to get an answer. The major approximation occurs with '0.100

- x.' Since x is rather small, it will not change the value of 0.100 by much, so we can

say:

0.100 - x approximately equals 0.100

We now write a new equation:

1.77 x 105 = {(x) (x)} / 0.100

which is very easy to solve. We move the 0.100 to the other side to get:

x2 = 1.77 x 106

Taking the square root (of both sides!!), we get:

x = 1.33 x 103 M

Take note of two things:

1) The Ka value is unitless, but x is a molarity.

2) Square root both sides. I have had students square root the x 2, but not the other side.

Weird, but true.

We finish by taking the pH to get a final answer of 2.876.

The final comment has to do with checking for 5%. The formula is:

( [H3O+] / [HAc] ) x 100 < 5%

In our case, we had 1.33%, which is acceptable.

Important note: all constants refered to: Kc, Kw, Ka, and Kb are temperature-dependant.

All discussions are assumed to be at 25 C, i.e. standard temperature.

Here's a second typical weak acid problem:

What is the pH of a 0.300 M solution of benzoic acid? K a = 6.46 x 105

These are the important equations:

HBz + H2O <==> H3O+ + Bz

Ka = ( [H3O+] [Bz] ) / [HBz] = 6.46 x 105

Bz refers to the benzoate ion. It is completely unimportant what its formula is.

As before, we want the [H3O+]. So we have:

[H3O+] = x

and

[Bz] = x

This is because of the one-to-one molar ratio between [H 3O+] and [Bz] that is created

as HBz molecules dissociate.

Remember, the [HBz] started at 0.300 M and went down as HBz molecules

dissociated. In fact, due to the one-to-one ratio, it went down by 'x' amount and wound

up at an ending value of 0.300 - x.

Next is our 'dropping the subtract x' trick:

0.300 - x approximately equals 0.300

We will check the validity of the trick after completing the calculation. If the

approximation exceeds 5%, then we have to use the quadratic.

We now have our equation:

6.46 x 105 = {(x) (x)} / 0.300

which is very easy to solve. We move the 0.300 to the other side to get:

x2 = 1.938 x 105

x = 4.40 x 103 M

Remember:

1) The Ka value is unitless, but x is a molarity.

2) Square root both sides. I have had students square root the x 2, but not the other side.

Weird, but true.

We finish by taking the pH to get a final answer of 2.356.

Checking for 5% we find we had 1.47%, which is acceptable.

mportant note: all constants refered to: Kc, Kw, Ka, and Kb are temperature-dependant.

All discussions are assumed to be at 25 C, i.e. standard temperature.

Here's a third typical weak acid problem:

What is the pH of a 0.250 M solution of cacodylic acid? K a = 6.4 x 107

You may have noticed that the solutions in parts one and two were exactly the same.

Both ended up with this:

x = (Ka times starting acid concentration)

When you're doing the 'drop subtract x' thing, this above equation always works for

weak acids.

I better add a cautionary note here: the equation works for

weak MONOPROTIC acids. However, the study of diprotic acids is not touched on

in high school chemistry nor really in Advanced Placement, so we're safe for the time

being.

So the solution to the above problem is:

x = (6.4 x 107 times 0.250) = 4.0 x 104

From this, the pH = 3.40

Checking the 5% rule, we get 0.16% error.

What is the pH of a 0.150 M solution of nitrous acid, HNO 2? Ka = 4.6 x 104

x = (4.6 x 104 times 0.150) = 8.31 x 103

Checking the 5% rule:

(8.31 x 103 / 0.15) x 100

we get 5.54% error.

In order to get a correct answer, we must turn to the quadratic method. In other words,

we cannot ignore the 'subtract x' portion in the denominator.

The equation to use is as follows (I left off the sub a on the K):

x = [-K + (K2 + 4KC)] / 2

The C stands for the starting concentration of the acid.

The solution is left to the reader.

Problem #1: A 0.120 M solution of a generic weak acid (HA) has a pH of 3.26.

Determine the Ka.

Notice that a generic weak acid is used, symbolized by the formula HA. No one cares

what the specific acid is because the technique to be explained works for all weak

acids. What happens is that some teachers will use the name of a specific weak acid

while others go the generic route.

Solution

1) Write the dissociation equation for the acid:

HA <===> H+ + A

2) Write the equilibrium expression:

Ka = ( [H+] [A] ) / [HA]

3) Our task now is to determine the three concentrations on the right-hand side of the

equilibrium expression since the Ka is our unknown.

a) We will use the pH to calculate the [H +]. We know pH = -log [H+], therefore [H+] =

10pH

[H+] = 103.26 = 5.4954 x 104 M

I've kept a couple guard digits; I'll round off the final answer to the proper number of

significant figures.

b) From the dissociation equation, we know there is a 1:1 molar ratio between [H +]

and [A]. Therefore:

[A] = 5.4954 x 104 M

c) the final value, [HA] is given in the problem. In the example being discussed, 0.120

M is the value we want. Some teachers will use 0.120, while others would say to

subtract the 5.4954 x 104 value from 0.120 first. Let's do both.

c1) Ka = [(5.4954 x 104) (5.4954 x 104)] / 0.120

Ka = 2.52 x 106

c2) Ka = [(5.4954 x 104) (5.4954 x 104)] / (0.120 minus 5.4954 x 104)

Ka = 2.53 x 106

In reality, it makes very little difference if we use the unmodified concentration of the

acid (the 0.120 value) or if we do the subtration. In the end, you do what your teacher

recommends. So, ask your teacher if you're not sure.

In this example, I'll use a real acid and numbers that lead to the actual K a for the acid.

Before that, a comment: one reason teachers might tend to avoid real substances in

this type of question is that you can just look up the answers on the Internet. For

example, I used this page to get the Ka for the following problem.

Problem #2: A 0.128 M solution of uric acid (HC5H3N4O3) has a pH of 2.39.

Calculate the Ka of uric acid.

Another reason for using the generic acid formula of HA is that this avoids the need to

constantly write a somewhat complex formula for the anion portion of the weak acid.

In fact, as I do this problem, I will write Ur for the anion portion of uric acid (the

C5H3N4O3).

Solution

a) [H+] = 10pH = 102.39 = 4.0738 x 103 M

b) [Ur] = [H+] = 4.0738 x 103 M

c) I will use 0.128 M

Problem #3: HC9H7O4 (MW = 180. g/mol) is prepared by dissolving 3.60 g into a

1.00 L solution. The pH of this solution was determined to be 2.60. What is the K a?

Solution

1) The only thing different about this problem is that you must calculate the molarity:

3.60 g / 180. g/mol = 0.0200 mol

0.0200 mol / 1.00 L = 0.0200 mol/L

2) Then apply the usual technique:

Ka = [(2.5 x 103) (2.5 x 103)] / 0.0200 = 3.2 x 104

weak acid and determines the pH to be 3.68. What is the K a of this

weak acid?

[A] = [H+] = 2.09 x 104 M

[HA] = 0.45 - 0.000209 = 0.45 (for all intents and purposes)

Ka = [(2.09 x 104) (2.09 x 104)] / 0.45

Ka = 9.7 x 108

Example #1: A student prepared a solution of salicylic acid (a monoprotic weak acid,

MW = 138.123 g mol1) and measured the pH of the solution to be 2.430. Then, she

evaporated 100.0 mL of the solution and collected 0.220 g of dry salicylic acid. What

is the Ka of salicylic acid?

Solution:

1) Write the dissociation equation for salicylic acid, HSal:

HSal ---> H+ + Sal

2) Write the Ka expression for HSal:

Ka = ([H+] [Sal]) / [HSal]

3) Use the pH to determine [H+] and [Sal]:

[H+] = 10pH = 102.20 = 3.71535 x 103 M (some guard digits)

4) Determine molarity of HSal:

1.59278 x 103 mol / 0.100 L = 1.59278 x 102 M

5) Calculate Ka:

Ka = [(3.71535 x 103) (3.71535 x 103)] / 1.59278 x 102

Ka = 8.67 x 104

Comment: I did some Internet searching on the K a of salicylic acid and found some

striking differences in reported values. For example, I found "Quantitative Chemical

Analysis" (by Daniel C. Harris) on Google Books. On page 183, he reports the pK a of

salicylic acid to be 2.97; from that we see the K a to be 1.07 x 103, almost a 20%

difference.

This is not to say any one number is wrong, just that various sources give different

values for the Ka of salicylic acid. I just haven't fond an authoritative source for the

value. Yet!

(abbreviated HCya), CH2CNCOOH has a pH of 1.77. What is the value of the K a?

Solution:

1) Write the dissociation equation for HCya:

HCya ---> H+ + Cya

2) Write the Ka expression for HCya:

Ka = ([H+] [Cya]) / [HCya]

3) Use the pH to determine [H+] and [Cya]:

[H+] = 10pH = 101.77 = 1.69824 x 102 M (I kept some guard digits)

4) Determine molarity of HCya:

8.40 g / 85.0618 g mol1 = 9.875 x 102 mol

1.59278 x 103 mol / 1.00 L = 9.875 x 102 M

5) Calculate Ka:

Ka = [(1.69824 x 102) (1.69824 x 102] / 9.875 x 102

Ka = 2.92 x 103

mportant note: all constants refered to: Kc, Kw, Ka, and Kb are temperature-dependant.

All discussions are assumed to be at 25 C, i.e. standard temperature.

The typical weak base problem to solve in high school classes looks like this:

What is the pH of a 0.100 M solution of ammonia? K b = 1.77 x 105

Some facts of importance:

1) you know this is a weak base because you memorized a short list of strong bases.

(You did, didn't you?) Everything else is weak.

2) The solution technique explained below applies to almost all weak bases. The only

things to change are the concentration and the K b, if doing another base.

You've seen these equations:

NH3 + H2O <==> NH4+ + OH

Kb = ( [NH4+] [OH] ) / [NH3] = 1.77 x 105

The key quantity we want is the [OH]. Once we have that, then the pH is easy to

calculate. Since we do not know the value, let's do this:

[OH] = x

I hope that, right away, you can see this:

[NH4+] = x

This is because of the one-to-on molar ratio between [OH] and [NH 4+] that is created

as NH3 molecules react.

So now, we have all but one value in our equation:

1.77 x 105 = {(x) (x)} / [NH3]

All we have to do is figure out [NH3] and we can calculate an answer to 'x.'

In this problem, the [NH3] started at 0.100 M and went down as NH3 molecules

reacted. In fact, due to the one-to-one ratio, it went down by 'x' amount and wound up

at an ending value of 0.100 - x.

So, here's the final set-up:

1.77 x 105 = {(x) (x)} / (0.100-x)

Since x is rather small, it will not change the value of 0.100 by much, so we can say:

0.100 - x approximately equals 0.100

We now write a new equation:

1.77 x 105 = {(x) (x)} / 0.100

which is very easy to solve. We move the 0.100 to the other side to get:

x2 = 1.77 x 106

Taking the square root (of both sides!!), we get:

x = 1.33 x 103 M

The next step is to negative log the concentration for an answer of 2.876.

However, this is the pOH, NOT THE pH!!!!! We have to do one more step with bases

that we don't do with acids.

We know pH + pOH = 14, so the pH = 14 - 2.876 = 11.124

The final comment has to do with checking for 5%. The formula is:

In our case, we had 1.33%, which is acceptable.

Important note: all constants refered to: Kc, Kw, Ka, and Kb are temperature-dependant.

All discussions are assumed to be at 25 C, i.e. standard temperature.

Here's a second typical weak base problem:

What is the pH of a 0.300 M solution of morphine? Kb = 1.62 x 106

These are the important equations:

Mor + H2O <==> MorH+ + OH

Kb = ( [MorH+] [OH] ) / [Mor] = 1.62 x 106

Mor refers to the morphine molecule and MorH + refers to the molecule after accepting

a proton. It is completely unimportant what its formula is.

As before, we want the [OH]. So we have:

[OH] = x

and

[MorH+] = x

This is because of the one-to-on molar ratio between [OH] and [MorH +] that is

created as Mor molecules react with the water.

Remember, the [Mor] started at 0.300 M and went down as Mor molecules reacted. In

fact, due to the one-to-one ratio, it went down by 'x' amount and wound up at an

ending value of 0.300 - x.

Next is our 'dropping the subtract x' trick:

0.300 - x approximately equals 0.300

We will check the validity of the trick after completing the calculation. If the

approximation exceeds 5%, then we have to use the quadratic.

We now have our equation:

1.62 x 106 = {(x) (x)} / 0.300

which is very easy to solve. We move the 0.300 to the other side to get:

x2 = 4.86 x 107

Taking the square root (of both sides!!), we get:

x = 6.97 x 104 M

Remember:

1) The Kb value is unitless, but x is a molarity.

2) Square root both sides. I have had students square root the x 2, but not the other side.

Weird, but true.

We take the pOH to get 3.157. Converting to pH (remember pH + pOH = 14), we get

a pH = 10.843

Checking for 5% we find we have 0.23%, which is acceptable.

Important note: all constants refered to: Kc, Kw, Ka, and Kb are temperature-dependant.

All discussions are assumed to be at 25 C, i.e. standard temperature.

Here's a third typical weak base problem:

What is the pH of a 0.250 M solution of strychnine? K b = 1.82 x 106

You may have noticed that the solutions in parts one and two were exactly the same.

Both ended up with this:

x = (Kb times starting base concentration)

When you're doing the 'drop subtract x' thing, this above equation always works for

weak bases.

weak MONOBASIC bases. However, the study of dibasic bases is not touched on in

high school chemistry nor really in Advanced Placement, so we're safe for the time

being.

To carry the similarity one step farther, you may have noticed the similiar wordings in

the Ka tutorials and the Kb tutorials. I wrote the Ka files tutorials and then just edited

copies with the appropriate changes in wordings. Just remember, when doing a

Kb problem, you wind up with the pOH and you have to do one more step involving

pH + pOH = 14.

Back to the problem. The solution to the above problem is:

x = (1.82 x 106 times 0.250) = 6.74 x 104

From this, the pH = 10.829

Checking the 5% rule, we get 0.27% error.

What is the pH of a 0.150 M solution of piperidine? K b = 1.7 x 103

x = (1.7 x 103 times 0.150) = 1.6 x 102

Checking the 5% rule:

(1.6 x 102 / 0.15) x 100

we get 10.6% error.

In order to get an answer, we must turn to the quadratic method. In other words, we

cannot ignore the 'subtract x' portion in the denominator.

The equation to use is as follows (I left off the sub b on the K):

x = [-K + (K2 + 4KC)] / 2

The C stands for the starting concentration of the base.

Problem #1: Consider the titration of 80.0 mL of 0.100 M Ba(OH) 2 by 0.400 M HCl?

What is the pH of the solution (a) before adding any acid and (b) after adding 20.0 mL

of HCl?

Solution:

1) Determine [OH], then pH:

Ba(OH)2 ---> Ba2+ + 2OH

Ba(OH)2 is a strong base, so it dissociates 100%. Remember also, that two hydroxides

are produced for every Ba(OH)2.

[OH] = 0.200 M

pOH = -log 0.200 = 0.699

pH = 14.000 - pOH = 14.000 - 0.699 = 13.301 (the answer to part a)

2) Determine moles of OH remaining after 20.0 mL of HCl is added:

moles H+ 0.400 mol/L x 0.0200 L = 0.00800 mol

(Remember, HCl dissociates 100%.)

moles [OH] 0.200 mol/L x 0.0800 L = 0.0160 mol

(Note use of 0.200 M for [OH]; the [Ba(OH)2] is 0.100 M.)

remaining OH 0.0160 mol - 0.00800 mol = 0.00800 mol

3) Determine [OH], then pH:

[OH] = 0.00800 mol / 0.100 L = 0.080 M

(Note the use of 100 mL, which comes from 80 + 20. There is an asumption that the

volumes are additive. In context - both solutions are aqueous - this is a pretty safe

assumpton to make.)

pOH = -log 0.080 = 1.097

pH = 14.000 - 1.097 = 12.903 (the answer to part b)

prepare the titrant. 25.00 mL of sulfuric acid were titrated with above titrant. It took

16.00 mL of sodium hydroxide solution to titrate to the end point. What is the

molarity of the sulfuric acid?

Solution:

1) Determine molarity of NaOH:

MV = grams divided by molar mass

(x) (0.2500 L) = 32.00 g / 40.00 g/mol

x = 3.200 M

2) Determine moles NaOH in 16.00 mL of 3.200 M solution:

moles NaOH (3.200 mol/L) (0.01600 L) = 0.05120 mol

3) Determine moles of H2SO4 that react:

2NaOH + H2SO4 ---> Na2SO4 + 2H2O

The molar ratio between NaOH and H2SO4 is 2:1

Therefore, 0.05120 moles of NaOH will neutralize 0.02560 moles of H 2SO4

4) Calculate molarity of H2SO4 solution:

0.02560 mol / 0.02500 L = 1.024 M

Problem #3: Consider the reaction:

How many mL of 0.7000 M HCl solution would just react with 8.000 g of Ba(OH) 2?

Solution:

1) Calculate moles of Ba(OH)2:

8.000 g / 171.3438 g/mol = 0.04669 mol

2) Determine moles of HCl required to neutralize:

The molar ratio between HCl and Ba(OH)2 is 2:1

Therefore, 0.09338 moles of HCl is required to neutralize 0.04669 moles of Ba(OH) 2

3) Determine volume of HCl required:

0.7000 mol/L = 0.09338 mol / x x = 0.1334 L = 133.4 mL

Problem #4: A 50.0 mL sample of 0.50 M HCl is titrated with 0.50 M NaOH. What is

the pH of the solution after 28.0 mL of NaOH have been added to the acid?

Solution:

1) Calculate moles of HCl and NaOH:

moles HCl (0.50 mol/L) (0.050 L) = 0.025 mol

moles NaOH (0.50 mol/L) (0.028 L) = 0.014 mol

2) Calculate moles HCl remaining:

Since HCl and NaOH react in a 1:1 molar ratio:

0.025 mol - 0.014 mol = 0.011 mol HCl remaining

3) Calculate [HCl] of new solution:

0.011 mol / 0.078 L = 0.141 M

Note volume of 78 mL, derived from 50 + 28.

4) Calculate pH:

pH = -log [H+]

Since HCl dissociates 100%:

pH = -log 0.141 = 0.85

Problem #5: How much anhydrous CaO would be needed to neutralize 0.900 L of

5.00 M H2SO4?

Solution:

1) CaO reacts with water as follows:

CaO + H2O ---> Ca(OH)2

2) Calcium hydroxide racts with sulfuric acid as folows:

Ca(OH)2 + H2SO4 ---> CaSO4 + 2H2O

3) Combining them gives:

CaO + H2SO4 ---> CaSO4 + H2O

The important point is that there is a 1:1 molar ratio between CaO and H 2SO4

4) Determine moles of H2SO4:

(0.900 L) (5.00 mol/L) = 4.50 mol

5) Determine grams of CaO required:

4.50 mol times 56.077 g/mol = 252 g (to three sig fig)

roblem #1: Consider the titration of a 24.0-mL sample of 0.105 M CH 3COOH with

0.130 M NaOH. What is . . .

a) the initial pH?

b) the volume of added base required to reach the equivalence point?

c) the pH at 6.00 mL of added base?

d) the pH at one-half of the equivalence point?

e) the pH at the equivalence point?

Solution to part a:

1) Insert values into the Ka expression for acetic acid. The Ka for acetic acid is 1.77 x

10-5.

1.77 x 10-5 = [(x) (x)] / 0.105

x = 1.3633 x 10-3 M

pH = 2.865

Solution to part b:

1) Calculate moles of acid present:

(0.105 mol/L) (0.0240 L) = 2.52 x 10-3 moles

2) Determine moles of base required to react equivalence point:

CH3COOH + NaOH ---> CH3COONa + H2O

There is a 1:1 molar ratio between acetic acid and sodium hydroxide.

Therefore, 2.52 x 10-3 moles of base required

3) Calculate volume of base solution required:

2.52 x 10-3 mol divided by 0.130 mol/L = 0.0194 L = 19.4 mL

Solution to part c:

1) Calculate moles of acid and base in solution before reaction:

CH3COOH: 2.52 x 10-3 mol

NaOH: (0.00600 L) (0.130 mol/L) = 7.80 x 10-4 mol

2) Determine amounts of acid and acetate ion after reaction:

CH3COOH: 2.52 x 10-3 mol - 7.80 x 10-4 mol = 1.74 x 10-3 mol

CH3COONa: 7.80 x 10-4 mol

3) Use Henderson-Hasselbalch equation to determine pH of (now) buffered solution:

pH = 4.752 + log (7.80 x 10-4 / 1.74 x 10-3)

pH = 4.752 + log 0.4483

pH = 4.404

Note that the new molarities were not calculated for the log term, rather the mole

amounts were used directly. This is because both mole amounts exist in the same 30.0

mL solution. There would be identical volume amounts in the numerator and

denominator of the log term, so they cancel out.

Solution to part d:

At one-half the equivalence, exactly one-half the acid (in this case) has been used up.

The half that was used up was made into the salt (sodium acetate in this case). The

two amounts (acid and salt) are equal in amount. Just below, I will use a '1' to

symbolize the amount. Keep in mind that it is not the actual amount.

1) Use the Henderson-Hasselbalch Equation:

pH = 4.752 + log (1/1)

pH = 4.752

You may use the actual number of moles if you wish. It simply does not matter since

the log term will always zero out at the half-equivalence point.

Note: pH = pKa at the half-equivalence point. Remember that. You stand a very good

chance of being asked a half-equivalence point question on your test.

Solution to part e:

The solution is now completely composed of a salt of a weak acid. The pH of this

solution will be basic.

1) Calculate molarity of sodium acetate:

2.52 x 10-3 mol / 0.0434 L = 0.0581 M

2) Calculate the Kb of sodium acetate:

Kw = KaKb

1.00 x 10-14 = (1.77 x 10-5 ) (x)

x = 5.65 x 10-10

3) Calculate pH of the solution:

5.65 x 10-10 = [(x) (x)] / 0.0581

x = 9.86 x 10-5 M (this is the hydroxide ion concentration)

pOH = 4.006

pH = 9.994

Problem #2: What is the pH when 25.00 mL of 0.20 M CH3COOH has been titrated

with 40.0 mL of 0.10 M NaOH?

Solution:

1) Determine moles of acid and base before reaction:

CH3COOH: (0.20 mol/L) (0.02500 L) = 0.0050 mol

NaOH: (0.10 mol/L) (0.04000 L) = 0.0040 mol

2) Determine moles of acid and salt after reaction:

CH3COOH: 0.0050 mol - 0.0040 mol = 0.0010 mol

CH3COONa: 0.0040 mol

3) Use Henderson-Hasselbalch Equation to determine pH:

pH = 4.572 + log (0.0040/0.0010)

pH = 4.572 + 0.602

pH = 5.354

Problem #3: A 0.552 g sample of ascorbic acid (Vitamin C) was dissolved in water to

a total volume of 20.0 mL and titrated with 0.1103 M KOH. The equivalence point

was reached at 28.42 mL and the pH of the solution at 10.0 mL of added base was

3.72. What is: (a) the molar mass of Vitamin C and (b) its K a?

Solution to part a:

1) Determine moles of base used to reach equivalence point:

(0.1103 mol/L) (0.02842 L) = 0.003134726 mol

2) Assuming ascorbic acid is monoprotic (a necessary assumption to solve the

problem!), calculate its molar mass:

Solution to part b:

1) Determine amounts of acid and salt at 10.0 mL of added base:

acid: 0.003134726 mol x (18.42/28.42) = 0.002031726 mol

base: 0.003134726 mol x (10.0/28.42) = 0.001103 mol

2) Use the Henderson-Hasselbalch Equation to determine the pK a:

3.72 = x + log (0.001103/0.002031726)

3.72 = x + (-0.265)

x = 3.46 (to two, not three, sig figs)

10-pKa yields the Ka

Problem #4: Calculate the pH at the points indicated below if 50.0 mL of 0.100 M

aniline hydrochloride is titrated with 0.185 M NaOH. (K a for aniline hydrochloride is

2.4 x 10-5)

C6H5NH3+ (aq) + OH (aq) ---> C6H5NH2 (aq) + H2O (l)

a) before the titration begins

b) at the equivalence point

c) at the midpoint of the titration

d) after 20 mL of NaOH has been added

e) after 30 mL of NaOH has been added

Solution to part a:

Aniline hydrochloride (formula is C6H5NH3+Cl) is a salt of the weak base aniline.

The salt will form an acidic solution.

C6H5NH3+ (aq) ---> C6H5NH2 (aq) + H3O+ (aq)

2.4 x 10-5 = [(x) (x)] / 0.100

x = 0.00155 M

pH = 2.810

Solution to part b:

1) Calculate moles of aniline hydrochloride initially present:

(0.100 mol/L) (0.0500 L) = 0.00500 mol

2) Calculate the volume of NaOH solution required to reach equivalence point:

(0.185 mol/L) (x) = 0.00500 mol

x = 0.0270 L = 27.0 mL

3) Calculate new molarity of aniline:

0.00500 mol / 0.0770 L = 0.064935 M

4) Calculate Kb for aniline:

(2.4 x 10-5) (x) = 1.00 x 10-14

x = 4.17 x 10-10

5) Calculate pH of solution:

4.17 x 10-10 = [(x) (x)] / 0.064935

x = 5.20364 x 10-6 M

pOH = -log 5.20364 x 10-6 = 5.284

pH = 8.716

Solution to part c:

A better term for midpoint of the titration is half-equivalence point. At the halfequivalence point, exactly half the weak acid (in this case) has been titrated. The half

that has been titrated has been converted into a base (in our case, named aniline). This

solution is a buffer, so we use the Henderson-Hasselbalch Equation:

pH = pKa + log ([base] / [acid])

However, the base/acid ratio at the half-equivalence always equals one, therefore:

pH = pKa

pH = - log 2.4 x 10-5

pH = 4.62

Solution to part d:

1) Calculate moles of each substance before reacting:

aniline hydrochloride: (0.100 mol/L) (0.0500 L) = 0.00500 mol

NaOH: (0.185 mol/L) (0.0200 L) = 0.00370 mol

2) Calculate moles of each substance after reacting:

aniline hydrochloride: 0.00500 mol - 0.00370 mol = 0.00130 mol

aniline: 0.00370 mol

3) Use the Henderson-Hasselbalch Equation:

pH = pKa + log ([base] / [acid])

pH = 4.620 + log (0.00370 / 0.00130)

pH = 5.07 (to two sig figs)

Solution to part e:

27.0 mL of the NaOH solution goes to converting aniline hydrochloride into aniline, a

weak base. 3.0 mL of 0.185 M NaOH are left over. Anytime you have a mixture of a

strong base and a weak base, ignore the weak and concentrate on the strong.

1) Find new molarity of NaOH:

M1V1 = M2V2

(0.185 mol/L) (3.0 mL) = (x) (80.0 mL)

x = 0.0069375 M

2) Find pOH, then pH:

pH = 14 - pOH = 11.841

Problem #5: 25.0 mL of 0.10 M acetic acid (HAc) is titrated with 0.10 M NaOH.

What is the pH at the equivalence point?

Solution:

1) We know the following:

HAc + OH ---> Ac + H2O

25.0 mL of NaOH is required to reach equivalence.

The total volume of the solution is 50.0 mL.

The moles of sodium acetate are 0.0025 mol

2) Calculate the molarity of the sodium acetate:

0.0025 mol / 0.050 L = 0.0050 M

3) Calculate the Kb of sodium acetate:

Kw = KaKb

1.00 x 10-14 = (1.77 x 10-5 ) (x)

x = 5.65 x 10-10

4) Calculate pH of the solution:

5.65 x 10-10 = [(x) (x)] / 0.0500

x = 5.315 x 10-6 M (this is the hydroxide ion concentration)

pOH = 5.274

pH = 8.726

Problem #6: What is the pH at the equivalence point in the titration of 0.250 M HX

(Ka = 5.2 x 10-6) with 0.250 M KOH?

Solution:

1) Determine concentration of KX at the equivalence point:

Assume 1.00 L of 0.250 M HX reacts with 1.00 L of 0.250 M KOH.

This produces 2.00 L of solution containing 0.250 mol of KX.

[KX] = 0.250 mol / 2.00 L = 0.125 M

2) Since KX is the salt of a weak acid, we need the K b of X

KaKb = Kw

(5.2 x 10-6) (x) = 1.0 x 10-14

x = 1.923 x 10-9

3) Solve for [OH] in the following reaction:

X + H2O <==> HX + OH

Kb = ([HX] [OH]) / [X]

1.923 x 10-9 = [(x) (x)] / 0.125

x = 1.55 x 10-5 M

4) Determine the pH:

pOH = -log [OH] = -log 1.55 x 10-5 = 4.81

pH = 14.00 - 4.81 = 9.19

Problem #7: What is the pH at the equivalence point in the titration of 100.0 mL of

0.100 M HCN (Ka = 4.9 x 10-10) with 0.100 M NaOH?

Solution:

The acid and base react in a 1:1 ratio. Therefore, equal volumes of the acid and base

are required.

This means, since the final volume doubles, that the [NaCN] is half that of the

concentrations of the acid and the base.

[NaCN] = 0.050 M

2) Since NaCN is the salt of a weak acid, we need the K b of CN

KaKb = Kw

(4.9 x 10-10) (x) = 1.0 x 10-14

x = 2.041 x 10-5

3) Solve for [OH] in the following reaction:

CN + H2O <==> HCN + OH

Kb = ([HCN] [OH]) / [CN]

2.041 x 10-5 = [(x) (x)] / 0.050

x = 1.01 x 10-3 M

4) Determine the pH:

pOH = -log [OH] = -log 1.01 x 10-3 = 3.00

pH = 14.00 - 3.00 = 11.00

HC2H3O2 with 0.10 M NaOH, what volume (in mL) of 0.10 M NaOH would need to

be added to 10.0 mL of 0.10 M HC2H3O2 to prepare a solution with pH = 5.50?

Solution:

Comment: In doing the salt (sodium acetate) and the acid (acetic acid), I'm going to

use moles rather than molarity. Since everything occurs in the same volume of

solution, the ratio of salt moles to acid moles is the same as the ratio of molarities.

Besides, we don't know the final molarities since we are adding an unknown volume

of NaOH solution.

1) We need to know the initial moles of acetic acid in the solution:

(0.010 L) (0.1 mol/L) = 0.001 mol

2) Let us insert values into the H-H equation:

pH = pKa + log (salt/acid)

5.50 = 4.752 + log (x / (0.001 - x))

4.752 is the pKa of acetic acid

x is the moles of sodium acetate produced by the NaOH reacting

0.001 - x is the amount of acetic acid remaining in solution.

The moles of acetate will give us moles of NaOH since there is a 1:1 molar ratio

between the two.

3) Continue solving:

log (x / 0.001 - x) = 0.748

antilog both sides

(x / 0.001 - x) = 5.598

cross multiply & simplify to get:

6.598x = 5.598 x 10-3

x = 8.5 x 10-4 moles

4) Let us determine the volume of NaOH required:

8.5 x 10-4 mol divided by 0.1 mol/L = 8.5 x 10-3 L = 8.5 mL

Problem #1: Calculate the pH of the solution that results when 40.0 mL of 0.100 M

NH3 is:

a) Diluted with 20.0 mL of distilled water.

b) Mixed with 20.0 mL of 0.200 M HCl solution.

c) Mixed with 20.0 mL of 0.200 M NH4Cl

Solution to part (a):

1) Use the dilution equation:

M1V1 = M2V2

(0.100 mol/L) (0.040 L) = (x) (0.060 L)

x = 0.0667 M

2) Use the Kb for ammonia to determine pH:

Kb = ([NH4+] [OH]) / [NH3]

1.77 x 105 = (x) (x) / (0.0667 - x)

Remember to ignore the x in 0.0667 - x.

x = 0.001086278 M (a few guard digits)

pOH = - log 0.001086278 = 2.964

pH = 11.036

Solution to part (b) and (c): Someday!

Problem #2: How many grams of ammonia are needed to make 1.25 L solution with a

pH of 11.68?

Solution:

1) Use the pH to get the hydroxide ion concentration:

pH = 11.68

pOH = 14.00 - 11.68 = 2.32

[OH] = 10pOH = 102.32

[OH] = 4.7863 x 103

2) Use the Kb expression to get the [NH3]:

Kb = ([NH4+] [OH]) / [NH3]

1.77 x 105 = (4.7863 x 103) (4.7863 x 103) / (x)

x = 1.294275 M (guard digits!)

3) Grams needed for 1.25 L

MV = g/molar mass

(1.294275 mol/L) (1.25 L) = x/17.031 g/mol

x = 27.6 g

Problem #3: Calculate the pH of a formic acid solution that contains 1.45% formic

acid by mass. (Assume a density of 1.01 g/mL for the solution.)

Solution:

1) Calculate volume of 100.0 g of solution:

100.0 g divided by 1.01 g/mL = 99.01 mL

2) Calculate molarity of 1.45% solution of HCOOH:

1.45 g divided by 46.025 g/mol = 0.0315 mol

0.0315 mol / 0.09901 L = 0.318 M

3) Calculate [H+] in 0.318 M HCOOH solution:

x = 7.5657 x 10-3 M (kept a couple guard digits)

4) Calculate pH:

-log 7.5657 x 10-3 = 2.12

Problem #4: A buffer solution contains 0.384 M KHCO3 and 0.239 M Na2CO3. If

0.0464 moles of potassium hydroxide are added to 225.0 mL of this buffer, what is the

pH of the resulting solution ? (Assume that the volume does not change upon adding

potassium hydroxide.)

Solution:

1) Calculate moles of bicarbonate and carbonate:

HCO3: (0.384 mol/L) (0.2250 L) = 0.0864 mol

CO32: (0.239 mol/L) (0.2250 L) = 0.053775 mol

2) The hydroxide reacts with the acid (the bicarbonate):

HCO3 decreases: 0.0864 - 0.0464 = 0.0400 mol

CO32 increases: 0.053775 + 0.0464 = 0.100175 mol

3) Need pKa of bicarbonate:

Ka of HCO3 is the same as the Ka2 of H2CO3.

Ka of HCO3 = 4.7 x 1011

pKa = 10.252

4) Use Henderson-Hasselbalch Equation:

pH = 10.328 + log (0.100 / 0.04)

pH = 10.328 + 0.398 = 10.726

Problem #5: A buffer solution contains 0.348 M ammonium chloride and 0.339 M

ammonia. If 0.0248 moles of hydrochloric acid are added to 125.0 mL of this buffer,

what is the pH of the resulting solution? (Assume that the volume does not change

upon adding hydrochloric acid.)

Solution:

A solution on video is provided for this problem.

Problem #6: How many mL of 4.50 M sodium hydroxide must be added to 250.0 mL

of a 0.200 M acetic acid solution to make a buffer with pH = 5.000?

Solution:

1) Use H-H Equation to determine required ratio of acetate to acid in solution:

5.000 = 4.752 + log [base] /[acid]

log [base] /[acid] = 0.248

[base] /[acid] = 1.77

2) Determine molar amount of base required to get pH = 5.000 (for convenience, I'm

going to use 1.00 L. I'll go to 250 mL at the end of this step):

1.77x + x = 0.200

x = 0.0722 mol (this is acetic acid needed in the solution)

0.200 - 0.0722 = 0.1278 mol of base required

0.1278 /4 = 0.03195 mol of acetate required in 250 mL

3) Determine volume of NaOH solution required:

4.50 mol/L = 0.03195 mol / x

x = 0.0071 L = 7.1 mL

4) Check everything:

[acetic acid] = 0.01805 mol / 0.2571 L = 0.070206 M

pH = 4.752 + log (0.12427 / 0.070206)

pH = 4.752 + log 1.77

pH = 4.752 + 0.248 = 5.000

Problem #7: If in a solution 10[H3O+] = [OH] then the pH of the solution is:

Solution:

1) Let:

[H3O+] = x

[OH] = y

2) Therefore, two equations in two unknowns:

10x = y

and

xy = 1.00 x 1014

3) Rearrange the second equation:

y = (1.00 x 1014) / x

4) Substitute into the first equation:

10x = (1.00 x 1014) / x

5) Rearrange and solve:

10x2 = 1.00 x 1014

x2 = 1.00 x 1015

x = 3.16 x 108 M

pH = -log 3.16 x 108 = 7.5

Problem #8: The solubility of CO2(g) in pure water is 0.0037 mol/L. Assuming that

dissolved CO2 is in the form of H2CO3(aq), what is the pH of a 0.0037 M solution of

dissolved CO2? Ka1 for H2CO3 = 4.3 x 10-7

Solution:

1) The relevant chemical equation is:

H2CO3 ---> H+ + HCO3

2) Substituting into the Ka expression, we find:

4.3 x 10-7 = [(x) (x)] / 0.0037

x = 3.989 x 10-5 M

3) Determine the pH:

pH = - log [H+] = -log 3.989 x 10-5

pH = 4.40 (to two sig figs)

Problem #9: A 0.484 g sample of impure NH4Br is treated with 25.00 mL of 0.2050

M NaOH and heated to drive off the NH3. The unreacted NaOH in the reaction

mixture after heating required 9.95 mL of 0.0525 M H 2C2O4 to neutralize. How many

grams of NH4Br were in the original sample?

Solution:

1) Determine moles of NaOH added to amonium bromide solution:

(0.2050 mol/L) (0.02500 L) = 5.125 x 103 mol

Keep in mind that only some of this NaOH reacted.

2) Determine moles of oxalic acid that reacted with excess NaOH:

3) Determine moles of unreacted NaOH:

This reaction:

H2C2O4(aq) + 2NaOH(aq) ---> Na2C2O4 + 2H2O(l)

demonstrates a 1:2 molar ratio between oxalic acid and NaOH.

Therefore, we multiply the oxalic acid amount by two:

5.22375 x 104 mol x 2 = 1.04475 x 103 mol

to determine the amount of NaOH that did not react with the ammonium bromide.

4) Determine moles of NaOH that did react with NH 4Br:

5.125 x 103 mol minus 1.04475 x 103 mol = 4.08025 x 103 mol

5) Determine grams of NH4Br:

4.08025 x 103 mol times 97.943 g/mol = 0.399632 g

To three sig figs, this is 0.400 g

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